CN112666152B - Probe for detecting iodine vapor and ECL detector - Google Patents
Probe for detecting iodine vapor and ECL detector Download PDFInfo
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- CN112666152B CN112666152B CN202011314660.9A CN202011314660A CN112666152B CN 112666152 B CN112666152 B CN 112666152B CN 202011314660 A CN202011314660 A CN 202011314660A CN 112666152 B CN112666152 B CN 112666152B
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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. 129 I has a value of 1.57X 10 7 The ultra-long half-life of the year can cause permanent pollution to the environment. In addition, to 131 I and 125 radioiodine isotopes represented by I may accumulate in the thyroid gland and emit harmful rays, causing carcinogenic risks. If a nuclear leak occurs, I 2 The 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 initiated 18 Bq and 1.53-1.60X 10 17 Of Bq 131 I into the atmosphere, has wide influence on the whole world, and even in northern Europe, the Hadokuai accident occurs and is detected 131 I. Thus, accurate monitoring of atmospheric radioactivity I 2 The vapor is of great significance in indicating nuclear leaks, providing early warning, and effectively handling radioactive iodine vapors.
Currently widely used assay I 2 The method of steam is primarily using a radiation monitoring system for continuous monitoring of radioactivity I in the surrounding air 2 The concentration of (c). However, these monitoring devices are large in size and are fixed to a special fixtureThe fixed position cannot be flexibly operated in a nuclear emergency scene. 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 polymers 2 There 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 I 2 Steam detection, to make up for this deficiency, requires a large amount of air compression, increasing energy consumption. Thus, the development of the radioactivity I 2 The 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 =1;
m is more than 0 and less than 1, n is more than 0 and less than 1; and m + n =1;
0＜m 2 ＜1，0＜n 2 is less than 1; and m is 2 +n 2 ＝1；
0＜m 3 ＜1，0＜n 3 Is less than 1; and m is 3 +n 3 ＝1；
0＜m 4 ＜1，0＜n 4 Less than 1; and m is 4 +n 4 ＝1；
In the formulae (1) to (5), R 1 Are all selected from one of the following structural formulas:
R 2 are all selected from one of the following structural formulas:
R 3 are all selected from one of the following structural formulas:
R 4 are all selected from one of the following structural formulas:
in the structural formula, R is C1-C10 alkyl; n1=1-10; x is halogen.
In the above structural formula, R 1 As a light-emitting group, R 2 As I 2 A responsive group due to the presence of a tertiary amine co-reactant therein, R 3 As the AIE group, there is an AIE effect. Preferably, R is a C2-C8 alkyl group. More preferably an ethyl group.
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, R 1 、R 2 、R 3 、R 4 The 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 hydrophilic polymer has a molecular weight of 500 to 10000.
Furthermore, the particle size of the conjugated polymer quantum dot is 10-300nm.
The conjugated polymers represented by the formulas (1) to (5) each contain a tertiary amine as I 2 Of a co-reactant of (A) can be used for 2 In response, detection of iodine vapor is achieved. Meanwhile, the conjugated polymers shown in the formulas (1) to (5) all contain a group 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 detector x I in iodine vapor to be measured 2 Unknown content, based on ECL Signal intensity A x In a graph of relationshipsThe corresponding relation determines I in iodine vapor to be measured 2 And (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: a is the ultraviolet absorption spectrum of the conjugated polymer THF solution, B is the fluorescence spectrum of the conjugated polymer in the THF-water mixed solvent with different water contents;
FIG. 2: a is a TEM map of Pdots, and B is a DLS map of Pdots;
FIG. 3: a is a glassy carbon electrode modified by Pdots and ECL of a conjugated polymer in a THF solution, B is a fluorescence emission spectrum of the glassy carbon electrode modified by the Pdots, and C is the ECL spectrum of the glassy carbon electrode modified by the Pdots;
FIG. 4: a is I in different concentrations 2 ECL signals of vapor treated Pdots modified GCE, B being I at various concentrations 2 ECL Strength and I of vapor treated Pdots modified GCE 2 Calibration curve of the logarithmic value of the vapour concentration, C being I at different concentrations 2 Of vapour treated PdotECL imaging;
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 K 2 CO 3 (1.30 g) in 5mL of water, and refluxed under Ar for 48 hours. With Na 2 SO 4 The 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 kettle containing 0.1g of K 2 CO 3 5mL 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:
1 H NMR(400MHz,CDCl 3 )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:M w ＝14510,M n ＝9880,PDI＝1.47。
(2) Preparation of Pdots
The conjugated polymer obtained in step (1) was dissolved in THF to prepare a solution of 500ppm, 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 filtered through a 0.22 μm pore size filter to give 10mL of an aqueous solution of Pdots (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 -5 mol/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 -5 And (3) testing the fluorescence spectra of the conjugated polymers in THF-water mixed solvents with different water contents at the excitation light wavelength of 370nm. As shown in fig. 1B, and showed significant AIE behavior in the 600-700nm region. In FIG. 1B, f w Refers to the volume fraction of water in the THF-water mixed solvent. When f is w =90% (vol%), the emission peak appears 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 Al 2 O 3 The GCE electrodes were polished with the powder, cleaned and activated with ultrasound, and 10. Mu.L of the Pdots aqueous solution (concentration of conjugated polymer: 100 ppm) 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) at 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), indicating that its ECL emission mechanism follows a band gap emission model. In fig. 3, scan rate =100mV s -1 (ii) a Photomultiplier tube (PMT) =750V; concentration of Pdots: 100ppm; lambda [ alpha ] ex =370nm. FIG. 3C ECL imaging of Pdots with scan rate =300mV s -1 。
Example 3
The ECL detector prepared in example 2 was used to detect iodine vapor by the following procedure:
the Pdots-modified GCE electrodes were exposed to iodine vapor at different concentrations for 5min at room temperature and ECL measurements were performed using an ECL detector, as above. At 25 ℃ in 0.1M pH 7.4PBS (PMT =750V (A)), with I 2 The ECL emission signal of the conjugated polymer Pdots can be gradually quenched as the vapor concentration increases from 0ppb to 100ppb (fig. 4A). ECL Strength I and I 2 The 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 I =7736-2029lg [ C ] (C [)]，R 2 =0.99823; and an extremely low detection limit (0.51 pM/0.13 ppt) was obtained, significantly lower than the known I 2 Vapor probes, FIG. 4C is through I at different concentrations (0. Mu.g/L, 10. Mu.g/L, 100. Mu.g/L) 2 ECL imaging of vapor treated conjugated polymers Pdot with scan rate =300mV s -1 Significant quenching was also observed in images imaged with ECL, indicating that it is visible in visualization I 2 Potential application in vapor ECL monitoring.
The interference of the complex substances in the nuclear emergency situation is the development of the high-efficiency I 2 Vapor monitoring is an important factor of the sensor. Humidity and some volatile organic vapors are atmospheric andthe main influencing factors in the post-processing of the nuclear industry, in FIG. 5, these factors are in I 2 No 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 I 2 Excellent selectivity of conjugated polymers Pdots in vapor monitoring. H 2 O, 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, I 2 The vapor concentration was 10ppb; the interfering vapor concentration is the saturated vapor pressure.
Other classes of conjugated polymers mentioned herein, all having tertiary amine groups, can generate 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 structural formula of a conjugated polymer in the conjugated polymer quantum dots is shown as the formula (1):
wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and x + y =1;
m is more than 0 and less than 1, n is more than 0 and less than 1; and m + n =1;
in the formula (1), R 1 The structural formula of (A) is as follows:
R 2 the structural formula of (A) is as follows:
R 3 the structural formula of (A) is as follows:
R 4 the structural formula of (A) is as follows:
in the structural formula, R is C1-C10 alkyl; n1=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 10-300nm.
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 of claim 8 for detecting iodine vapor 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 detector x I in the iodine vapor to be measured 2 Content unknown, according to ECL Signal intensity A x Determining I in iodine vapor to be detected in correspondence of the correlation maps 2 And (4) content.
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