CN111007038A - Device and method for quantitatively detecting arsenic ions in water based on laser photo-thermal interference - Google Patents

Device and method for quantitatively detecting arsenic ions in water based on laser photo-thermal interference Download PDF

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CN111007038A
CN111007038A CN201911200610.5A CN201911200610A CN111007038A CN 111007038 A CN111007038 A CN 111007038A CN 201911200610 A CN201911200610 A CN 201911200610A CN 111007038 A CN111007038 A CN 111007038A
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CN111007038B (en
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张校亮
田耀宗
李晓春
于化忠
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Taiyuan University of Technology
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Abstract

The invention belongs to the field of optical biochemical detection, and the traditional detection method comprises large-scale instrument methods such as atomic absorption spectrometry, atomic fluorescence spectrometry and the like, and is characterized by high accuracy and quantitative detection, but has the defects of complex operation, long detection period, high equipment cost and the like. The invention can be widely applied to the fields of environment, food detection, medical diagnosis and the like.

Description

Device and method for quantitatively detecting arsenic ions in water based on laser photo-thermal interference
Technical Field
The invention relates to the technical field of optical biochemical detection, in particular to a device and a method for quantitatively detecting arsenic ions in water based on laser photothermal interference.
Background
In recent years, with the continuous improvement of the industrialization degree, the discharge of industrial wastewater is more and more, and some enterprises discharge the generated industrial wastewater into rivers directly without treatment in order to reduce the cost, so that drinking water sources are polluted to different degrees, and the health of people is seriously damaged by pollutants in the water. Trivalent arsenic ion As (III) is one of pollutants in water, can damage human arterioles and capillaries, can cause serious damage to organ organs, and can cause carcinogenesis and even death. Therefore, the detection of As (III) in water is particularly important. The conventional detection method of As (III) mainly comprises the following steps: the large-scale instruments such as atomic absorption spectrometry, atomic fluorescence spectrometry, etc. are characterized by high accuracy and quantitative detection, but have the defects of complex operation, long detection period, high equipment cost, etc.
When the wavelength of the laser is close to the absorption peak of the sample to be detected, the colored substances in the sample to be detected can absorb the laser, so that the temperature of the sample solution is increased, the refractive index of the solution is changed, the laser interference fringes are moved, and the movement amount of the interference fringes is in positive correlation with the concentration of the light absorbing substance in a certain range. In 1995, Bornhop et al used a single He-Ne laser to irradiate a cylindrical capillary through which a liquid flows, the laser reflected and refracted at each interface of the circular capillary, and the reflected and refracted laser interfered around the capillary axis and generated bright and dark interference fringes, which is called "Back-scattering interference" (BSI) (Bornhop D J. Microvolume index of interaction detectors by B. interference detectors Applied optics, 1995, 34(18): 3234-. In 2014, chuminsjo et al used two lasers emitting lasers with different wavelengths to form a pump-detection optical path structure, the pump laser emitted 532nm laser to irradiate a Capillary tube containing a blood sample to be detected, hemoglobin in the blood sample absorbed the pump laser to cause the temperature of the sample to rise and the refractive index to change, and a camera was used to detect the movement of an interference fringe generated by the detection light at 650nm, so as to detect hemoglobin in erythrocytes (Kim U, Song J, Lee D, et al, Capillary-scale measurement of hemoglobin coherence of hemoglobin concentrations, Biosensors and Bioelectronics, 2015,74: 469-.
The nano gold particles are one of stable metal nano particles, and have the advantages of uniform particle size, stable chemical property, easy modification and the like, and also have unique photoelectric characteristics. The aptamer is a small segment of DNA or RNA fragment, can be specifically combined with a target molecule, and has the characteristics of high specificity, high affinity, wide target range, short screening period, easiness in modification and the like compared with the common antigen-antibody. In 2002, Li Yingfu et al used an aptamer capable of specifically recognizing ATP and combined with the principle of fluorescence energy resonance transfer to realize quantitative detection of ATP according to the magnitude of fluorescence energy (Nutiu, R.; Li, Y. F. Structure-switching signaling aptamers. J. Am. chem. Soc., 2003, 125, 4771-4778.). In 2013, Chengliang et al utilize specific binding between aptamer chains and sulfonamide antibiotics (SDM), when SDM exists in a substance to be detected, the SDM is bound with the aptamer chains to cause the aptamer chains to be separated from the surface of the nanogold, the color of the solution is changed from red to blue-purple under the action of high-concentration salt, and the relationship between the maximum absorption peak value of the solution and the concentration of the SDM is established, so that quantitative detection of the SDM (Chen, A. L.; Yang, S.M. et al high sensitive vertical visual detection of refractory by Label-freesource, Biosens. Bioelectron, 2013, 42, 419-425.) is realized.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a device and a method for quantitatively detecting arsenic ions in water based on laser photothermal interference.
In order to achieve the purpose, the invention provides the following technical scheme:
a quantitative detection device for arsenic ions in water based on laser photothermal interference comprises a first laser and a second laser, wherein the first laser and the second laser are vertically distributed, and the first laser controls laser irradiation time through a first laser shutter; the second laser controls the laser irradiation time through a second laser shutter; the dichroic mirror is positioned at the intersection point of the lasers emitted by the two lasers, the direction of the dichroic mirror is the same as the angular bisector of an included angle formed by the laser beams emitted by the two lasers, and the reflector for reflecting the lasers is fixed right above the microchannel chip and forms an included angle of 45 degrees with the horizontal plane; the micro-channel chip is fixedly arranged on the micro-channel chip fixing platform and comprises a sample inlet for mixing reaction solution, a sample outlet for discharging detection liquid and a detection area for laser irradiation, wherein the sample inlet comprises a first sample inlet, a second sample inlet and a third sample inlet; interference fringes generated by light rays reflected and refracted by the light beams through the micro-channel are received by a photoelectric detector, and the photoelectric detector is connected with a computer.
Furthermore, the wavelength range of the first laser is 500-550 nm, the wavelength range of the second laser is 600-650 nm, and the laser intensity of the two lasers is 0.5-1.5W/cm2。
Further, the cross section of the micro-channel is circular or semicircular or square.
Further, the diameter range of the cross section of the circular and semicircular micro-channels is 200-2000 μm, and the width range of the cross section of the square micro-channel is 200-2000 μm.
A method for quantitatively detecting arsenic ions in water based on laser photothermal interference comprises the following steps:
s1, preparing an As (III) aptamer chain solution and a nano-gold particle solution and mixing the As (III) aptamer chain solution and the nano-gold particle solution to obtain a reaction solution; preparing As (III) standard substance solutions with different concentrations of 0 mg/L, 1mg/L, 2mg/L, 3mg/L, 4mg/L, 5mg/L, 6mg/L, 7mg/L and 8mg/L respectively; preparing a high-concentration NaCl solution.
S2, introducing the reaction solution, the ultrapure water and the NaCl solution into the micro-channel chip respectively through a first sample inlet, a second sample inlet and a third sample inlet of the micro-channel chip in sequence, so that the reaction solution is mixed with the ultrapure water in a confluence channel, then mixed with the NaCl solution in a detection channel and flows through a detection zone.
S3, stopping the solution in the sample inlet, opening the first laser shutter after the solution in the detection area stops flowing, closing the second laser shutter, irradiating the detection area for 90-150S by the laser beam of the first laser, continuously recording the change of interference fringe signals through a photoelectric detector, and taking the difference value of the fringe signals at the end moment of irradiation of the first laser relative to the initial moment as the ultrapure water photo-thermal signal PT0-1。
S4, closing the first laser shutter, opening the second laser shutter, irradiating the detection area with the laser from the second laser for the same time as the irradiation time in step S3, continuously recording the change of interference fringe signal by the photoelectric detector, and using the difference between the final irradiation time of the second laser and the initial interference fringe signal as the photo-thermal signal PT of ultrapure water0-2。
S5, sequentially carrying out the following operations on all the As (III) standard solution with different concentrations prepared in the step S1:
s5.1, introducing the reaction solution, the As (III) standard solution and the NaCl solution into the micro-channel chip respectively through a first sample inlet, a second sample inlet and a third sample inlet of the micro-channel chip in sequence, so that the reaction solution is mixed with the As (III) standard solution in a converging channel, then mixed with the NaCl solution in a detection channel and flows through a detection zone.
S5.2, stopping introducing the solution of the sample inlet, opening the first laser shutter after the solution in the detection area stops flowing, closing the second laser shutter, irradiating the detection area for 90-150S by the laser beam of the first laser, continuously recording the change of interference fringe signals through a photoelectric detector, and taking the difference value of the irradiation end time of the first laser relative to the fringe signals at the starting time As an As (III) standard solution photo-thermal signal PT-1.
And S5.3, closing the first laser shutter, opening the second laser shutter, continuously recording the change of interference fringe signals through a photoelectric detector when the laser emitted by the second laser irradiates the detection area is the same As the irradiation time in the step S5.2, and taking the difference value of the interference fringe signals of the irradiation end moment of the second laser relative to the starting moment As the As (III) standard solution photo-thermal signal PT-2.
S5.4 subtracting the photo-thermal signal PT-1 of ultrapure water from the photo-thermal signal PT-1 of As (III) standard solution0-1 obtaining an As (III) standard solution calibration photothermal signal CPT-1 under the irradiation of the first laser, and subtracting an ultrapure water photothermal signal PT from an As (III) standard solution photothermal signal PT-20-2 obtaining an As (III) standard solution calibration photothermal signal CPT-2 under the irradiation of the second laser.
And S6, taking the concentration of the As (III) standard substance solution with different concentrations As an abscissa, and taking the difference D between the CPT-2 of the As (III) standard substance solution calibration photothermal signal irradiated by the second laser and the CPT-1 of the As (III) standard substance solution calibration photothermal signal irradiated by the first laser As an ordinate to draw a standard curve.
S7, introducing a to-be-detected sample with unknown concentration into the substitute As (III) standard solution through the second sample inlet, repeating the steps S5.1-S5.4, and substituting the difference into the standard curve to obtain the As (III) concentration in the to-be-detected sample; in the above steps, the irradiation time interval of the laser beams of the two lasers to the same liquid introduced into the second sample inlet is 2 minutes, and the laser intensities of the ultrapure water, the As (III) standard solution and the solution to be detected irradiated by the two lasers are the same; before the liquid introduced from the second sample inlet is replaced, the former solution in the microchannel chip needs to be cleaned.
Furthermore, the concentration range of the NaCl solution is 2-5 mol/L.
Further, the speed ratio of the liquid introduced into the sample inlet is 85:13: 2.
Further, the signal of the interference fringe in the steps S3-S5 is the light intensity distribution curve of the interference fringe and the phase value of the curve after the fast fourier transform, and the difference value of the signal of the interference fringe is the phase difference of the light intensity distribution curve of the fringe at the end time and the start time of the laser irradiation after the fast fourier transform.
In conclusion, the invention has the following beneficial effects:
the invention provides a device and a method for quantitatively detecting arsenic ions in water based on laser photothermal interference, aiming at the problems of large sample and reagent consumption, long detection time consumption, difficult integration, difficult reduction of detection limit and the like of the traditional large instrument. The micro-channel is used as a reaction area, and detection can be completed only by a trace amount of sample to be detected; the whole detection process adopts a temperature control system to avoid the influence of the external environment temperature change on the experimental result; the double laser beams are adopted to respectively excite the photothermal effect to enhance the detection signal, the photothermal signal intensity can be enhanced and the detection limit can be reduced by improving the power of the laser beam in the detection area, and the fringe movement information collected by the photoelectric detector is converted into the phase change through Fourier transform, so that the data processing precision can be improved.
Drawings
FIG. 1 is a schematic diagram of a first laser turning on and a second laser turning off according to the present invention;
FIG. 2 is a schematic diagram of the present invention showing the second laser turned on and the first laser turned off;
FIG. 3 is a schematic view of a microchannel chip used in the detection apparatus of the present invention;
FIG. 4 is a graph showing the relationship between As (III) and detection signals at different concentrations according to the present invention.
In the figure: 1. the device comprises a first laser, 2, a first laser shutter, 3, a second laser, 4, a second laser shutter, 5, a dichroic mirror, 6, a reflector, 7, a microchannel chip, 7-1, a first sample inlet, 7-2, a second sample inlet, 7-3, a third sample inlet, 7-4, a sample outlet, 7-5, a detection zone, 7-6, a detection channel, 7-12, a converging channel, 8, a microchannel chip fixing platform, 9, a photoelectric detector, 10 and a computer.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
As shown in figures 1-4, a device for quantitatively detecting arsenic ions in water based on laser photothermal interference comprises a first laser 1 and a second laser 3, wherein the first laser 1 and the second laser 3 are vertically distributed, the first laser 1 controls laser irradiation time through a first laser shutter 2, the second laser 3 controls laser irradiation time through a second laser shutter 4, the wavelength range of the first laser 1 is 500-550 nm, the wavelength range of the second laser 3 is 600-650 nm, and the laser intensities of the two lasers are both 0.5-1.5W/cm2(ii) a The dichroic mirror 5 is positioned at the intersection point of the lasers emitted by the two lasers, the direction of the dichroic mirror 5 is the same as the angular bisector of an included angle formed by the laser beams emitted by the two lasers, and both the dichroic mirror and the two laser beams form an included angle of 45 degrees, so that the propagation directions of the two laser beams after passing through the dichroic mirror 5 are consistent, the laser beams irradiate to the reflecting mirror 6, and the reflecting mirror 6 for reflecting the laser beams is fixed right above the microchannel chip 7 and forms an included angle of 45 degrees with the horizontal plane; the micro-channel chip 7 is fixedly arranged on a micro-channel chip fixing platform 8, the micro-channel chip fixing platform 8 comprises a temperature control system, the temperature control system belongs to the prior art and is used for keeping the temperature of the environment where the micro-channel chip is located constant, the micro-channel chip 7 is made of PDMS or PMMA or PC, the micro-channel chip 7 comprises a sample inlet used for mixing reaction solution, a sample outlet 7-4 used for discharging detection liquid and a detection area 7-5 used for laser irradiation, the sample inlet comprises a first sample inlet 7-1, a second sample inlet 7-2 and a third sample inlet 7-3, the first sample inlet 7-1 and the second sample inlet 7-2 are converged through a micro-channel to form a converging channel 7-12, and the converging channel 7-12 is converged through the micro-channel and the third sample inlet 7-3 to form a detection channel 7-6, the detection area 7-5 is positioned in the middle of the detection channel 7-6, the tail end of the detection channel 7-6 is provided with a sample outlet 7-4, the cross section of the micro-channel is circular, semicircular or square, the diameter range of the cross section of the circular and semicircular micro-channels is 200-2000 mu m, and the width range of the cross section of the square micro-channel is 200-2000 mu m; interference fringes generated by light rays reflected and refracted by the light beams through the micro-channel are received by the photoelectric detector 9, the photoelectric detector 9 is connected with the computer 10, and the received spatial light intensity distribution data of the interference fringes are transmitted to the computer 10.
Two lasers respectively emit two beams of red and green lasers, the lasers pass through a dichroic mirror 5 and are reflected by a plane reflector 6 and then irradiate a detection area 7-5 of a micro-channel, As (III) in the solution is specifically combined with an aptamer chain wrapped on the surface of the nano-gold, a high-concentration NaCl solution is added to cause the aggregation of nano-gold particles, the solution is changed from wine red to blue purple, the laser beams irradiating the micro-channel are reflected and refracted by a plurality of interfaces of the channel and then interfere, and interference fringes are received by a photoelectric detector; the photothermal effect can change the temperature of the solution after light absorption to cause interference fringes to move, the concentration of As (III) in the solution is quantitatively detected by measuring the difference value of red and green two-beam laser photothermal signals, and based on the principle and the device, the method for quantitatively detecting the arsenic ions in the water based on the laser photothermal interference comprises the following steps:
s1, preparing an As (III) aptamer chain solution and a nano-gold particle solution and mixing the As (III) aptamer chain solution and the nano-gold particle solution to obtain a reaction solution; preparing As (III) standard substance solutions with different concentrations of 0 mg/L, 1mg/L, 2mg/L, 3mg/L, 4mg/L, 5mg/L, 6mg/L, 7mg/L and 8mg/L respectively; preparing a high-concentration NaCl solution, wherein the concentration range of the NaCl solution is 2-5 mol/L.
S2, introducing the reaction solution, the ultrapure water and the NaCl solution into the micro-channel chip respectively through a first sample inlet 7-1, a second sample inlet 7-2 and a third sample inlet 7-3 in sequence, so that the reaction solution is mixed with the ultrapure water in a converging channel 7-12, then mixed with the NaCl solution in a detection channel 7-6 and flows through a detection zone 7-5.
S3, stopping the introduction of the solution at the sample inlet, opening the first laser shutter 2 after the solution in the detection area 7-5 stops flowing, closing the second laser shutter 4, irradiating the detection area for 90-150S by the laser beam of the first laser 1, continuously recording the change of interference fringe signals through the photoelectric detector 9, and taking the difference value of the fringe signals at the end moment of irradiation of the first laser 1 relative to the initial moment as the ultrapure water photo-thermal signal PT (potential transformer) PT0-1。
S4, closing the first laser shutter 2, opening the second laser shutter 4, irradiating the detection area 7-5 with the laser from the second laser 3 for the same time as the irradiation time in step S3, continuously recording the change of interference fringe signal by the photodetector 9, and using the irradiation end time of the second laser 3 to be oppositeTaking the difference value of the interference fringe signals at the starting moment as an ultrapure water photo-thermal signal PT0-2; in steps S3 and S4, ultrapure water is used as a detection target, and ultrapure water is used as a blank solution as a control group for the first laser 1 and the second laser 3 in the subsequent steps.
S5, sequentially carrying out the following operations on all the As (III) standard solution with different concentrations prepared in the step S1:
s5.1, introducing a reaction solution, an As (III) standard solution and a NaCl solution into the micro-channel chip respectively through a first sample inlet 7-1, a second sample inlet 7-2 and a third sample inlet 7-3 in sequence, so that the reaction solution is firstly mixed with the As (III) standard solution in a converging channel 7-12, then is mixed with the NaCl solution in a detection channel 7-6 and then flows through a detection zone 7-5;
s5.2, stopping introducing the solution of the sample inlet, opening the first laser shutter 2 after the solution in the detection area 7-5 stops flowing, closing the second laser shutter 4, irradiating the detection area for 90-150S by the laser beam of the first laser 1, continuously recording the change of interference fringe signals through the photoelectric detector 9, and taking the difference value of the irradiation end time of the first laser 1 relative to the fringe signals at the starting time As an As (III) standard solution photo-thermal signal PT-1.
And S5.3, closing the first laser shutter 2, opening the second laser shutter 4, continuously recording the change of interference fringe signals through the photoelectric detector 9 when the laser emitted by the second laser 3 irradiates the detection area in the same time As the irradiation time in the step S5.2, and taking the difference value of the interference fringe signals of the irradiation end time of the second laser 3 relative to the starting time As an As (III) standard solution photo-thermal signal PT-2.
S5.4 subtracting the photo-thermal signal PT-1 of ultrapure water from the photo-thermal signal PT-1 of As (III) standard solution0-1 obtaining an As (III) standard solution calibration photothermal signal CPT-1 under the irradiation of the first laser 1, and subtracting an ultrapure water photothermal signal PT from an As (III) standard solution photothermal signal PT-202, obtaining an As (III) standard solution calibration photothermal signal CPT-2 irradiated by the second laser 3.
And S6, drawing a standard curve by taking the concentration of the As (III) standard substance solution with different concentrations As an abscissa and the difference D between the calibration photothermal signal CPT-2 of the As (III) standard substance solution irradiated by the second laser 3 and the calibration photothermal signal CPT-1 of the As (III) standard substance solution irradiated by the first laser 1 As an ordinate.
And S7, introducing the sample to be detected with unknown concentration into the substitute As (III) standard solution through the second sample inlet 7-2, repeating the operation of the steps S5.1-S5.4, and substituting the signal value of the sample to be detected with unknown concentration into the standard curve to obtain the As (III) concentration in the sample to be detected.
In the above steps, the speed ratio of the liquid introduced into the sample inlet is 85:13:2, the irradiation interval of the laser beams of the two lasers to the same liquid introduced into the second sample inlet 7-2 is 2 minutes, and the laser intensities of the ultrapure water irradiated by the two lasers, the As (III) standard solution and the solution to be detected are the same; before the liquid introduced from the second sample inlet 7-2 is replaced, the former solution in the microchannel chip 7 needs to be cleaned.
And the signal of the interference fringe in the steps S3-S5 is the light intensity distribution curve of the interference fringe and the phase value of the curve after fast Fourier transform, and the difference value of the signal of the interference fringe is the phase difference of the light intensity distribution curve of the fringe at the end moment and the start moment of laser irradiation after fast Fourier transform.
Example (b):
in this embodiment, the device has the following component parameters: the wavelength of the first laser 1 is 532nm, the wavelength of the second laser 3 is 640nm, the dichroic mirror 5 is a green-reflecting red-transmitting dichroic mirror, the microchannel chip 7 is PDMS, the side length of a square in the microchannel chip 7 is 200 mu m, and the photoelectric detector 9 is a linear array CCD.
Preparing nano gold particles: the diameter of the nano gold particles used in the experiment is 10nm, 1mL of 1% sodium citrate solution is stirred and added into 100mL of 0.01% chloroauric acid solution at room temperature, 1mL of sodium borohydride solution is added into the mixed solution after 1 minute, and the stirring is ceaselessly carried out until the color of the solution becomes wine red; adding the prepared As (III) aptamer solution into the prepared nanogold solution at room temperature to obtain a reaction solution, sequentially and respectively introducing the reaction solution, ultrapure water and a NaCl solution with the concentration of 3 mol/L from injection ports 7-1, 7-2 and 7-3 of the microchannel chip at the speed ratio of 85:13:2, so that the reaction solution is mixed with the ultrapure water, then is mixed with the NaCl solution, and finally flows through a detection zone 7-5.
As shown in FIGS. 1 and 2, the first laser emits a laser beam with a wavelength of 532nm, the second laser emits a laser beam with a wavelength of 640nm, and the laser intensity of the two lasers irradiating the detection area is 1.2W/cm2Because of the action of the dichroic mirror 5, the laser beam emitted by the second laser 3 and the laser beam emitted by the first laser 1 can irradiate the detection area of the microchannel after being reflected by the reflecting mirror 6, the laser generates a multi-beam interference phenomenon through the reflection and refraction of the channel and the solution interface, the channel and the air interface of the detection area 7-5 of the microchannel chip 7, the light reflected and refracted by different interfaces generates interference fringes in the space, and the information of the light intensity, the frequency, the phase and the like of the interference fringes displayed on the photoelectric detector is recorded by the photoelectric detector connected with the computer and is transmitted to the computer; firstly, stopping the introduction of a solution at a sample inlet, stopping the flow of the solution in a detection channel 7-6 of a detection area 7-5, opening a first laser shutter 2, closing a second laser shutter 4, irradiating a reaction area 120s by a laser beam of a first laser 1, continuously recording the variation of interference fringe signals through a photoelectric detector 9, and calculating an ultrapure water photo-thermal signal PT0-1; closing the first laser shutter 2, opening the second laser shutter 4 after 2 minutes to enable the laser emitted by the second laser 3 to irradiate the reaction area 120s, continuously recording the variation of the interference fringe signal through the photoelectric detector 9 and calculating the ultrapure water photo-thermal signal PT0-2。
Introducing a reaction solution, an As (III) standard solution and a NaCl solution with the concentration of 3 mol/L from a sample inlet of a micro-channel chip 7 in sequence respectively, wherein the introduction speed ratio is 85:13:2, so that the reaction solution is firstly mixed with the As (III) standard solution and then mixed with the NaCl solution, and finally flows through a detection area 7-5, the concentrations of the As (III) standard solution are respectively 0 mg/L, 1mg/L, 2mg/L, 3mg/L, 4mg/L, 5mg/L, 6mg/L, 7mg/L and 8mg/L, and the solvent is water; according to the photothermal signal PT of the ultrapure water being measured0-1 and photothermal signal PT0-2 measuring photothermal signals PT-1 and PT-2 of the As (III) standard solution, subtracting the photothermal signals PT-1 from the As (III) standard solutionPure water photo-thermal signal PT0-1 obtaining a calibration photothermal signal CPT-1 of the As (III) standard solution under the irradiation of the first laser 1, and subtracting the ultrapure water photothermal signal PT from the photothermal signal PT-2 of the As (III) standard solution02, obtaining an As (III) standard solution calibration photothermal signal CPT-2 irradiated by the second laser 3.
Taking the concentration of the As (III) standard substance solution with different concentrations As an abscissa, and taking a difference D obtained by subtracting a CPT-1 calibration photothermal signal of the standard substance solution under the irradiation of the first laser (1) from a CPT-2 calibration photothermal signal of the As (III) standard substance solution under the irradiation of the second laser 3 As an ordinate to draw a standard curve; cleaning an As (III) standard substance solution in the microchannel chip 7, sequentially and respectively introducing a reaction solution, a solution to be detected and a NaCl solution with the concentration of 3 mol/L from a sample inlet of the microchannel chip 7 at a speed ratio of 85:13:2, so that the reaction solution is firstly mixed with the solution to be detected, then is mixed with the NaCl solution and finally flows through a detection area 7-5; according to the step of measuring the photo-thermal signals of ultrapure water and As (III) standard solution, measuring and calculating the difference value of the calibration photo-thermal signal CPT-2 of the solution to be measured under the irradiation of the second laser 3 minus the calibration photo-thermal signal CPT-1 of the solution to be measured under the irradiation of the first laser 1, substituting the difference value into a standard curve to obtain the concentration of As (III) in the solution to be measured, wherein the higher the concentration of the As (III) solution is, the higher the aggregation degree of the gold nanoparticles is, the lower the absorbance at 532nm is, the higher the absorbance at 640nm is, under the irradiation of the laser with the wavelength of 640nm emitted by the second laser and the laser with the wavelength of 532nm emitted by the first laser, the gold nanoparticles solution is red and is bluish-purple after aggregation, the more the higher the aggregation degree is, the more obvious the change of the photo-thermal effect intensity is, the more obvious the change, compared with single-wavelength detection, the difference between the two signals is used for amplifying the signals, and the amplification of the photo-thermal signals is realized.
The method for acquiring the interference fringe signal in the steps comprises the following steps: the linear array CCD is set to be in a continuous acquisition mode, the sampling frequency is set to be 10 Hz, the sampling interval is 0.15s, all interference patterns generated by laser irradiation solution in the whole irradiation end stage are acquired from the beginning of laser irradiation, a light intensity curve in the interference patterns is processed by adopting fast Fourier transform, the phase value of the light intensity curve of the interference patterns is obtained, and the phase difference of the fringe light intensity distribution curve of the laser irradiation end time and the initial time after the fast Fourier transform is used as a photo-thermal signal.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.

Claims (8)

1. The utility model provides an aquatic arsenic ion quantitative determination device based on laser light and heat is interfered, includes first laser instrument (1) and second laser instrument (3), its characterized in that: the first laser (1) and the second laser (3) are vertically distributed, and the laser irradiation time of the first laser (1) is controlled through a first laser shutter (2); the second laser (3) controls the laser irradiation time through a second laser shutter (4); the dichroic mirror (5) is positioned at the intersection point of the lasers emitted by the two lasers, the direction of the dichroic mirror (5) is the same as the angular bisector of an included angle formed by the laser beams emitted by the two lasers, and the reflector (6) for reflecting the lasers is fixed right above the microchannel chip (7) and forms an included angle of 45 degrees with the horizontal plane; the micro-channel chip (7) is fixedly arranged on a micro-channel chip fixing platform (8), the micro-channel chip (7) comprises a sample inlet for mixing reaction solution, a sample outlet (7-4) for discharging detection liquid and a detection area (7-5) for laser irradiation, the sample inlet comprises a first sample inlet (7-1), the device comprises a second sample inlet (7-2) and a third sample inlet (7-3), wherein the first sample inlet (7-1) and the second sample inlet (7-2) are converged through a micro-channel to form a converging channel (7-12), the converging channel (7-12) is converged through the micro-channel and the third sample inlet (7-3) to form a detection channel (7-6), the detection zone (7-5) is positioned in the middle of the detection channel (7-6), and the tail end of the detection channel (7-6) is provided with a sample outlet (7-4);
interference fringes generated by light rays reflected and refracted by the light beams through the micro-channels are received by a photoelectric detector (9), and the photoelectric detector (9) is connected with a computer (10).
2. The device for quantitatively detecting the arsenic ions in the water based on the laser photothermal interference as claimed in claim 1, wherein: the wavelength range of the first laser (1) is 500-550 nm, the wavelength range of the second laser (3) is 600-650 nm, and the laser intensity of the two lasers is 0.5-1.5W/cm2。
3. The device for quantitatively detecting the arsenic ions in the water based on the laser photothermal interference as claimed in claim 1, wherein: the cross section of the micro-channel is circular or semicircular or square.
4. The device for quantitatively detecting the arsenic ions in the water based on the laser photothermal interference as claimed in claim 3, wherein: the diameter range of the cross section of the round and semicircular micro-channels is 200-2000 mu m, and the width range of the cross section of the square micro-channel is 200-2000 mu m.
5. A method for quantitatively detecting arsenic ions in water based on laser photothermal interference is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing an As (III) aptamer chain solution and a nano-gold particle solution and mixing the As (III) aptamer chain solution and the nano-gold particle solution to obtain a reaction solution; preparing As (III) standard substance solutions with different concentrations of 0 mg/L, 1mg/L, 2mg/L, 3mg/L, 4mg/L, 5mg/L, 6mg/L, 7mg/L and 8mg/L respectively; preparing a high-concentration NaCl solution;
s2, introducing a reaction solution, ultrapure water and a NaCl solution into the micro-channel chip respectively through a first sample inlet (7-1), a second sample inlet (7-2) and a third sample inlet (7-3) in sequence, so that the reaction solution is mixed with the ultrapure water in a converging channel (7-12), then is mixed with the NaCl solution in a detection channel (7-6), and then flows through a detection zone (7-5);
s3, stopping the introduction of the solution at the sample inlet, and stopping the flow of the solution at the detection area (7-5)Opening a first laser shutter (2), closing a second laser shutter (4), continuously recording the change of interference fringe signals by a photoelectric detector (9) in a laser beam irradiation detection area (7-5) 90-150 s of a first laser (1), and taking the difference value of the irradiation end time of the first laser (1) relative to the initial time fringe signals as an ultrapure water photo-thermal signal PT0-1；
S4, closing the first laser shutter (2), opening the second laser shutter (4), continuously recording the change of the interference fringe signal by the photoelectric detector (9) when the laser emitted by the second laser (3) irradiates the detection area (7-5) with the same irradiation time as the irradiation time in the step S3, and taking the difference value of the interference fringe signal of the irradiation end time of the second laser (3) relative to the initial time as the ultrapure water photo-thermal signal PT0-2；
S5, sequentially carrying out the following operations on all the As (III) standard solution with different concentrations prepared in the step S1:
s5.1, introducing a reaction solution, an As (III) standard solution and a NaCl solution into a first sample inlet (7-1), a second sample inlet (7-2) and a third sample inlet (7-3) of a micro-channel chip respectively in sequence, so that the reaction solution is firstly mixed with the As (III) standard solution in a converging channel (7-12), then is mixed with the NaCl solution in a detection channel (7-6) and then flows through a detection zone (7-5);
s5.2, stopping introducing the solution of the sample inlet, opening the first laser shutter (2) after the solution in the detection area (7-5) stops flowing, closing the second laser shutter (4), irradiating the detection area for 90-150S by using the laser beam of the first laser (1), continuously recording the change of interference fringe signals through a photoelectric detector (9), and taking the difference value of the irradiation end time of the first laser (1) relative to the fringe signals at the starting time As an As (III) standard solution photo-thermal signal PT-1;
s5.3, closing the first laser shutter (2), opening the second laser shutter (4), continuously recording the change of interference fringe signals through a photoelectric detector (9) when the laser emitted by the second laser (3) irradiates the detection area (7-5) at the same time As the irradiation time in the step S5.2, and taking the difference value of the interference fringe signals of the irradiation end time of the second laser (3) relative to the starting time As an As (III) standard solution photo-thermal signal PT-2;
s5.4 subtracting the photo-thermal signal PT-1 of ultrapure water from the photo-thermal signal PT-1 of As (III) standard solution0-1 obtaining an As (III) standard solution calibration photothermal signal CPT-1 under the irradiation of the first laser (1), and subtracting an ultrapure water photothermal signal PT from an As (III) standard solution photothermal signal PT-20-2 obtaining an As (III) standard solution calibration photothermal signal CPT-2 under the irradiation of the second laser (3);
s6, taking the concentration of the As (III) standard substance solution with different concentrations As an abscissa, and taking the difference D, obtained by subtracting the CPT-1 calibration photothermal signal of the As (III) standard substance solution irradiated by the first laser (1) from the CPT-2 calibration photothermal signal of the As (III) standard substance solution irradiated by the second laser (3), As an ordinate, drawing a standard curve;
s7, introducing a to-be-detected sample with unknown concentration into the substitute As (III) standard solution through the second sample inlet (7-2), repeating the steps S5.1-S5.4, and substituting the difference into the standard curve to obtain the As (III) concentration in the to-be-detected sample;
in the above steps, the irradiation time interval of the laser beams of the two lasers to the same liquid introduced from the second sample inlet (7-2) is 2 minutes, the two lasers irradiate the ultrapure water, the As (III) standard solution and the solution to be tested, and the former solution in the microchannel chip (7) needs to be cleaned before the liquid introduced from the second sample inlet (7-2) is replaced.
6. The method for quantitatively detecting the arsenic ions in the water based on the laser photothermal interference according to claim 5, which is characterized in that: the concentration range of the NaCl solution is 2-5 mol/L.
7. The method for quantitatively detecting the arsenic ions in the water based on the laser photothermal interference according to claim 5, which is characterized in that: the liquid is introduced into the sample inlet at a speed ratio of 85:13: 2.
8. The method for quantitatively detecting the arsenic ions in the water based on the laser photothermal interference according to claim 5, which is characterized in that: and the signal of the interference fringe in the steps S3-S5 is a phase value after the light intensity distribution curve of the interference fringe and the curve are subjected to fast Fourier transform, and the difference value of the signal of the interference fringe is the phase difference after the fast Fourier transform of the light intensity distribution curve of the fringe at the end moment and the start moment of laser irradiation.
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