CN112268895A - Device and method for detecting concentration of trace superoxide radical free radicals in water by adopting chemiluminescence reagent - Google Patents
Device and method for detecting concentration of trace superoxide radical free radicals in water by adopting chemiluminescence reagent Download PDFInfo
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- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 title claims abstract description 55
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- -1 superoxide ions Chemical class 0.000 claims abstract description 26
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
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- KNJDBYZZKAZQNG-UHFFFAOYSA-N lucigenin Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.C12=CC=CC=C2[N+](C)=C(C=CC=C2)C2=C1C1=C(C=CC=C2)C2=[N+](C)C2=CC=CC=C12 KNJDBYZZKAZQNG-UHFFFAOYSA-N 0.000 description 1
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- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
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Abstract
The invention relates to a device and a method for detecting the concentration of trace superoxide radical ions in water by adopting a chemiluminescence reagent. The device comprises a water body container bottle to be detected, a chemiluminescent reagent container bottle, a peristaltic pump, a spiral light-emitting tube, a photon counter, a computer and a waste liquid bottle. The water body container bottle to be measured and the chemiluminescent reagent container bottle are respectively communicated with the liquid inlet end of the spiral luminotron through a peristaltic pump. The photon counter is arranged on one side of the spiral luminous tube and used for recording light signals in the spiral luminous tube. The photon counter is connected with the computer. The waste liquid bottle is connected with the liquid outlet end of the spiral luminous tube. The chemiluminescent reagent bottle contains a chemiluminescent reagent solution. The method adopts a chemiluminescence reagent to react with a water body solution to be detected containing superoxide ions to generate an optical signal, and performs first-level attenuation fitting according to a kinetic trajectory of the optical signal to deduce the concentration of the superoxide ions in the water body to be detected.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a device and a method for detecting the concentration of trace superoxide radical ions in water by adopting a chemiluminescent reagent.
Background
In recent years, advanced oxidation technology is widely used in the field of water treatment, and the technology utilizes generated active oxygen species to oxidize pollutants in water so as to achieve the purpose of purifying water quality. Superoxide radical (O)2 ·-) Due to its reducing properties, it becomes an important active oxygen species in aqueous environments. Oxygen forms superoxide ions by accepting excited electrons from an electron donor. Superoxide ion can also be combined with hydrogen ion to form hydroperoxyl radical (HO)2 ·) Is present with an acidity coefficient pKa of 4.48. Superoxide ions, which are unstable in water due to the presence of lone pair electrons, are attenuated by self-coupling and can also react with HO2 ·Disproportionation reaction occurs to generate hydrogen peroxide and oxygen.
HO2 ·+HO2 ·→H2O2+O2 (1)
HO2 ·+O2 ·-+H+→H2O2+O2 (2)
This process is the major source of other reactive oxygen species in advanced oxidation technologies. For example, the generated hydrogen peroxide causes generation of hydroxyl radicals having strong oxidation properties by fenton reaction under the action of a trace amount of iron ions present in the aqueous solution.
The existing detection methods of superoxide ions comprise the following methods: superoxide assay, fluorescence, chemiluminescence, and electron paramagnetic capture. Although the electron paramagnetic method has the advantage of high sensitivity in qualitative and quantitative determination of free radicals, the complex and expensive equipment cannot be applied to the detection process of environmental water. The superoxide oxidase and the fluorescence method have the defect that the reagent is difficult to store. The chemiluminescence method is the first choice for detecting trace superoxide ions in environmental water due to high sensitivity and simple operation, but the existing luminescent reagents such as lucigenin and luminol are easily interfered by metal ions and have poor selectivity.
Therefore, the device and the method for quantitatively detecting the concentration of the superoxide radical ions in the water body by adopting the more sensitive and reliable chemiluminescence reagent have very important values for deeply understanding the removal mechanism of the advanced oxidation technology and improving the removal efficiency.
Disclosure of Invention
The invention aims to provide a device and a method for detecting the concentration of trace superoxide radical free radicals in water by adopting a chemiluminescence reagent, and the device and the method can be used for quantitatively detecting the concentration of superoxide radical ions in water.
In order to achieve the purpose, the invention adopts the following technical scheme:
the device for detecting the concentration of trace superoxide radical in water by adopting a chemiluminescent reagent comprises a water body container bottle to be detected, a chemiluminescent reagent container bottle, a peristaltic pump, a spiral light-emitting tube, a photon counter, a computer and a waste liquid bottle. The water body container bottle to be detected and the chemiluminescent reagent container bottle are respectively communicated with the liquid inlet end of the spiral light-emitting tube through peristaltic pumps. The photon counter is arranged on one side of the spiral light-emitting tube and used for recording light signals in the spiral light-emitting tube. And the photon counter is connected with the computer through a USB data line. The waste liquid bottle is connected with the liquid outlet end of the spiral luminous tube. And a chemiluminescent reagent solution is contained in the chemiluminescent reagent container bottle.
Further, the chemiluminescent reagent in the chemiluminescent reagent solution is 2-methyl-6- (4-methylphenyl) -3, 7-dihydroimidazo [1,2-A ] pyrazin-3-one hydrochloride (MCLA, CAS: 128322-44-1). The chemiluminescence reagent MCLA and superoxide radical ions can generate specific chemiluminescence reaction, and is a specific reagent for detecting superoxide radical ions by a chemiluminescence method.
Further, the water body container bottle to be detected and the chemiluminescent reagent container bottle are respectively connected with a peristaltic pump through a hose; the peristaltic pump is connected with the liquid inlet end of the spiral light-emitting tube through a hose; the liquid outlet end of the spiral luminous tube is connected with the waste liquid bottle through a hose.
Furthermore, a magnetic stirring meter is arranged below the water body container bottle to be detected and the chemiluminescent reagent container bottle.
Further, the concentration range of the chemiluminescence reagent solution is 1-10 mu mol/L, and the preferred concentration is 1-2 mu mol/L; the pH value range of the chemiluminescence reagent solution is 4.5-7, and the preferable pH value is 6.
Further, the working voltage of the photon counter is 660-880 mV, and the recording rate is 0.5 count/second. Preferably, the operating voltage of the photon counter is 880 mV.
Furthermore, the spiral luminous tube is made of quartz.
Furthermore, the peristaltic pump adopts an eight-channel micro peristaltic pump, and the constant flow rate of the peristaltic pump is 6 mL/min.
Further, the spiral luminous tube is arranged on the supporting platform.
The invention also relates to a detection method of the device for detecting the concentration of the trace superoxide radical in water by adopting the chemiluminescence reagent, which comprises the following steps:
(1) and (3) introducing the water solution containing the superoxide ions in the water body container bottle to be detected and the chemiluminescent reagent solution in the chemiluminescent reagent container bottle into the spiral light-emitting tube by adopting a peristaltic pump.
(2) The water solution containing superoxide radical ions to be detected and the chemiluminescence reagent solution react in a spiral luminotron to send out light signals.
(3) The photon counter collects the light signal in the spiral luminous tube and transmits the light signal to the computer.
(4) And the computer adopts a dynamic method to fit according to the change process of the optical signal to obtain the concentration of the superoxide radical ions in the water body to be detected. The solution in the spiral luminous tube is discharged into a waste liquid bottle.
The invention has the advantages that:
(1) the invention adopts MCLA chemiluminescence reagent to establish a detection method for detecting superoxide radical ions with lower concentration in water for the first time, and fills the blank of the detection field of the superoxide radical ions in environmental water in China at present. Compared with the prior superoxide radical ion detection method, the superoxide radical ion detection device provided by the invention has high sensitivityThe lower limit of the measurement is 10-10mol/L) and selectivity specificity (MCLA and superoxide radical ion selective chemiluminescence reaction, without interference from other free radicals and metal ions). The method adopts a chemiluminescence reagent to react with a water body solution to be detected containing superoxide ions to generate an optical signal, and performs first-level attenuation fitting according to a kinetic trajectory of the optical signal to deduce the concentration of the superoxide ions in the water body to be detected. The chemiluminescence reagent MCLA adopted by the invention is a specific reagent for detecting superoxide ions, has specific selectivity on the superoxide ions, reduces the interference of other impurities in the environment on the detection result, and ensures the accuracy and reliability of the detection result.
(2) The invention adopts the peristaltic pump to directly mix the water solution to be detected and the chemiluminescent reagent solution, and has simple operation process. The device has the characteristics of small volume, convenience in carrying, easiness in operation and the like, can be used for detecting samples on site, and is suitable for industrial application. The device can directly measure the content of superoxide ions in the environmental water body without a complex pretreatment process, and the detection process takes very short time (less than 5 minutes), so the device has very strong portability and rapid measurement advantages for the existing electron paramagnetic capture or spectrum measuring instrument.
Drawings
FIG. 1 is a schematic view of the structure of the apparatus of the present invention.
Wherein:
1. the device comprises a water body container bottle to be detected, 2, a chemiluminescent reagent container bottle, 3, a magnetic stirring meter, 4, a peristaltic pump, 5, a supporting platform, 6, a spiral light-emitting tube, 7, a photon counter, 8, a computer, 9 and a waste liquid bottle.
Detailed Description
The invention is further described below with reference to the accompanying drawings:
the device for detecting the concentration of trace superoxide radical in water by using a chemiluminescent reagent shown in figure 1 comprises a water body container bottle 1 to be detected, a chemiluminescent reagent container bottle 2, a peristaltic pump 4, a spiral light-emitting tube 6, a photon counter 7, a computer 8 and a waste liquid bottle 9. The water body container bottle 1 to be detected and the chemiluminescent reagent container bottle 2 are respectively communicated with the liquid inlet end of the spiral light-emitting tube 6 through the peristaltic pump 4. The photon counter 7 is arranged on one side of the spiral luminous tube 6 and is used for recording light signals in the spiral luminous tube 6. The photon counter 7 is connected to a computer 8. The waste liquid bottle 9 is connected with the liquid outlet end of the spiral luminous tube 6. The chemiluminescent reagent bottle 2 is filled with a chemiluminescent reagent solution. The water body solution to be detected is contained in the water body container bottle 1 to be detected. The concentration of the superoxide radical ions in the water body solution to be detected is 5-73 nmol/L (nanomole/liter), but the method is not limited to this. The computer is provided with dynamics software Matlab2015, which can be purchased through the company official website and recorded for 1 minute.
Further, the chemiluminescent reagent in the chemiluminescent reagent solution is 2-methyl-6- (4-methylphenyl) -3, 7-dihydroimidazo [1,2-A ] pyrazin-3-one hydrochloride (MCLA, CAS: 128322-44-1). The chemiluminescence reagent MCLA and superoxide radical ions can generate specific chemiluminescence reaction, and is a specific reagent for detecting superoxide radical ions by a chemiluminescence method. Research shows that the accuracy of the detection result of the concentration of the superoxide radical ions in the water body is obviously influenced by the selection of the chemiluminescence reagent. The chemiluminescence reagent has specific selectivity on superoxide radical ions, and the selection of a specific chemiluminescence reagent in the process of detecting superoxide radical radicals in water based on the chemiluminescence reagent requires creative labor of technicians in the field, and the selection of different chemiluminescence reagents obviously influences the detection result.
Further, the water body container bottle 1 to be detected and the chemiluminescent reagent container bottle 2 are respectively connected with a peristaltic pump 4 through a hose; the peristaltic pump 4 is connected with the liquid inlet end of the spiral luminous tube 6 through a hose. The liquid outlet end of the spiral luminous tube 6 is connected with a waste liquid bottle 9 through a hose. Under the drive of the peristaltic pump 4, the water solution to be detected in the water container bottle 1 to be detected and the chemiluminescent reagent solution in the chemiluminescent reagent container bottle enter the spiral light-emitting tube 6 to be mixed under the drive of the peristaltic pump 4, and the mixed liquid in the spiral light-emitting tube 6 is discharged into the waste liquid bottle 9 under the drive of the peristaltic pump 4. The hose is a 1.3 x 0.9mm silicone tube.
Further, a magnetic stirring meter 3 is arranged below the water body container bottle 1 to be detected and the chemiluminescent reagent container bottle 2, so that the solution is uniformly mixed.
Furthermore, based on experimental results obtained by researchers of the invention through creative work, the concentration range of the chemiluminescence reagent solution is 1-10 mu mol/L, and the preferable concentration is 1-2 mu mol/L; the pH value range of the chemiluminescence reagent solution is 4.5-7, and the preferable pH value is 6.
Further, based on experimental results obtained by inventive work of researchers, the working voltage of the photon counter 7 is 660-880 mV, and the recording rate is 0.5 count/second. Preferably, the operating voltage of the photon counter 7 is 880 mV.
Further, the spiral light emitting tube 6 is made of quartz. The spiral light-emitting tube 6 is used for the luminous reaction of the chemiluminescence reagent and superoxide radical ions.
Furthermore, the peristaltic pump 4 adopts an eight-channel micro peristaltic pump, and the constant flow rate of the eight-channel micro peristaltic pump is 6 mL/min. The water body container bottle 1 to be detected and the chemiluminescence reagent container bottle 2 are respectively connected with one channel of the peristaltic pump. The peristaltic pump 4 is used for driving the water solution to be detected in the water container bottle 1 and the chemiluminescent reagent solution in the chemiluminescent reagent container bottle 2 to flow into the spiral luminescent tube 6.
Further, the spiral light-emitting tube 6 is mounted on the supporting platform 5, and the supporting platform 5 plays a role in supporting and fixing the spiral light-emitting tube 6.
The invention also relates to a detection method of the device for detecting the concentration of the trace superoxide radical in water by adopting the chemiluminescence reagent, which comprises the following steps:
(1) and (3) introducing the water solution containing superoxide ions in the water body container bottle 1 to be detected and the chemiluminescent reagent solution in the chemiluminescent reagent container bottle 2 into a spiral light-emitting tube 6 by using a peristaltic pump 4.
(2) The water solution containing superoxide radical ions to be detected and the chemiluminescence reagent solution react in the spiral luminescent tube 6, specifically, the superoxide radical ions in the water solution to be detected and the 2-methyl-6- (4-methylphenyl) -3, 7-dihydroimidazo [1,2-A ] pyrazine-3-ketone hydrochloride in the chemiluminescence reagent solution react to generate 455nm and 380nm optical signals.
The initial reaction between superoxide ion and MCLA chemiluminescent reagent is the hydroxyl radical (HO)2 ·) And MCLA by single electron transfer-Free radicals, which then rapidly react with a second superoxide ion back to MCLA. MCLA-The autoxidation process of (a) produces a singlet anion (OMCLA)-)*Unstable singlet state (OMCLA)-)*Fluorescence at 380nm and 455nm is emitted upon falling back to the ground state. The number of photon signals generated by the process has a linear corresponding relation with the concentration of superoxide radical ions.
(3) The photon counter 7 is arranged at one side of the spiral luminous tube 6, and the probe of the photon counter 7 is aligned with the spiral luminous tube 6. The photon counter 7 collects the light signal in the spiral light emitting tube 6 and transmits the light signal to the computer 8.
(4) And the computer 8 obtains the concentration of the superoxide root ions in the water body to be detected by adopting dynamic software through fitting according to the change process of the optical signal.
When the device is used for detecting the concentration of superoxide ions in the water body, the working voltage of the photon counter is adjusted to 880mV, and the signal recording time is 1 minute. The optical signal generated by superoxide ion and chemical luminous reagent is acted on the photoresistor of photon counter and converted into electric signal by multiplier tube, and the electric signal is inputted into computer. The concentration of superoxide radical ions in the water body can be deduced by performing first-order attenuation fitting on the dynamic trajectory of the optical signal.
In order to understand the effect of the device and the method for detecting the concentration of the superoxide radical ions in the water body, the test process configures the superoxide radical ion solution samples with the concentrations of 5nmol/L, 13nmol/L, 20nmol/L, 36nmol/L and 73nmol/L, and the good linear relation exists between the concentration of the superoxide radical ions in the concentration range (the pH value is 7) and a detection signal, and the correlation coefficient is 0.99, which shows that the concentration of the superoxide radical ions and a luminescent signal have extremely strong response correlation, and the determination method is feasible. The ratio between superoxide ion concentration and signal units (counts) was 1238counts per nanomole per liter. In addition, the invention also discusses the influence of the type and concentration of the chemiluminescence reagent, the pH value and the working voltage of the photon counter on the detection effect, and obtains the following results:
influence of one or more chemiluminescent reagents on the detection
Setting the experimental conditions: the working voltage of the photon counter is 880mV, the flow rate of the peristaltic pump is 6mL/min, the concentration of the chemiluminescent reagent is 1 mu mol/L, and the pH value of the chemiluminescent reagent solution is 6. Under the condition, a series of superoxide radical ions are subjected to standard curve by using a chemiluminescence reagent MCLA, a luminol chemiluminescence reagent (CAS number: 521-31-3) and an acridinium ester chemiluminescence reagent (CAS number: 194357-64-7) respectively, and the obtained linear correlation coefficients are 0.99, 0.23 and 0.16 respectively. The chemiluminescence reagent MCLA is a specific reagent for detecting superoxide radical ions.
Secondly, the influence of the concentration of the chemical luminescent reagent MCLA on the detection effect
Setting the experimental conditions: under the condition that the working voltage of a photon counter is 880mV, the flow rate is 6mL/min, the pH value of MCLA solution is 6, MCLA concentration is 1 mu mol/L, MCLA concentration is 2 mu mol/L, MCLA concentration is 5 mu mol/L and MCLA concentration is 10 mu mol/L respectively, standard curves are made for the superoxide radical ions with the series of concentrations, and linear correlation coefficients are 0.98, 0.99, 0.95 and 0.91 respectively. Experimental results show that the MCLA concentration of 2 mu mol/L has the best response relation and the best detection effect.
Third, the influence of MCLA solution pH value on the detection of superoxide radical ion concentration by chemiluminescence method
Setting conditions: the working voltage of a photon counter is 880mV, the flow rate is 6mL/min, the concentration of the chemiluminescence reagent MCLA is 2 mu mol/L, and under the condition, the water bodies with the pH values of 4.5, 5, 6 and 7 and containing the superoxide radical ion concentration are respectively detected. The correlation coefficients of the standard curve between superoxide ion concentration and signal were 0.88, 0.97, 0.99 and 0.84, respectively. The experimental result shows that the pH value concentration of 6 has the best response relation and the best detection effect.
Fourthly, the influence of different working voltages of the photon counter on the detection of the concentration of the superoxide radical ions by the chemiluminescence method
Setting the test conditions: the influence of the multiplier tube voltages of the photon counter of 660mV, 750mV, 880mV and 920mV on the detection of superoxide ions by a chemiluminescence method is discussed under the condition that the peristaltic pump flow rate is 6mL/min, the concentration of the chemiluminescence reagent MCLA is 2 mu mol/L and the pH of the MCLA luminous reagent solution is 6. Under this condition, the voltage of 660mV can not detect superoxide radical ion with the concentration less than 100 nmol/L. At other test voltages, the correlation coefficients of the standard curves were 0.92, 0.99 and 0.95, respectively. Experimental results show that the photon counter has the best response relation when the voltage is 880mV, and the detection effect is the best.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (10)
1. Adopt the chemiluminescent reagent to detect the device of trace superoxide radical free radical concentration in water, its characterized in that: comprises a water body container bottle to be detected, a chemiluminescent reagent container bottle, a peristaltic pump, a spiral light-emitting tube, a photon counter, a computer and a waste liquid bottle; the water body container bottle to be detected and the chemiluminescent reagent container bottle are respectively communicated with the liquid inlet end of the spiral luminotron through peristaltic pumps; the photon counter is arranged on one side of the spiral light-emitting tube and is used for recording light signals in the spiral light-emitting tube; the photon counter is connected with the computer; the waste liquid bottle is connected with the liquid outlet end of the spiral light-emitting tube; and a chemiluminescent reagent solution is contained in the chemiluminescent reagent container bottle.
2. The device for detecting the concentration of trace superoxide radical in water using chemiluminescence reagent according to claim 1, wherein: the chemiluminescence reagent in the chemiluminescence reagent solution is 2-methyl-6- (4-methylphenyl) -3, 7-dihydroimidazo [1,2-A ] pyrazine-3-ketone hydrochloride.
3. The device for detecting the concentration of trace superoxide radical in water using chemiluminescence reagent according to claim 1, wherein: the water body container bottle to be detected and the chemiluminescent reagent container bottle are respectively connected with a peristaltic pump through a hose; the peristaltic pump is connected with the liquid inlet end of the spiral light-emitting tube through a hose; the liquid outlet end of the spiral luminous tube is connected with the waste liquid bottle through a hose.
4. The device for detecting the concentration of trace superoxide radical in water using chemiluminescence reagent according to claim 1, wherein: and a magnetic stirring meter is arranged below the water body container bottle to be detected and the chemiluminescent reagent container bottle.
5. The device for detecting the concentration of trace superoxide radical in water using chemiluminescence reagent according to claim 2, wherein: the concentration range of the chemiluminescence reagent solution is 1-10 mu mol/L; the pH value range of the chemiluminescence reagent solution is 4.5-7.
6. The device for detecting the concentration of trace superoxide radical in water using chemiluminescence reagent according to claim 1, wherein: the working voltage of the photon counter is 660-880 mV, and the recording rate is 0.5 count/second.
7. The device for detecting the concentration of trace superoxide radical in water using chemiluminescence reagent according to claim 1, wherein: the spiral luminous tube is made of quartz.
8. The device for detecting the concentration of trace superoxide radical in water using chemiluminescence reagent according to claim 1, wherein: the peristaltic pump adopts an eight-channel micro peristaltic pump, and the constant flow rate of the peristaltic pump is 6 mL/min.
9. The device for detecting the concentration of trace superoxide radical in water using chemiluminescence reagent according to claim 1, wherein: the spiral luminous tube is arranged on the supporting platform.
10. The method for detecting the concentration of the superoxide radical in water by using the chemiluminescence reagent as claimed in any one of claims 1 to 9, wherein the method comprises the following steps: the method comprises the following steps:
(1) introducing a water body solution to be detected containing superoxide ions in a water body container bottle to be detected and a chemiluminescent reagent solution in a chemiluminescent reagent container bottle into a spiral luminescent tube by adopting a peristaltic pump;
(2) the water solution to be detected containing the superoxide radical ions and the chemiluminescence reagent solution react in a spiral luminotron to send out a light signal;
(3) the photon counter collects the optical signal in the spiral luminous tube and transmits the optical signal to the computer;
(4) and the computer obtains the concentration of the superoxide radical ions in the water body to be detected through fitting according to the change process of the optical signal.
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