CN109738408A - A kind of organic MOFS wraps up the application of fluorescein composite material and its detection mercury ion - Google Patents
A kind of organic MOFS wraps up the application of fluorescein composite material and its detection mercury ion Download PDFInfo
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- CN109738408A CN109738408A CN201910010936.5A CN201910010936A CN109738408A CN 109738408 A CN109738408 A CN 109738408A CN 201910010936 A CN201910010936 A CN 201910010936A CN 109738408 A CN109738408 A CN 109738408A
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Abstract
The invention belongs to mercury ion detecting fields, and in particular to a kind of organic MOFS wraps up the application of fluorescein composite material and its detection mercury ion.Using DNA as ion identification group, Hg2+Stable T-Hg can be formed in conjunction with the thymidine high degree of specificity in DNA2+- T structure；Fluorescein has many advantages, such as absorbing wavelength and launch wavelength it is known that stability is good as fluorophor.Using the porous material of hydro-thermal method synthesis as MOFSMaterial adsorbs fluorescein, using in DNA and porous material imidazate ring, after the interaction of pi-pi bond is packaged between functional group as mercury ion fluorescence probe, this be a kind of instrument used be simple and convenient to operate, high sensitivity and highly selective Hg2+Detection method.
Description
Technical field
The invention belongs to mercury ion detecting fields, and in particular to a kind of organic MOFS package fluorescein composite material and its inspection
Survey the application of mercury ion.
Background technique
Now, heavy metal pollution is got worse, and mercury is one of numerous strongest heavy metals of pollutant Poisoning, so in water
The analysis detection of mercury ion is quite important in environment.Mercury ion is detected there are many method, when mercury content is lower in sample to be tested, is led to
Frequently with the common enrichment method such as acid hydrolyzation, alkaline hydrolysiss, extraction, Microwave Digestion to sample pretreatment, to improve detection
Accuracy and sensitivity.After the concentration of mercury reaches the detectable range of instrument, then carry out Accurate Determining.
Currently, mercury detection technique is increasingly mature also with the development of instrument analysis technology, spectrophotometer, atomic absorption light
The instruments such as spectrometer (AAS), Atomic Fluorescence Spectrometer (AFS), icp ms (ICP-MS) are all used for mercury
Detection, also had been built up respective unique detection method.Spectrophotometry is although at low cost, it is easy to detect, have compared with
High detection sensitivity, but have experiment condition harshness, poor selectivity, sensitivity is not high enough, need using organic solvent etc. lack
Point.Although atomic absorption spectrography (AAS) cost is not high, interference is few, relative error is small, detection limit is low, has a wide range of application, it
Remolding sensitivity it is poor, sample needs extremely complex pretreatment process, and the time used is long, reduce the efficiency of analytic process and
For equipment requirement height.The cost of atomic fluorescence spectrometry is not also high, has lower detection limit, high sensitivity, spectral line simple, and
Spectrum between element does not interfere with each other substantially, but there are Fluorescence quenching effect, scatter the problems such as interference of light, and this method is used for
The sample measurement of complicated substrate is relatively difficult.Although the pretreatment of inductively coupled plasma mass spectrometry sample is simple, is applicable in model
Enclose that wide, the range of linearity is good, can analyze multielement, sensitivity is also superior to other test equipments, but its operating cost is higher, and
It cannot be widely used.Due to the method for traditional detection mercury ion all have the defects that it is certain, so need it is a kind of it is easy, at
The detection mercury ion method of this quick analysis detection of cheap and energy is most important.
Metal-organic framework material (Metal-Organic Frameworks, MOFS) it is by metal ion and organic to match
Body is formed by covalent bond or ion covalent bond self-assembly, they have a regular mesh topology.Since metal is organic
Frame material can be coordinated by transformation metal ion from different organic ligands, so design synthesize different pore size,
The porous material of different structure, therefore this material has compared with such as inorganic zeolite of traditional inorganic porous material, porous carbon
There are low large specific surface area, density of material and structure designability and hole Scalability.
Summary of the invention
The purpose of the invention is to overcome shortcoming and defect of the existing technology, and provide a kind of organic MOFS package
Fluorescein composite material and its application for detecting mercury ion.
The technical solution used in the present invention is as follows: a kind of organic MOFS package fluorescein composite material, preparation include
Following steps:
(1) zinc source and imidazole radicals organic ligand are taken, is dissolved in two parts of deionized waters respectively, it is under stiring, zinc source solution is quick
It pours into imidazole radicals organic ligand solution, obtains troubled liquor, troubled liquor is poured into reaction kettle, in 140-160 after closing
2.5-3.5h is reacted at DEG C, taking-up is cooled to room temperature, and to be centrifuged 5-15min under the revolving speed of 10000-14000rmp/min, is obtained
White solid is put into 35-40 DEG C of constant-humidity constant-temperature chamber 20-28 hours with dehydrated alcohol centrifuge washing, is ground after drying
At white fine powder shape particle；
(2) saturated fluorescence element solution is configured, the white fine powder shape particle that step (1) obtains is added, is stirred 4-6 minutes, it is quiet
It sets until solution colour is no longer thin out, white particle becomes yellowish coloured particles；
(3) centrifuge tube equipped with DNA is taken, centrifugation makes DNA be settled down to bottom, saturated fluorescence element solution is added, rocking disperses DNA
In the solution, solution is then moved to white particle in step (2) to become in the troubled liquor of yellowish coloured particles, stirs 20-
It places 20-28 hours at 40min, 0-8 DEG C, to be centrifuged 8-12min under the revolving speed of 10000-14000rmp/min, obtains orange-yellow
Solid particle, and with deionized water centrifuge washing, obtain organic MOFS package fluorescein composite material.
In step (1), imidazole radicals organic ligand is 2-methylimidazole, and molar ratio is Zn in troubled liquor2+:HmIM:H2O=
1:70:1238。
In step (3), DNA sequence dna number: TTC gTT TCg TTC CCC TTC gTT TCg TT.
The application of above-mentioned organic MOFS package fluorescein composite material detection mercury ion.
Beneficial effects of the present invention are as follows: the present invention is prepared for a kind of MOFS composite material for wrapping up fluorescein, utilizes DNA
Effect with MOFS is used as mercury ion fluorescence probe after being packaged.Based on the mechanism of T-Hg2+-T mispairing, by fluorescein
Release, with sepectrophotofluorometer fluorescence intensity, to realize the detection to mercury ion.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention, for those of ordinary skill in the art, without any creative labor, according to
These attached drawings obtain other attached drawings and still fall within scope of the invention.
Fig. 1 is the BET map for the white fine powder shape particle that step (1) obtains；
Fig. 2 is to wrap up the MOFS composite material of fluorescein in various concentration Hg2+Solution in fluorescence intensity；
Fig. 3 is fluorescence intensity of the MOFS composite material of package fluorescein sodium in the solution of various concentration Hg2+.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with attached drawing
Step ground detailed description.
The MOFS composite material of package fluorescein is prepared by following steps:
(1) 0.1619g zinc acetate and 4.2384g2- methylimidazole are weighed with electronic balance, be dissolved in respectively 1.5ml deionized water and
In 15ml deionized water.Under conditions of magnetic agitation, zinc source precursor solution is quickly poured into organic ligand precursor solution
In, clear solution gradually becomes cloudy, and finally obtaining milky white solution, (final molar ratio is Zn2+: HmIM:H2O=1:70:1238).
Milky white solution is all poured into after mixing evenly in the stainless steel cauldron of 100ml polytetrafluoroethyllining lining, is put into after tightening
3 hours in 150 DEG C of electric heating constant-temperature blowing drying box.Reaction kettle is taken out into cooled to room temperature after 3 hours, will be gathered after cooling
Solution in tetrafluoroethene liner pours into large size centrifuge tube, puts into a centrifuge and is centrifuged under the revolving speed with 12000rmp/min
10min obtains white solid, then with dehydrated alcohol centrifuge washing 3 times, is finally putting into 24 in 37.5 DEG C of constant-humidity constant-temperature chamber
Hour, it is put into glass mortar after drying, is ground into white fine powder shape particle.
The specific surface area for the white fine powder shape particle being prepared is larger, is 1350m2/ g carries out BET survey to it
Examination, for the BET spectrogram tested as shown in Figure 1, white fine powder shape particle is porous material, pore-size distribution is relatively uniform, puts down
Equal aperture is about 3.5nm, belongs to mesoporous material.
(2) saturated fluorescence element solution (yellow solution) is configured, takes 20ml saturated fluorescence element solution in 50ml beaker, adds
Enter the white fine powder shape particle that 0.1g step (1) obtains, under conditions of magnetic agitation, stirring after five minutes, stands observation
Until solution colour is no longer thin out, illustrate that adsorbing fluorescein reaches saturation, white particle becomes yellowish coloured particles.
(3) two small centrifuge tube (DNA sequence dnas number: TTC gTT TCg TTC CCC TTC gTT TCg that DNA is housed are taken
TT), put into a centrifuge after being centrifuged 5min with the revolving speed of 10000rmp/min, DNA is made to be settled down to bottom.It is respectively added with liquid-transfering gun
1ml saturated fluorescence element solution firmly rocks 1 minute into small centrifuge tube, make DNA dispersion in the solution, after by solution all move
It takes in the troubled liquor that white particle becomes yellowish coloured particles into step (2), under conditions of magnetic agitation, stirs 30min
Afterwards, beaker is sealed with preservative film, is put into refrigerator 24 hours.After 24 hours, solution is poured into large size centrifuge tube, be put into from
To be centrifuged 10min under the revolving speed of 12000rmp/min in scheming, orange/yellow solid particle is obtained, and with deionized water centrifuge washing
3 times, obtain the MOFS composite material of package fluorescein.
The MOFS composite material of fluorescein will be wrapped up to various concentration Hg2+It is tested:
Using the MOFS composite material for wrapping up fluorescein as ion fluorescence probe, it is added with a certain amount of 90%50mM MgCl2With
10%200mM Tris-Hcl mixed liquor, makes orange/yellow solid even particulate dispersion in the solution.It is pipetted with liquid-transfering gun and contains this
The solution 1ml of ion fluorescence probe and 10-6g/ml、10-7g/ml、10-8g/ml、10-9g/ml、10-10The various concentration of g/ml
Each 1ml of mercury ion solution, mixing are added in 5ml liquid storage bottle, separately take the solution 1ml and 90% containing the ion fluorescence probe
50mMMgCl2With 10%200mMTris-Hcl mixed liquor 1ml, mixing is added in 5ml liquid storage bottle, does blank assay.By liquid storage bottle
It is put into 37.5 DEG C of constant-humidity constant-temperature chamber after 1 hour, surveys solution fluorescence intensity with F-7000 sepectrophotofluorometer.Detection
As a result as shown in Fig. 2, experiment shows: with Hg2+The increase of concentration, it is stronger that detection obtains fluorescence signal.Because of Hg2+It can be with
Thymidine high degree of specificity in DNA, which combines, forms stable T-Hg2+- T structure keeps DNA single-stranded gradually from porous material table
Emaciated face is from it is more to release fluorescein in porous material, so to obtain fluorescence signal stronger for detection.Fluorescein is in low concentration
When, the fluorescence intensity of fluorescein increases with concentration and is increased in aqueous solution.
Shearing enzyme can break ring Hg2+Stable T-Hg is formed in conjunction with the thymidine high degree of specificity in DNA2+- T structure,
Improve Hg2+Utilization rate, make DNA is single-stranded to be rapidly separated porous material, make release fluorescein it is more, the fluorescence intensity of solution
It is stronger.
It replaces fluorescein as fluorophor using fluorescein sodium, prepares the ion fluorescence probe, detect various concentration Hg2+'s
The MOFS composite material of solution, other experiment conditions and package fluorescein is to various concentration Hg2+Solution test condition it is identical.
Testing result is as shown in figure 3, experiment shows: replacing fluorescein as fluorophor, the ion fluorescence of preparation using fluorescein sodium
Probe cannot distinguish between 10-7g/ml、10-8g/ml、10-9g/ml、10-10The mercury ion solution and no mercury ion of g/ml isoconcentration
Solution, sensitivity is too poor.It may be to be easy to run out from porous material because fluorescein sodium molecule is too small, DNA encapsulation effect
Caused by fruit is bad.
To sum up, using DNA as ion identification group, Hg2+It can be formed in conjunction with the thymidine high degree of specificity in DNA steady
Fixed T-Hg2+- T structure；Fluorescein has many advantages, such as absorbing wavelength and launch wavelength it is known that stability is good as fluorophor.
Using the porous material of hydro-thermal method synthesis as MOFSMaterial adsorbs fluorescein, using in DNA and porous material imidazate ring,
Mercury ion fluorescence probe is used as after the interaction of pi-pi bond is packaged between functional group, this be a kind of instrument used it is simple,
Easy to operate, highly sensitive and highly selective Hg2+Detection method.
The above disclosure is only the preferred embodiments of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, therefore equivalent changes made in accordance with the claims of the present invention, is still within the scope of the present invention.
Claims (4)
1. a kind of organic MOFS wraps up fluorescein composite material, it is characterised in that its prepare the following steps are included:
(1) zinc source and imidazole radicals organic ligand are taken, is dissolved in two parts of deionized waters respectively, it is under stiring, zinc source solution is quick
It pours into imidazole radicals organic ligand solution, obtains troubled liquor, troubled liquor is poured into reaction kettle, in 140-160 after closing
2.5-3.5h is reacted at DEG C, taking-up is cooled to room temperature, and to be centrifuged 5-15min under the revolving speed of 10000-14000rmp/min, is obtained
White solid is put into 35-40 DEG C of constant-humidity constant-temperature chamber 20-28 hours with dehydrated alcohol centrifuge washing, is ground after drying
At white fine powder shape particle；
(2) saturated fluorescence element solution is configured, the white fine powder shape particle that step (1) obtains is added, is stirred 4-6 minutes, it is quiet
It sets until solution colour is no longer thin out, white particle becomes yellowish coloured particles；
(3) centrifuge tube equipped with DNA is taken, centrifugation makes DNA be settled down to bottom, saturated fluorescence element solution is added, rocking disperses DNA
In the solution, solution is then moved to white particle in step (2) to become in the troubled liquor of yellowish coloured particles, stirs 20-
It places 20-28 hours at 40min, 0-8 DEG C, to be centrifuged 8-12min under the revolving speed of 10000-14000rmp/min, obtains orange-yellow
Solid particle, and with deionized water centrifuge washing, obtain organic MOFS package fluorescein composite material.
2. organic MOFS according to claim 1 wraps up fluorescein composite material, it is characterised in that: in step (1), imidazoles
Base organic ligand is 2-methylimidazole, and molar ratio is Zn in troubled liquor2+:HmIM:H2O=1:70:1238。
3. organic MOFS according to claim 1 wraps up fluorescein composite material, it is characterised in that: in step (3), DNA
Sequence number: TTC gTT TCg TTC CCC TTC gTT TCg TT.
4. the application of the described in any item organic MOFS package fluorescein composite material detection mercury ions of claim 1-3.
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| CN201910010936.5A CN109738408B (en) | 2019-01-07 | 2019-01-07 | Organic MOFS (metal organic fluoride) coated fluorescein composite material and application thereof in detection of mercury ions |
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| CN201910010936.5A CN109738408B (en) | 2019-01-07 | 2019-01-07 | Organic MOFS (metal organic fluoride) coated fluorescein composite material and application thereof in detection of mercury ions |
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