CN107192694A - Preparation and application of solid-phase fluorescence sensor based on BODIPY (BODIPY) - Google Patents
Preparation and application of solid-phase fluorescence sensor based on BODIPY (BODIPY) Download PDFInfo
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- CN107192694A CN107192694A CN201610152313.8A CN201610152313A CN107192694A CN 107192694 A CN107192694 A CN 107192694A CN 201610152313 A CN201610152313 A CN 201610152313A CN 107192694 A CN107192694 A CN 107192694A
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- solid phase
- heavy metal
- metal ion
- fluorescent sensor
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- 239000007790 solid phase Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 16
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 10
- 239000003068 molecular probe Substances 0.000 claims abstract description 10
- 238000001514 detection method Methods 0.000 claims abstract description 8
- 239000004793 Polystyrene Substances 0.000 claims abstract description 5
- 239000004005 microsphere Substances 0.000 claims abstract description 5
- 229920002223 polystyrene Polymers 0.000 claims abstract description 5
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 claims description 13
- 150000003233 pyrroles Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000013461 design Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims 1
- 238000011895 specific detection Methods 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 239000000523 sample Substances 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 238000002715 modification method Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000006557 surface reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical group [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 5
- 230000005284 excitation Effects 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- -1 p formylbenzoic acid methyl esters Chemical class 0.000 description 2
- GOUHYARYYWKXHS-UHFFFAOYSA-N para-formylbenzoic acid Natural products OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 206010011224 Cough Diseases 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 231100000704 bioconcentration Toxicity 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- 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
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- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to preparation and application of a solid-phase fluorescence sensor based on BODIPY heavy metal ions, and the structural formula is as follows. The carrier is chloracetyl-acylated polystyrene microspheres, a fluorescent molecular probe of BODIPY derivatives is selected, and the solid-phase fluorescent sensor with the function of identifying metal ions is prepared in one step by adopting a surface modification method. The solid-phase fluorescence sensor has the advantages of uniform particle size distribution, large specific surface area, good adsorbability, strong surface reaction capability, simple preparation, convenient use and the like. The invention can quickly detect heavy metal ions, and the EDTA is utilized to complex the heavy metal ions, thereby realizing the separation of the solid-phase fluorescence sensor and the actual sample and recycling. The detection method has the characteristics of high sensitivity, good selectivity, small sample consumption and the like.
Description
Technical field
The invention belongs to field of food safety, the pyrroles's heavy metal ion solid phase fluorescent sensor of fluorine boron two is based on the present invention relates to one kind
Preparation and application, the solid phase fluorescent sensor be applied to heavy metal ion quick detection analysis technical field.
Technical background
With the development of modern science and technology and global industry, various pollution problems are increasingly severe, and because of heavy metal pollution
Caused food-safety problem is especially prominent.Heavy metal pollution can be by the bioconcentration of biological chain in organism and human body
Inside reach very high concentration, into human body after have stronger cumulative toxicity be difficult discharge, have carcinogenic, teratogenesis and mutagenesis.
Therefore, quantitative detecting method is carried out to the content of beary metal in food and just seems particularly important.Although have at present many sensitivity and
Selectivity all very high instrument analytical methods, it is such as ultraviolet can AAS (UV), atomic absorption method (AAS), atomic fluorescence
Method (AFS), inductively coupled plasma atomic emission spectrometry (ICP-AES), X fluorescence spectrum method (XRF), inductance coupling
Plasma mass spectrometry (ICP-MS) etc. is closed, but these instruments are complicated, need high energy consumption and high cost etc..Instrumental Analysis detection side
Method needs the complicated sample pretreatment of carry out process, operates comparatively laborious.
Not only preparation method is simple, cheap for solid phase fluorescent sensor, easy to use, can the different heavy metal ion of quick detection,
And complexing of metal ion is got off using EDTA, the recycling of solid phase fluorescent sensor is realized, detection method has sensitive
The features such as degree is high, the good, amount of samples of selectivity is few and environment-friendly.
The pyrroles of fluorine boron two has very superior characteristic as fluorescence probe：1. molar extinction coefficient is very big；2. ultraviolet absorption peak and glimmering
Light emitting peak is all relatively more sharp；3. the very high derivative of fluorescence quantum yield 4. is relatively good to polarity and pH tolerance, Er Qie
It is highly stable under physiological environment.Advantage based on more than, BODIPY class probes have been widely used in protein and DNA
The field such as mark and light treatment medicine.
At present, most widely used fluorescent microsphere is that organic dyestuff is incorporated into the microballoon prepared in polystyrene.The pyrroles of fluorine boron two is normal
Often being selected as fluorescent parent is used for the design synthesis of metal-ion fluorescent molecular probe.In the present invention, fluorescence probe 1 is a kind of allusion quotation
The fluorescence probe of the PET mechanism of type, fluorogen is the pyrroles of fluorine boron two (BODIPY), the aryl knot that acceptor portion replaces for contraposition
Structure, and acceptor portion is to combine mercury ion position.When Photo-induced electron transfer (PET) occurs before mercury ion is combined for acceptor
Process, so fluorescence probe is weaker；When there is mercury ion in detection architecture, acceptor portion can the combination of rapid and mercury ion, resistance
Disconnected PET processes, so that the fluorescence of probe recovers rapidly, fluorescence quantum yield also increases sharply, and causes fluorescence intensity significantly to increase
By force, so as to realize the Selective recognition to mercury ion.
The content of the invention
It is an object of the present invention to provide a kind of preparation and application based on the pyrroles's heavy metal ion solid phase fluorescent sensor of fluorine boron two.
To achieve the above object, the present invention is adopted the following technical scheme that：
By chloracetyl chloride microballoon, BODIPY classes fluorescent molecular probe and dimethyl sulfoxide solvent hybrid reaction, solid phase fluorescent is made
Sensor.
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described implementation example
Among scope.
(1) method for preparing fluorescent molecular probe 1：2,4- dimethyl -3- ethyls-pyrroles and p formylbenzoic acid methyl esters are taken through dehydration
Condensation and hydrolysis, are made pyrroles's (BODIPY) class fluorescent molecular probe 1 of fluorine boron two.
(2) method for preparing chloracetyl chloride microballoon：Polystyrene microsphere, acylting agent and catalyst are fed intake by certain mol proportion,
Methylene chloride is added, nitrogen is passed through, chloracetyl chloride polystyrene microsphere is made in the lower normal-temperature reaction of stirring.
(3) method for preparing solid phase fluorescent sensor：Chloracetyl chloride microballoon, fluorescent molecular probe 1 and dimethyl sulfoxide solvent are mixed
Reaction, is made solid phase sensor.
Embodiment 1
(1) the design synthesis of fluorescent molecular probe 1
2,4- dimethyl -3- ethyls-pyrroles and p formylbenzoic acid methyl esters are taken through dehydrating condensation and hydrolysis, the pyrrole of fluorine boron two is made
Cough up (BODIPY) class fluorescent molecular probe 1.
(2) synthesis of solid phase fluorescent sensor
Chloracetyl chloride microballoon, fluorescent molecular probe 1 and dimethyl sulfoxide solvent are mixed into (volume ratio is 1: 1-1: 5), 60 DEG C -70 DEG C
Agitating and heating is reacted, and is washed with methanol for several times, suction filtration, surname extraction 24h, and solvent is methanol, 70 DEG C -80 DEG C of bath temperature,
Constant weight is dried under vacuum to, solid phase sensor is obtained.
(3) apply
Appropriate solid phase fluorescent sensor is weighed, 1ml acetonitriles are first added into solid phase fluorescent sensor, is added dropwise respectively every time different dense
Spend metal ion solution, it is ensured that liquor capacity is certain in each cuvette and concentration of metal ions increases.Metal ion in cuvette
Solution concentration gradient gradually increases, at excitation wavelength 520nm, scans respectively under various concentrations metal ion, and solid phase fluorescent is passed
Sensor launches fluorescence spectrum.
The EDTA solution of various concentrations is separately added into again, it is ensured that liquor capacity is certain in each cuvette and EDTA concentration increases.
EDTA solution concentrations gradient gradually increases in cuvette, at excitation wavelength 520nm, and scanning solid phase fluorescent sensor emission is glimmering
Light spectrogram.
The above-mentioned solid phase fluorescent sensor for being complexed metal ion is washed with acetonitrile for several times, the first step is repeated, in excitation wavelength 520nm
Place, is scanned under various concentrations metal ion, solid phase fluorescent sensor emission fluorescence spectrum respectively.
EDTA is added dropwise into the solid phase fluorescent sensor of above-mentioned recycling, again be complexed solid phase fluorescent sensor on metal from
Son, repeats second step, at excitation wavelength 520nm, scans solid phase fluorescent sensor emission fluorescence spectra.
It is finally noted that, the purpose for publicizing and implementing mode is that help further understands the present invention.But the skill of this area
Art personnel are appreciated that：In the spirit and scope for not departing from the claims in the present invention, various substitutions and modifications are all possible.
Therefore, the present invention should not be limited to embodiment disclosure of that.The scope of protection of present invention is defined with claims
Scope is defined.
Claims (4)
1. a kind of preparation and application based on the pyrroles's heavy metal ion solid phase fluorescent sensor of fluorine boron two, it is characterised in that：Used carrier is the polystyrene microsphere of chloroacetylation, and the solid phase fluorescent sensor with identification metal ion function is prepared using the method for surface modification.
2. one kind described in claim 1 contains following structure based on the pyrroles's heavy metal ion solid phase fluorescent sensor of fluorine boron two：
3. the design synthetic method based on the pyrroles's heavy metal ion solid phase fluorescent sensor of fluorine boron two described in claim 2 has following characteristics：
By chloracetyl chloride microballoon, the pyrroles of fluorine boron two (BODIPY) class fluorescent molecular probe 1 and dimethyl sulfoxide solvent hybrid reaction, it is made and is based on the pyrroles's heavy metal ion solid phase sensor of fluorine boron two.
4. the solid phase fluorescent sensor described in claim 2 has following characteristics：
(1) the minimum detectability value of solid phase fluorescent sensor detection heavy metal ion is 1ppm.
(2) reusable more than 5 times of the solid phase fluorescent sensor, detection property retention is preferable.
(3) heavy metal ion that the solid phase fluorescent sensor can be used in specific detection environment, food.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610152313.8A CN107192694A (en) | 2016-03-15 | 2016-03-15 | Preparation and application of solid-phase fluorescence sensor based on BODIPY (BODIPY) |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610152313.8A CN107192694A (en) | 2016-03-15 | 2016-03-15 | Preparation and application of solid-phase fluorescence sensor based on BODIPY (BODIPY) |
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| CN201610152313.8A Pending CN107192694A (en) | 2016-03-15 | 2016-03-15 | Preparation and application of solid-phase fluorescence sensor based on BODIPY (BODIPY) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109211857A (en) * | 2018-09-17 | 2019-01-15 | 南京工业大学 | Solid-phase fluorescence sensor capable of simultaneously detecting mercury, cadmium, lead and arsenic heavy metal ions |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2507252A1 (en) * | 2009-11-12 | 2012-10-10 | Centre National De La Recherche Scientifique CNRS | Heat-sensitive spin-transition materials doped with one or more fluorescent agents |
| CN103342766A (en) * | 2013-07-18 | 2013-10-09 | 南京工业大学 | Synthesis and preparation of novel hydrophobic polystyrene resin |
| US9006459B2 (en) * | 2010-07-19 | 2015-04-14 | University Of Ottawa | Fluorescent markers and use thereof for labeling specific protein targets |
| CN104845612A (en) * | 2015-04-29 | 2015-08-19 | 南华大学 | Polystyrene mercury ion fluorescence recognition materials and preparation method thereof |
| CN104910301A (en) * | 2015-07-07 | 2015-09-16 | 南京工业大学 | Polystyrene microsphere with fluorescent response to pH value and preparation method thereof |
-
2016
- 2016-03-15 CN CN201610152313.8A patent/CN107192694A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2507252A1 (en) * | 2009-11-12 | 2012-10-10 | Centre National De La Recherche Scientifique CNRS | Heat-sensitive spin-transition materials doped with one or more fluorescent agents |
| US9006459B2 (en) * | 2010-07-19 | 2015-04-14 | University Of Ottawa | Fluorescent markers and use thereof for labeling specific protein targets |
| CN103342766A (en) * | 2013-07-18 | 2013-10-09 | 南京工业大学 | Synthesis and preparation of novel hydrophobic polystyrene resin |
| CN104845612A (en) * | 2015-04-29 | 2015-08-19 | 南华大学 | Polystyrene mercury ion fluorescence recognition materials and preparation method thereof |
| CN104910301A (en) * | 2015-07-07 | 2015-09-16 | 南京工业大学 | Polystyrene microsphere with fluorescent response to pH value and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 尹振东: ""用于荧光探针的氟硼二吡咯衍生物的设计、合成与光物理性质研究"", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109211857A (en) * | 2018-09-17 | 2019-01-15 | 南京工业大学 | Solid-phase fluorescence sensor capable of simultaneously detecting mercury, cadmium, lead and arsenic heavy metal ions |
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Application publication date: 20170922 |