CN113624741A - Method and system for rapidly detecting benzimidazole pesticide residues in citrus based on Surface Enhanced Raman Spectroscopy (SERS) technology - Google Patents

Method and system for rapidly detecting benzimidazole pesticide residues in citrus based on Surface Enhanced Raman Spectroscopy (SERS) technology Download PDF

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CN113624741A
CN113624741A CN202110941267.0A CN202110941267A CN113624741A CN 113624741 A CN113624741 A CN 113624741A CN 202110941267 A CN202110941267 A CN 202110941267A CN 113624741 A CN113624741 A CN 113624741A
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CN113624741B (en
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陈全胜
潘海辉
王志敏
王丽
欧阳琴
李欢欢
林颢
郭志明
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Jiangsu University
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Abstract

The invention discloses a method and a system for rapidly detecting benzimidazole pesticide residues in citrus based on a Surface Enhanced Raman Spectroscopy (SERS) technology. The detection device comprises a shell, an SERS detection vessel, a sample box, a switch, a miniature integrated Raman spectrometer, a control circuit, a charging power supply, a laser probe and a mobile terminal. The detection method comprises the steps of collecting SERS spectral data of the oranges by using the portable detection device, and wirelessly transmitting the data to the terminal equipment through the Bluetooth module. The terminal device calculates and processes the spectrum data through a built-in baseline correction algorithm, a spectrum matching algorithm and a detection model, and a detection result is displayed on a human-computer interaction terminal interface. The portable detection device has the advantages of high integration level, small volume, detection speed block, low cost and the like. According to the invention, the prediction capability of the spectral model can be effectively improved by processing SERS spectral data, and the rapid detection of the benzimidazole pesticide residue in the citrus is realized.

Description

Method and system for rapidly detecting benzimidazole pesticide residues in citrus based on Surface Enhanced Raman Spectroscopy (SERS) technology
Technical Field
The invention relates to the field of food pesticide residue detection, optical machinery and instrument subjects, in particular to a detection system for benzimidazole pesticide residues in citrus by using a surface-enhanced Raman spectroscopy technology.
Background
Citrus is one of indispensable foods in life of people and is an important material source for people to obtain nutrition. At present, the measures for preventing the diseases and insect pests and the fungal infection during the citrus planting are still chemical pesticides. However, because of the difficult degradability of the pesticide, the citrus fruits have certain content of pesticide residues. The national relevant organization makes relevant regulations on the maximum residual quantity of the benzimidazole pesticides in citrus, and if the pesticide residue exceeds the maximum limit, the maximum residual quantity of the benzimidazole pesticides can pose a serious threat to the health of human bodies. Therefore, it is necessary to detect the residual benzimidazole pesticide in citrus. The conventional detection method and device for the citrus benzimidazole pesticides have corresponding defects in the analysis and detection process, and are mainly embodied in the aspects of detection cost, detection speed, detection places and the like. Therefore, a portable rapid detection system for the benzimidazole pesticide residues in the citrus needs to be researched, so that the rapid detection of the pesticide residues is ensured, and a certain detection precision is ensured.
The spectrum detection technology is a technology which develops rapidly in recent decades and has wide application prospect. In the field of rapid detection of food, spectroscopic techniques represented by near infrared spectroscopy, Raman spectroscopy and fluorescence spectroscopy have significant breakthroughs in the aspects of theory and application. The surface enhanced Raman spectrum is an enhanced spectrogram of a common Raman signal, inherits the advantages of the Raman spectrum compared with other spectrums, and breaks through the key bottlenecks of weak signals and low detection limit of the traditional Raman spectrum. Therefore, the application of surface enhanced Raman spectroscopy to the field of rapid detection of security quality in citrus is a very valuable direction of the technology.
At present, detection devices for raman spectroscopy are numerous, however most of these devices are only adaptable to laboratory studies. On one hand, the instrument has large volume and high requirement on detection environment, so that the instrument is inconvenient to carry; on the other hand, compared with the common raman, the surface enhanced raman is more complex in sample preparation and data processing, and the existing raman instrument equipment with only the spectrum acquisition function cannot well realize pesticide residue detection in citrus. In order to solve the problems, a system for rapidly detecting the benzimidazole pesticide residues in the citrus based on the surface enhanced raman spectroscopy technology needs to be designed, and the system comprises a detection method and a detection device. Therefore, the problems of complex sample preparation, complex data processing and difficulty in carrying the equipment are solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a rapid detection system for the benzimidazole pesticide residues in citrus based on a surface enhanced Raman spectroscopy technology, which realizes the portability of a detection device and the rapid acquisition of the surface enhanced Raman spectroscopy information of a detected substance, establishes a spectral data processing and model detection method and improves the accuracy and reliability of detection.
Aiming at the method and the device, the technical scheme is specifically adopted as follows:
a method for detecting imidazole pesticide residues in oranges based on a Surface Enhanced Raman Spectroscopy (SERS) technology comprises the following steps:
the method comprises the following steps: surface enhancement amplification of Raman signals of the benzimidazole pesticide residues in the citrus: a two-channel SERS detection dish is used as a substance reaction and detection site. The pretreated orange extracting solution and the SERS reinforcing material are respectively injected into the SERS detection vessel through different channels, and the detection vessel is inserted into a clamping groove of the sample detection box. Through a certain temperature control function in the sample detection box, substances in the citrus extract are rapidly distributed in the SERS enhancing material, so that the surface enhanced Raman effect is achieved.
Step two: collecting surface enhanced Raman spectra of the citrus benzimidazole pesticide residues: the laser probe of the portable Raman spectrum detection device is inserted into a sliding groove of the sample detection box, and the current surface enhanced Raman spectrum data of the detected substance is rapidly acquired by controlling a laser transmitter and a Raman photoelectric converter of the miniature Raman spectrum detection device. And then, further transmitting the data packet of the surface enhanced Raman spectrum to a human-computer interaction terminal operated by a user through a low-power-consumption Bluetooth module or a serial port module.
Step three: data processing and result calculation of surface enhanced Raman spectroscopy of the benzimidazole pesticide residues in the citrus: according to the related Raman spectrum baseline correction and the method of combining variable screening with quantitative prediction and the like, the rapid label-free data processing and prediction process of the Raman spectrum of the benzimidazole pesticide residues in the citrus is constructed, and the final qualitative and quantitative detection of the pesticide residues is realized.
Further, in the step one, the citrus extract is obtained by soaking in an organic solution, centrifuging at a high speed, and extracting and filtering in a solid phase. The SRES reinforced material refers to a reinforced substrate made of gold, silver, copper and other nano particles.
Further, in the first step, the whole SERS detection vessel is made of opaque frosted quartz, and only the reaction chamber is provided with a light-transmitting glass sheet, so that laser emitted by the laser can transmit through the light-transmitting glass sheet. The sample detection box is provided with a clamping groove to ensure that the position of each detection is not changed, and the position error of the detection is avoided. In addition, the built-in temperature control device is used for adjusting the temperature, so that molecular substances in the orange extracting solution are accelerated to be uniformly attached to the SERS reinforcing material, and the surface reinforcing effect of the measured substances can be ensured.
Furthermore, the excitation light wave bands of the laser probe and the laser emitter in the second step are both 785nm, so that Raman spectrum signals of molecules in the measured object can be effectively obtained. The laser probe, the laser transmitter and the Raman photoelectric converter are all micro devices, and can be guaranteed to be integrated in the portable Raman spectrum detection device. In addition, the depth of the sliding groove between the laser probe and the sample detection box in the step two is the length of the laser probe plus one time of the focal length. Thereby ensuring that the measured substance is at the focal length of the laser probe and eliminating the spectral signal error caused by the distance change.
Further, in step threeThe baseline correction method is an adaptive iterative penalty least squares Air-PLS. And substituting the acquired spectral signal vector into an Air-PLS formula (1), setting an initial penalty coefficient w and a roughness coefficient lambda, and iterating for t times until the fitting requirement is met. Wherein Q is a balance function of fidelity and smoothness, x is the collected spectral signal vector, z is the fitting vector, m is the spectral vector length, dtIs formed by xiAnd
Figure BDA0003214954860000031
negative numbers in t iterations. The method for variable screening combined with quantitative prediction in the third step is ACO-PLS, the initial pheromone attenuation coefficient rho, the significance factor Q and the maximum iteration times are set according to the formula (2), and then the root mean square error RMSE, y of different variable combinations is usediFor the actual value of the sample to be measured,
Figure BDA0003214954860000032
and selecting an optimal variable combination for predicting the value, wherein N is the total amount of samples, P is the selected probability of the variable, N is the total amount of the variable, tau is the pheromone of each variable, and F is an objective function. And finally, establishing a PLS multiple linear regression detection model of the citrus benzimidazole pesticide residues, wherein the model calculation method is as shown in a formula (3), wherein X is a spectral variable screened by ACO, a is a variable coefficient, b is an offset, Y is a model detection value, k is the number of screened variables, and i and j are position indexes of traversal data.
Figure BDA0003214954860000041
Figure BDA0003214954860000042
Figure BDA0003214954860000043
The technical scheme of the detection device is as follows:
a rapid detection system for benzimidazole pesticide residues in oranges based on a Surface Enhanced Raman Spectroscopy (SERS) technology is disclosed, wherein a portable Raman spectrum detection device comprises a shell, an LED state indication screen, a human-computer interaction terminal, a switch, a sample detection box and an SERS detection vessel; the detection device is internally provided with a Raman photoelectric converter, a control mainboard, a laser probe, a laser emitter and a rechargeable battery.
The laser probe (7) is connected with the Raman photoelectric converter (5) and the laser emitter (8) through miniature optical fibers. Thereby establishing a complete laser path. The LED state indicating screen (2), the Raman photoelectric converter (5) and the laser emitter (8) are connected to the control main board (6) through flat cables. The switch (4) and the rechargeable battery (9) are connected to the control mainboard (6) in a wire welding mode.
The LED state indicating screen, the switch, the Raman photoelectric converter, the control mainboard, the laser probe, the laser transmitter and the rechargeable battery are fixed in the shell through screws, clamping grooves and other methods, and therefore the portable Raman detector is integrated. The SERS detection vessel, the sample detection box and the integrated portable Raman detector are connected in a physical slot mode. The man-machine interaction terminal is connected with the integrated portable Raman detector through low-power Bluetooth or a serial port.
The length of the shell (1) is not more than 170mm, the width is not more than 90mm, and the height is not more than 65mm, so that the portability of the device can be ensured. A clamping groove slightly larger than the human-computer interaction terminal is formed above the device and used for placing the human-computer interaction terminal. The control mainboard is integrated with FPGA and STM32 chips, and the performance of Raman spectrum data processing and transmission is ensured. The state indicating screen is embedded in the upper surface of the shell and displays the current state of the instrument.
The SERS detection dish is 30mm long, 5mm wide and 50mm high. The top end is respectively provided with an extracting solution sample injection channel and an SERS reinforcing material injection channel, and the diameters of the extracting solution sample injection channel and the SERS reinforcing material injection channel are phi 3 mm. The middle part is provided with a round transparent detection window with the diameter phi of 12 mm. The sample detection box is 50mm long, 30mm wide and 50mm high, a slot of an SERS detection vessel is arranged at the top end, and the depth is 40 mm; the middle part is provided with a laser probe circular groove with the diameter phi of 12.8 mm.
The circular transparent detection window of SERS detection ware and the laser probe groove of sample detection box and the centre of a circle of laser probe all be on same straight line, when laser probe put into laser probe circular slot completely, laser probe is one time's focus with the distance of circular transparent detection window foremost.
Compared with the prior art, the invention has the advantages that:
(1) the SERS detection vessel and the sample detection box provided by the invention can be combined with a portable Raman spectrometer to rapidly acquire the surface enhanced Raman spectrum of the sample, and meanwhile, the focal length of the sample is ensured to be unchanged during each acquisition, and the error caused by the change of the measurement distance is greatly reduced.
(2) The invention inherits the spectrum correction, the pretreatment, the variable screening and the model prediction algorithm into a rapid detection system, and simplifies the steps of collecting, exporting and processing the Raman spectrum data. The device can rapidly obtain the detection result of the benzimidazole pesticide residue in the citrus on site.
Drawings
Fig. 1 is a schematic diagram of the overall assembly of a system for detecting the residual benzimidazole pesticides in citrus based on the surface enhanced raman spectroscopy technology.
Fig. 2 is a schematic diagram of the internal structure of a system for detecting the residual benzimidazole pesticides in citrus based on the surface enhanced raman spectroscopy technology.
FIG. 3 is a schematic diagram of the structure of the SERS detection dish.
FIG. 4 is a schematic view of a sample detection cartridge.
FIG. 5 is a graph of the results of the baseline correction of Air-PLS.
Detailed Description
The rapid detection method for the residual benzimidazole pesticides in the citrus has universality, so that the method only selects the residual probenazole in the citrus to be detected as an implementation example, and the method of the implementation example can be referred to for the detection of other benzimidazole pesticides in the citrus.
Example 1:
in the example, the residual content of thiabendazole in the citrus is detected, and the residual content is overproof according to the national standard GB2763-2019, wherein the content of thiabendazole is more than or equal to 10 mg/kg.
The implementation steps of this example are described in detail below with reference to the accompanying drawings:
(1) preparing a citrus sample:
the citrus was minced using a centrifuge, and 20g of each citrus paste was weighed and dissolved in 100mL of a mixed solution of acetonitrile and water (V/V5/1), and thiabendazole solutions (10,5,1,0.5, 0.1. mu.g/mL) were added to the solution at different concentrations, and finally citrus extract was obtained by high-speed centrifugation, solid-phase extraction and filtration.
(2) Preparation of SERS enhancing material:
gold nanorods (Au NRs) were prepared as a substrate for enhancing the substance using a gold seed growth method, and stored in a refrigerator at 4 ℃.
(3) Acquisition of surface enhanced raman spectra:
the structure of the rapid detection device for pesticide residues in citrus based on the Surface Enhanced Raman Spectroscopy (SERS) technology is shown in figures 1 and 2, and comprises a shell (1), an LED state indication screen (2), a human-computer interaction terminal (3), a switch (4), a sample detection box (14) and an SERS detection vessel (10); the detection device is internally provided with a Raman photoelectric converter (5), a control mainboard (6), a laser probe (7), a laser transmitter (8) and a rechargeable battery (9).
The treated orange extract and the prepared Au NRs are respectively injected into two channels (11, 12) of a SERS detection dish (10). Inserting the SERS detection dish (10) into a clamping groove (15) of the sample detection box. The temperature in the detection box is controlled to be 55 ℃, so that molecules in the citrus are uniformly attached to Au NRs. A laser probe (7) of the device is inserted into a circular slot (16), and the circle centers of the laser probe (7), the circular slot (16) and the circular transparent detection window (13) are all on the same straight line.
The switch (4) is opened to start the device. And operating the human-computer interaction terminal (3) to send a spectrum acquisition command through Bluetooth. The current acquisition state and parameters of the equipment are displayed on the LED state screen (2). One detection cycle includes the steps of turning on the laser, receiving data, turning off the laser, and returning data. And finally, the human-computer interaction terminal (3) obtains the collected surface enhanced Raman spectrum data.
(4) Processing of Raman spectrum data:
the acquired surface enhanced raman spectrum contains background signals and noise, and the data volume is large and complex. The information related to the thiabendazole pesticide can be extracted from the thiabendazole pesticide and the content of the residual can be calculated by processing the thiabendazole pesticide by using a spectral processing method and a model prediction algorithm.
To eliminate the background signal and the influence of overlapping peaks in the raman spectrum, the interference background of the raman spectrum is first subtracted using the Air-PLS baseline correction algorithm, the subtraction effect is shown in fig. 5, and then pre-processed using 1st Der (first derivative algorithm). And establishing a model calculation relation of the processed spectrum information and the physicochemical treatment value by using an ACO-PLS (ant colony-partial least squares) algorithm according to a large number of sample Raman spectra and the thiabendazole physicochemical residual value, and storing the model calculation relation in a detection system. The collected and processed surface enhanced raman spectra were substituted into the established ACO-PLS. Firstly, 18 wave bands are screened out from 600 spectrum wave bands: 482.82nm, 634.78nm, 661.97nm, 747.16nm, 766.35nm, 1004.40nm, 1037.7nm, 1235.00nm, 1426.4nm, 1442.00nm, 1507.30nm, 1539.50nm, 1586.10nm, 1589.70nm, 1615.50nm, 1621.00nm and 1631.90 nm. And substituting the Raman spectrum intensity at the selected wave band into the established multiple linear regression prediction formula (4), and returning the calculation result to an interface of the human-computer interaction terminal.
Y＝－0.07X1+0.07X2+0.22X3+0.28X4－0.04X5－0.08X6+0.01X7－0.07X8+0.08X9－0.07X10+0.12X11+0.07X12+0.12X13+0.07X14－0.03X15+0.32X16+0.25X17+0.06X18+2.54(X1……X18For Raman intensity at the selected band) (4)
By applying the spectrum processing method and the calculation formula and performing spectrum calculation on the collected citrus sample, the detection of the pesticide residue of the probenazole can be realized. The specific results are shown in Table 1-1.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
TABLE 1-1
Figure BDA0003214954860000081
Tables 1-1 show the surface enhanced raman spectroscopy measurements of 3 citrus samples, each sample being subjected to a different probenazole residue.

Claims (9)

1. A method for rapidly detecting benzimidazole pesticide residues in citrus based on a Surface Enhanced Raman Spectroscopy (SERS) technology is characterized by comprising the following steps:
the method comprises the following steps: surface enhancement amplification of Raman signals of the benzimidazole pesticide residues in the citrus: the method comprises the following steps that a SERS detection vessel (10) with two channels is used as a substance reaction and detection place, pretreated orange extracting solution and an SERS reinforcing material are respectively injected into the SERS detection vessel (10) through different channels, the detection vessel is inserted into a clamping groove (15) of a sample detection box (14), and substances in the orange extracting solution are rapidly distributed in the SERS reinforcing material through a certain temperature control function in the sample detection box so as to achieve the effect of surface enhanced Raman;
step two: collecting the benzimidazole pesticide residues in the citrus by using a surface enhanced Raman spectrum: inserting a laser probe (7) of a portable Raman spectrum detection device into a sliding groove (16) of a sample detection box (14), rapidly acquiring the current surface enhanced Raman spectrum data of a detected substance by controlling a laser transmitter (8) and a Raman photoelectric converter (5) of the miniature Raman spectrum detection device, and then transmitting a data packet of the surface enhanced Raman spectrum to a human-computer interaction terminal (3) operated by a user through a low-power-consumption Bluetooth module or a serial port module;
step three: data processing and result calculation of surface enhanced Raman spectroscopy of the benzimidazole pesticide residues in the citrus: according to the related Raman spectrum baseline correction and variable screening combined quantitative prediction method, a rapid label-free data processing and prediction flow of the Raman spectrum of the benzimidazole pesticide residue in the citrus is constructed, and the final qualitative and quantitative detection of the pesticide residue is realized.
2. The method for rapidly detecting the benzimidazole pesticide residues in the citrus based on the surface enhanced Raman spectroscopy SERS technology according to claim 1, wherein in the first step, the citrus extract is obtained by soaking in an organic solution, high-speed centrifugation, solid-phase extraction and filtration, and the SRES enhancing material is an enhancing substrate made of gold, silver, copper and other nanoparticles.
3. The method for rapidly detecting the benzimidazole pesticide residues in the citrus based on the surface enhanced Raman spectroscopy SERS technology according to claim 1, wherein in the first step, the whole SERS detection vessel (10) is made of opaque frosted quartz, only the reaction chamber is provided with a round transparent detection window (13) for transmitting laser emitted by a laser, the sample detection box (14) is provided with a clamping groove (15) for ensuring that the position of each detection does not change, so as to avoid the position error of the detection, and in addition, a built-in temperature control device is used for adjusting the temperature, so that molecular substances in an orange extracting solution are uniformly attached to an SERS enhancing material, and the surface enhancement effect of the detected substances can be ensured.
4. The method for rapidly detecting the benzimidazole pesticide residues in the citrus based on the surface enhanced Raman spectroscopy SERS technology according to claim 1, wherein the excitation light wave bands of the laser probe (7) and the laser emitter (8) in the second step are 785nm, so as to obtain Raman spectrum signals of molecules in the measured object, the laser probe (7), the laser emitter (8) and the Raman photoelectric converter (5) are all micro devices, so as to ensure that the laser probe, the laser emitter (8) and the Raman photoelectric converter are integrated in a portable Raman spectrum detection device, and in addition, the depth of the sliding chute (16) between the laser probe (7) and the sample detection box (14) is the length of the laser probe plus the length of one time of the focal length, so that the measured object is ensured to be at the focal length of the laser probe, and spectrum signal errors caused by distance changes are eliminated.
5. The method for rapidly detecting the benzimidazole pesticide residues in the citrus based on the surface enhanced Raman spectroscopy SERS technology according to claim 1, wherein the baseline correction method in the third step is an adaptive iterative penalty least squares (ARS) Air-PLS. And substituting the acquired spectral signal vector into an Air-PLS formula (1), setting an initial penalty coefficient w and a roughness coefficient lambda, and iterating for t times until the fitting correction requirement is met. Wherein Q is a balance function of fidelity and smoothness, x is the collected spectral signal vector, z is the fitting vector, m is the spectral vector length, dtIs formed by xiAnd
Figure FDA0003214954850000021
negative numbers in t iterations. The method for variable screening combined with quantitative prediction in the third step is ACO-PLS, the initial pheromone attenuation coefficient rho, the significance factor Q and the maximum iteration times are set according to the formula (2), and then the root mean square error RMSE, y of different variable combinations is usediFor the actual value of the sample to be measured,
Figure FDA0003214954850000022
and selecting an optimal variable combination for predicting the value, wherein N is the total amount of samples, P is the selected probability of the variable, N is the total amount of the variable, tau is the pheromone of each variable, and F is an objective function. Finally, a PLS multiple linear regression detection model of the citrus benzimidazole pesticide residues is established, and the model calculation method is as shown in a formula (3), wherein X is a spectral variable screened by ACO, a is a variable coefficient, b is an offset, Y is a model detection value, k is the number of screened variables, and subscripts i and j are position indexes of traversal data;
Figure FDA0003214954850000031
Figure FDA0003214954850000032
Figure FDA0003214954850000033
6. a rapid detection system for benzimidazole pesticide residues in oranges based on a Surface Enhanced Raman Spectroscopy (SERS) technology is characterized by comprising a shell (1), an LED state indicating screen (2), a man-machine interaction terminal (3), a switch (4), a sample detection box (14) and an SERS detection vessel (10); the detection device is internally provided with a Raman photoelectric converter (5), a control mainboard (6), a laser probe (7), a laser transmitter (8) and a rechargeable battery (9);
the laser probe (7) is connected with the Raman photoelectric converter (5) and the laser transmitter (8) through miniature optical fibers, so that a complete laser light path is established, and the LED state indicating screen (2), the Raman photoelectric converter (5) and the laser transmitter (8) are connected to the control mainboard (6) through flat cables; the switch (4) and the rechargeable battery (9) are connected to the control mainboard (6) in a wire welding mode;
the LED state indicating screen (2), the switch (4), the Raman photoelectric converter (5), the control main board (6), the laser probe (7), the laser emitter (8) and the rechargeable battery (9) are all fixed in the shell (1) through screws and clamping grooves, so that the portable Raman detector is integrated; SERS detects ware (10), sample detection box (14) and the portable raman detector who integrates all are connected through physical slot mode, human-computer interaction terminal (3) and the portable raman detector who integrates are through low-power consumption bluetooth or serial ports connection.
7. The system for rapidly detecting the benzimidazole pesticide residues in the citrus based on the surface enhanced Raman spectroscopy SERS technology according to claim 6, wherein the length of the housing (1) is not more than 170mm, the width is not more than 90mm, and the height is not more than 65mm, and a clamping groove larger than the human-computer interaction terminal (3) is formed above the device and used for placing the human-computer interaction terminal (3); the control mainboard (6) is integrated with FPGA and STM32 chip, ensures the performance of Raman spectrum data processing and transmission, and state indication screen (2) is embedded on the upper surface of shell (1), shows the current state of instrument.
8. The system for rapidly detecting the benzimidazole pesticide residues in the citrus based on the surface enhanced Raman spectroscopy SERS technology according to claim 6, wherein the SERS detection dish (10) is 30mm long, 5mm wide and 50mm high, an extract solution injection channel (11) and an SERS enhanced material injection channel (12) are respectively arranged at the top end, the diameters of the SERS detection dish are phi 3mm, and a circular transparent detection window (13) with the diameter of phi 12mm is arranged in the middle; the sample detection box (14) is 50mm long, 30mm wide and 50mm high, a slot of the SERS detection dish (10) is formed at the top end, and the depth is 40 mm; the middle part is provided with a laser probe circular groove with the diameter phi of 12.8 mm.
9. The system for rapidly detecting the benzimidazole pesticide residues in the citrus based on the surface enhanced Raman spectroscopy SERS technology according to claim 8, wherein the circular transparent detection window of the SERS detection dish (10), the laser probe groove of the sample detection box (14) and the circle center of the laser probe (7) are all on the same straight line, and when the laser probe (7) is completely placed in the laser probe circular groove, the distance between the foremost end of the laser probe and the circular transparent detection window is one time of the focal length.
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