CN112666152A - Probe for detecting iodine vapor and ECL detector - Google Patents
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- 238000002189 fluorescence spectrum Methods 0.000 description 4
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The present invention relates to a probe for detecting iodine vapor and an ECL detector. The probe for detecting iodine vapor comprises conjugated polymer quantum dots with AIECL and ECL properties, can respond to iodine vapor, and an ECL detector based on the probe has extremely high sensitivity and selectivity on trace iodine vapor.
Description
Technical Field
The invention relates to the technical field of iodine vapor detection, in particular to a probe for detecting iodine vapor and an ECL (electron cyclotron resonance) detector.
Background
At present, the safe disposal and the efficient monitoring of radioactive wastes become important guarantees for the sustainable development of the nuclear industry and are also an important subject in the environmental field. Radioactive iodine (I)2) Isotopes are the major volatile fission products produced during the reprocessing of nuclear fuels。129I has a value of 1.57X 107The ultra-long half-life of the year can cause permanent pollution to the environment. In addition, to131I and125radioiodine isotopes represented by I may accumulate in the thyroid gland and emit harmful rays, causing carcinogenic risks. If a nuclear leak occurs, I2The volatility of radioisotope vapors can lead to global contamination. In the event of the Chernobeli and Fukushima nuclear accidents, respectively, 1.76 x 10 of the release was initiated18Bq and 1.53-1.60X 1017Of Bq131I into the atmosphere, has wide influence on the whole world, and even in northern Europe, the Hadokuai accident occurs and is detected131I. Thus, accurate monitoring of atmospheric radioactivity I2The vapor is of great significance in indicating nuclear leaks, providing early warning, and effectively handling radioactive iodine vapors.
Currently widely used assay I2The method of steam is primarily using a radiation monitoring system for continuous monitoring of radioactivity I in the surrounding air2The concentration of (c). However, these monitoring devices are large in size and fixed in a specific location, and cannot be flexibly operated in a nuclear emergency scenario. Furthermore, the presence of other radioactive aerosols in the atmosphere during a nuclear accident can cause interference and cause major errors, as it is monitored by the amount of radiation. At present, based on metal organic frameworks and fluorescent conjugated polymers2There are also many reports on gas sensors, and the iodine vapor is detected in a photoelectric manner or the like, thereby realizing miniaturization of instruments and equipment. But not sensitive enough to carry out traces of I2Steam detection, to make up for this deficiency, requires a large amount of air compression, increasing energy consumption. Thus, the development of the radioactivity I2The portable rapid detection instrument and method with high sensitivity are necessary for real-time early nuclear emergency warning.
Disclosure of Invention
In order to solve the problems of heavy instrument, obvious interference, high detection limit and the like existing in the current iodine vapor detection, the invention aims to provide a probe for detecting iodine vapor and an ECL detector.
The invention discloses an application of a conjugated polymer in preparing a probe for detecting iodine vapor, and particularly discloses a probe for detecting iodine vapor, which comprises conjugated polymer quantum dots (Pdots) with AIECL and ECL properties, wherein the conjugated polymer in the conjugated polymer quantum dots is shown in one of structural formulas (1) to (5):
wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and x + y is 1;
m is more than 0 and less than 1, n is more than 0 and less than 1; and m + n is 1;
0＜m2＜1，0＜n2less than 1; and m is2+n2＝1；
0＜m3＜1，0＜n3Less than 1; and m is3+n3＝1；
0＜m4＜1，0＜n4Less than 1; and m is4+n4＝1；
In the formulae (1) to (5), R1Are all selected from one of the following structural formulas:
R2are all selected from one of the following structural formulas:
R3are all selected from one of the following structural formulas:
R4are all selected from one of the following structural formulas:
in the structural formula, R is C1-C10 alkyl; n1 is 1-10; x is halogen.
In the above structural formula, R1As a light-emitting group, R2As I2A responsive group due to the presence of a tertiary amine co-reactant therein, R3As the AIE group, there is an AIE effect. Preferably, R is a C2-C8 alkyl group. More preferably ethyl.
Preferably, X is bromine.
Preferably, the structural formula of the conjugated polymer in the conjugated polymer quantum dot is shown as the formula (1).
More preferably, R1、R2、R3、R4The following groups are selected in order:
wherein, R is preferably C2-C4 alkyl, and n1 is preferably 6-10.
Further, the conjugated polymer quantum dot also comprises a hydrophilic polymer.
Further, the mass ratio of the conjugated polymer to the hydrophilic polymer in the conjugated polymer quantum dot is 10: 1-1: 2.
further, the hydrophilic polymer is selected from polyethylene glycol (PEG), polystyrene maleic anhydride, carboxymethyl cellulose, polyacrylamide, etc.
Further, the molecular weight of the hydrophilic polymer is 500-10000.
Furthermore, the particle size of the conjugated polymer quantum dot is 10-300 nm.
The conjugated polymers represented by the formulae (1) to (5) each contain a tertiary amine as I2Of a co-reactant of (A) can be used for2In response, detection of iodine vapor is achieved. At the same time(1) The conjugated polymers shown in (5) all contain groups with AIE effect, so that the probe has AIECL and ECL properties.
The second objective of the present invention is to provide an ECL detector for detecting iodine vapor, which comprises a working electrode modified with the above-mentioned probe for detecting iodine vapor of the present invention.
Further, the working voltage of the working electrode is-2V to 2V.
A third object of the present invention is to provide a method for detecting iodine vapor, using the above ECL detector for detecting iodine vapor, comprising the steps of:
(1) testing the ECL signal intensity of iodine vapor with known concentration by using an ECL detector, and establishing a correlation diagram between the concentration of the uranium iodine vapor and the ECL signal intensity according to a detection result;
(2) detecting ECL signal intensity A of iodine vapor to be detected by using ECL detectorxI in iodine vapor to be measured2Unknown content, based on ECL Signal intensity AxDetermining I in iodine vapor to be detected in correspondence of the correlation maps2And (4) content.
By the scheme, the invention at least has the following advantages:
(1) the invention provides an ECL probe for detecting iodine vapor, which comprises a conjugated polymer with aggregation-induced electrochemiluminescence (AIECL) and self-enhanced Electrochemiluminescence (ECL) properties, and the use of ECL technology greatly improves the sensitivity of iodine vapor detection.
(2) The ECL technology has the advantages of no background signal interference, simple and convenient operation, good reproducibility, miniaturization of instruments and the like, and has the most outstanding advantage of extremely high sensitivity. The miniaturization characteristic of the ECL instrument realizes real-time, rapid and accurate detection in a nuclear emergency scene.
(3) The invention realizes the high-sensitivity detection of the trace iodine vapor, the detection limit of the trace iodine vapor reaches 0.51pM/0.13ppt, the trace iodine vapor probe is obviously lower than the known iodine vapor probe, the trace iodine vapor probe has extremely high selectivity to the iodine vapor, and the high-efficiency detection of the nuclear emergency trace iodine vapor can be realized.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
FIG. 1 is a UV absorption spectrum of a conjugated polymer THF solution and fluorescence spectra of the conjugated polymer in THF-water mixed solvents with different water contents;
FIG. 2 is a TEM and DLS map of Pdots;
FIG. 3 shows fluorescence emission spectra and ECL spectra of Pdots-modified glassy carbon electrodes and ECL of conjugated polymers in THF solutions;
FIG. 4 is I at different concentrations2ECL Signal, ECL intensity and I of vapor treated Pdots modified GCE2Calibration curve of logarithmic values of vapor concentration and I of different concentrations2ECL imaging of the vapour treated Pdot;
fig. 5 illustrates the selectivity of the conjugated polymers Pdots.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
The invention relates to a preparation method of an ECL probe for detecting iodine vapor, which comprises the following steps:
(1) synthesis of AIE active conjugated polymers
The conjugated polymer is synthesized by three monomers through Suzuki coupling polymerization reaction, and a tertiary amine coreaction group is modified, and the synthetic route and the steps are as follows:
m-1(0.101g, 0.207mmol), M-2(0.011g, 0.023mmol), M-3(0.150g, 0.23mmol) and Pd (PPh)3)4(0.030g, 5% eq) in 10mL of toluene, 5mL of ethanol and a solution containing K2CO3(1.30g) in 5mL of waterRefluxing for 48h under Ar atmosphere. With Na2SO4The organic phase was dried and spin dried, and the resulting mixture was dissolved in 2mL THF and added dropwise to 300mL hexane to give a dark red solid (P-1).
The solid was added directly to a solution containing 0.1g K2CO35mL of diethylamine and 20mL of THF. After refluxing for 4 days under Ar atmosphere, the solvent was spin-dried, dissolved in 2mL of THF, dropped into 300mL of hexane, and filtered to obtain 0.14g of a conjugated polymer. The conjugated polymers were characterized as follows:
1H NMR(400MHz,CDCl3)δ7.84-7.65(m,2.6H),7.65-7.30(m,8H),7.27-7.03(m,12.2H),4.02-3.79(m,1.6H),3.69-3.30(m,3H),2.47-1.77(m,6.9H),1.77-1.22(m,12H),1.10(s,7.5H),0.85(m,5H).GPC data:Mw＝14510,Mn＝9880,PDI＝1.47。
(2) preparation of Pdots
The conjugated polymer obtained in step (1) was dissolved in THF to prepare a 500ppm solution, and an equivalent amount of PEG5k was added to the solution. Under sonication, 2mL of THF was immediately poured into 10mL of deionized water, the THF was removed by distillation under reduced pressure, and the filtrate was filtered through a 0.22 μm pore size filter to give a 10mL aqueous solution of PDDOTs (conjugated polymer concentration: 100 ppm).
The conjugated polymer prepared in step (1) was dissolved in THF at a concentration of 1X 10 to test the photoelectric properties of the conjugated polymer and Pdots-5mol/L, the UV absorption spectrum of the conjugated polymer THF solution was tested. As shown in FIG. 1A, the conjugated polymer has two distinct absorption peaks at 368nm and 529nm, respectively. The peak at 368nm is the absorption peak of the conjugated backbone of the polymer, while the absorption peak at long wavelength corresponds to the Intramolecular Charge Transfer (ICT) process.
In addition, THF-water solutions of conjugated polymers with different concentrations were prepared, the ratio of THF to water in the solutions was different, and the concentration of conjugated polymer was 1X 10-5And (3) testing the fluorescence spectra of the conjugated polymers in THF-water mixed solvents with different water contents at the excitation light wavelength of 370 nm. As shown in fig. 1B, and shows significant AIE behavior in the 600-700nm region. In FIG. 1B, fwRefers to the water body in the THF-water mixed solventThe integral number. When f iswAt 90% (vol%), the emission peak appeared at 650 nm. As the proportion of water continues to increase, the effective concentration of polymer decreases due to large particle aggregates in the aqueous solution and the fluorescent signal exhibits a slight quenching.
As shown in FIG. 2, the TEM spectrum and DLS data show that the average particle size of Pdots is around 100 nm.
Example 2
An ECL detector was prepared using the probe of example 1, comprising the steps of:
using Al2O3The GCE electrodes were polished with the powder, cleaned and activated with ultrasound, and 10. mu.L of the Pdots aqueous solution (conjugated polymer concentration: 100ppm) prepared in example 1 was applied to each GCE electrode.
The modified electrode was inserted into a luminescence cell containing 0.1M Phosphate Buffered Saline (PBS) pH 7.4. Meanwhile, a counter electrode and an Ag/AgCl reference electrode are inserted, and then a test is carried out by taking an electrode modified by Pdots as a working electrode.
As shown in FIG. 3A, Pdots produced a significant anodic ECL signal in PBS with an emission peak at +1.39V and a peak potential of + 1.19V. Compared to Pdots in water, no significant ECL emission signal was observed in THF for the conjugated polymer prepared in example 1 step (1) (fig. 3A), and therefore the conjugated polymer exhibited significant AIECL behavior. As shown in fig. 3B, the ECL spectrum of Pdots (curve B) substantially coincides with its fluorescence spectrum (curve a), which indicates that its ECL emission mechanism follows a bandgap emission model. In FIG. 3, the scanning rate is 100mV s-1(ii) a Photomultiplier tube (PMT) 750V; concentration of Pdots: 100 ppm; lambda [ alpha ]ex370 nm. FIG. 3C is ECL imaging of Pdots at a scan rate of 300mV s-1。
Example 3
The ECL detector prepared in example 2 was used to detect iodine vapor by the following procedure:
the GCE electrode modified with Pdots was exposed to iodine vapor of different concentrations for 5min at room temperature, and ECL test was performed using an ECL detector, in the same manner as above. With I at 25 ℃ in 0.1M pH 7.4PBS (PMT 750V (A)))2Steam concentration from 0ppb increased to 100ppb (fig. 4A), the ECL emission signal of the conjugated polymer Pdots can be gradually quenched. ECL Strength I and I2The logarithmic value of the vapor concentration C showed excellent linearity in the region of 0.1ppb to 100ppb (FIG. 4B), and the fitted curve was I7736-2029 lg [ C ]]，R20.99823; and an extremely low detection limit (0.51pM/0.13ppt) was obtained, significantly lower than the known I2Vapor probes, FIG. 4C is through I at different concentrations (0. mu.g/L, 10. mu.g/L, 100. mu.g/L)2ECL imaging of vapor treated conjugated polymers Pdot at scan rate of 300mV s-1Significant quenching was also observed in images imaged with ECL, indicating that it is visible in visualization I2Potential application in vapor ECL monitoring.
The interference to cope with complex substances in nuclear emergency scenarios is the development of efficient I2Vapor monitoring is an important factor of the sensor. Humidity and some volatile organic vapors are the main contributing factors in the post-processing of atmospheric and nuclear industries, and in FIG. 5, these factors are at I2No significant interference was shown in the vapor monitoring, which could confirm that the structure of the conjugated polymer could maintain its stability in these interfering atmospheres. The results can also be confirmed in I2Excellent selectivity of conjugated polymers Pdots in vapor monitoring. H2O, cyclohexane and ethanol vapors do not have a center of positive charge, indicating that they cannot bind to lone pairs of electrons on the tertiary amine group. In FIG. 5, I2The vapor concentration was 10 ppb; the interfering vapor concentration is the saturated vapor pressure.
Other classes of conjugated polymers mentioned in the present invention, all having tertiary amine groups, can produce similar iodine vapor response signals as the conjugated polymers in the above examples.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. Use of a conjugated polymer in the preparation of a probe for detecting iodine vapor, characterized in that: the probe comprises conjugated polymer quantum dots, wherein the conjugated polymer in the conjugated polymer quantum dots is represented by one of structural formulas (1) to (5):
wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and x + y is 1;
m is more than 0 and less than 1, n is more than 0 and less than 1; and m + n is 1;
0＜m2＜1，0＜n2less than 1; and m is2+n2＝1；
0＜m3＜1，0＜n3Less than 1; and m is3+n3＝1；
0＜m4＜1，0＜n4Less than 1; and m is4+n4＝1；
In the formulae (1) to (5), R1Are all selected from one of the following structural formulas:
R2are all selected from one of the following structural formulas:
R3are all selected from one of the following structural formulas:
R4are all selected from one of the following structural formulas:
in the structural formula, R is C1-C10 alkyl; n1 is 1-10; x is halogen.
2. The probe for detecting iodine vapor according to claim 1, wherein: r is C2-C8 alkyl.
3. The probe for detecting iodine vapor according to claim 1, wherein: x is bromine.
4. The probe for detecting iodine vapor according to claim 1, wherein: the conjugated polymer quantum dot also comprises a hydrophilic polymer.
5. The probe for detecting iodine vapor according to claim 4, wherein: the hydrophilic polymer is selected from one or more of polyethylene glycol, polystyrene maleic anhydride, carboxymethyl cellulose and polyacrylamide.
6. The probe for detecting iodine vapor according to claim 4, wherein: the molecular weight of the hydrophilic polymer is 500-10000.
7. The probe for detecting iodine vapor according to claim 1, wherein: the particle size of the conjugated polymer quantum dot is 10-300 nm.
8. An ECL detector for detecting iodine vapor, characterized by: comprising a working electrode modified with the probe for detecting iodine vapor according to any one of claims 1 to 7.
9. The ECL detector of claim 8, wherein: the working voltage of the working electrode is-2V to 2V.
10. A method of detecting iodine vapor, comprising: use of the ECL detector for detecting iodine vapor of claim 8, comprising the steps of:
(1) testing the ECL signal intensity of iodine vapor with known concentration by using the ECL detector, and establishing a correlation diagram between the concentration of the uranium iodine vapor and the ECL signal intensity according to the detection result;
(2) detecting ECL signal intensity A of iodine vapor to be detected by using the ECL detectorxI in the iodine vapor to be measured2Unknown content, based on ECL Signal intensity AxDetermining I in iodine vapor to be detected in correspondence of the correlation maps2And (4) content.
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| CN202011314660.9A Active CN112666152B (en) | 2020-11-20 | 2020-11-20 | Probe for detecting iodine vapor and ECL detector |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110082415A (en) * | 2019-05-30 | 2019-08-02 | 吉林大学 | A kind of optical electro-chemistry detection probe, preparation method and applications based on conjugated polymer nanoparticle |
| CN110596082A (en) * | 2019-10-17 | 2019-12-20 | 苏州大学 | Probe for detecting trace uranyl ions and portable ECL detector based on probe |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110082415A (en) * | 2019-05-30 | 2019-08-02 | 吉林大学 | A kind of optical electro-chemistry detection probe, preparation method and applications based on conjugated polymer nanoparticle |
| CN110596082A (en) * | 2019-10-17 | 2019-12-20 | 苏州大学 | Probe for detecting trace uranyl ions and portable ECL detector based on probe |
Non-Patent Citations (2)
| Title |
|---|
| LIN CUI ET AL: "《Tetraphenylenthene-Based Conjugated Microporous Polymer for Aggregation-Induced Electrochemiluminescence》", 《APPLIED MATERIALS & INTERFACES》 * |
| MOHAMAD SALEH ALSALHI ET AL: "《Recent Advances in Conjugated Polymers for Light Emitting Devices》", 《INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES》 * |
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