CN214668750U - On-spot quick detection device of perfluor carboxylic acid - Google Patents
On-spot quick detection device of perfluor carboxylic acid Download PDFInfo
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- CN214668750U CN214668750U CN202120524066.6U CN202120524066U CN214668750U CN 214668750 U CN214668750 U CN 214668750U CN 202120524066 U CN202120524066 U CN 202120524066U CN 214668750 U CN214668750 U CN 214668750U
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Abstract
The utility model relates to an on-spot short-term test device of perfluorocarboxylic acid, including shielding shell, operating module and circuit module, operating module includes left groove, the mesotrough, right side groove, accuse temperature circulating line and passageway electrode, miniature preliminary treatment pond is equipped with in the left side groove, the dehydration condensation reaction tank is equipped with in the mesotrough, chip capsule has been put in right side groove, accuse temperature circulating line encircles in right side groove outsidely, it keeps electrolyte temperature to heat the accuse temperature through the resistance wire, operating module and circuit module are all installed inside shielding shell, the inside position that corresponds with the chip capsule of shielding shell is provided with a needle, the needle punctures chip capsule when closed shielding shell and makes electrolyte flow. Adopted the utility model discloses a perfluor carboxylic acid on-spot quick detection device fuses nanotechnology and perfluor carboxylic acid detection technique, provides the new approach for perfluor carboxylic acid pollutant's detection, will detect the instrument set in the suit box, easy operation is nimble, easily controls, has reduced the probability of misdetection, has strengthened the adaptability to complicated changeable environment.
Description
Technical Field
The utility model relates to an electrochemistry detects technical field, especially relates to fluorocarboxylic acid compound detection area, specifically indicates a perfluorocarboxylic acid on-the-spot short-term test device.
Background
Perfluoroalkylcarboxylic acids (PFCAs) are a class of Persistent Organic Pollutants (POPs) consisting of a carbon backbone (typically 4-14 a in length) linked to fluorine atoms and a carboxylic acid functional group. The water repellency, oil repellency, heat resistance and surfactant property of the perfluoroalkyl carboxylic acid make the perfluoroalkyl carboxylic acid widely exist in the environment at present and can be accumulated in organisms, so that the perfluoroalkyl carboxylic acid is widely applied to civil and industrial use and has the tolerance to the traditional sewage treatment technology.
In various studies, PFCAs have been found to be toxic to the reproductive, developmental, blood, neurological aspects of organisms. Accordingly, regulations are increasingly promulgated around the world that restrict and prohibit the use of PFCAs. In 2015, perfluorooctanoic acid, its salts and precursors (collectively referred to as PF0A), and its salts were proposed to be incorporated into the stockholm convention. In 2016, canada "ban on regulations on specific hazardous substances" increased the development requirements for PF0A, long-chain perfluorocarboxylic acids and salts thereof and precursors thereof (collectively referred to as LC-PFCAs), and banned the production, use, sale, supply or import of products containing PF0A and LC-PFCAs. In the same year, the national environmental protection agency of the United states has put policy on the concentration of PF0A in drinking water to be less than 0.07. mu.g/L.
In the existing research reports on detection of perfluorocarboxylic acid, most of the reports take a gas chromatography tandem mass spectrometry method or a liquid chromatography tandem mass spectrometry as a way to research the perfluorocarboxylic acid. The research method is traditional, the principle is simple, the precision is low, the detection limit is high, the basic standard deviation is large, the response time is long, the detection capability is limited, the isomeride cannot be detected, and many meaningful detection results cannot be implemented due to high cost. The Teflon pipeline of the liquid chromatography-tandem mass spectrometry method is a precursor containing perfluorooctanoic acid, namely perfluoropoly (telomeric alcohol) (8: FT07), and can cause pipeline pollution and cause over-detection.
The Nanopore analysis (Nanopore SMS) studied so far can reach an analytical range of 0.1pM, which is not reached by the mass spectrometry (LS-MS/MS) on the market, which has an analytical range of only 10 pM. Our linear range can also reach an order of magnitude of 106Order of magnitude higher than 10 for LS-MS4An order of magnitude. Nanopore analysis can yield accurate data in less than 10 minutes over reaction time, whereas mass spectrometry can only yield data between 30 and 60 minutes. In terms of cost, nanopore devices require only 20,000 dollars, while mass spectrometers require a capital equipment cost of greater than 1,000,000 dollars. These data are still continuously perfected and will reach a higher level in the future.
SUMMERY OF THE UTILITY MODEL
The utility model aims at overcoming the shortcomings of the prior art and providing a perfluor carboxylic acid on-site rapid detection device which has the advantages of good portability, good flexibility and high accuracy.
In order to achieve the above purpose, the utility model discloses a perfluor carboxylic acid on-site rapid detection device is as follows:
the on-site rapid detection device for the perfluorocarboxylic acid is mainly characterized by comprising a shielding shell, an operation module and a circuit module, wherein the operation module comprises a left groove, a middle groove, a right groove, a temperature control circulating pipeline and a channel electrode, the left groove is provided with a micro pretreatment pool, the middle groove is provided with a dehydration condensation reaction groove, the right groove is provided with a chip capsule, the temperature control circulating pipeline surrounds the outside of the right groove, the temperature of electrolyte is kept by heating and controlling the temperature through a resistance wire, the operation module and the circuit module are both arranged inside the shielding shell, a needle is arranged in the shielding shell at a position corresponding to the chip capsule, and the needle punctures the chip capsule when the shielding shell is closed so as to enable the electrolyte to flow out; the circuit module is respectively connected with the channel electrode and the temperature control circulating pipeline.
Preferably, miniature preliminary treatment pond by protection film, filter screen, solid phase filler, go up the sieve, sieve and trompil are constituteed down, protection film cover miniature preliminary treatment pond top, the filter screen locate miniature preliminary treatment pond's inside top, suspended particles such as silt and other solid impurity in the filtration await measuring sample, solid phase filler be located the sieve and down between the sieve, miniature preliminary treatment pond's right side be equipped with the trompil, and be located solid phase filler and down between the sieve, the below space of lower sieve store the waste liquid.
Preferably, the polypeptide probe reagent and the electrolyte are added into the middle tank, a conductivity meter electrode is arranged at the bottom of the middle tank and connected with the circuit module, the polypeptide probe reagent and the object to be detected are subjected to dehydration condensation, and the electrolyte is diluted.
Preferably, the chip capsule placed in the right groove consists of a protein nanopore chip and a capsule, wherein 4 protein nanopores are uniformly integrated on the protein nanopore chip, and the capsule contains electrolyte.
Preferably, the circuit module comprises an upper half circuit structure and a lower half circuit structure, the upper half circuit structure consists of two identical inverting operational amplifiers, an in-phase operational amplifier and a first power supply, the two identical inverting operational amplifiers are sequentially connected with a current input end, the in-phase operational amplifier is connected with a current output end, and the first power supply is connected with the electrode of the conductivity meter, the resistance wire of the temperature control circulating pipeline and the channel electrode in parallel and supplies current;
the lower half circuit structure comprises catholyte equivalent resistance, nanopore equivalent resistance, anolyte equivalent resistance, a plurality of resistances, resistance box and second power supply, catholyte equivalent resistance, nanopore equivalent resistance and anolyte equivalent resistance establish ties in proper order, catholyte equivalent resistance's one end be connected with in-phase operational amplifier's normal phase input, anolyte equivalent resistance one end be connected with reverse phase operational amplifier's output, resistance box and second power supply establish ties to establish ties at nanopore equivalent resistance's both ends through the resistance.
Preferably, the device further comprises a matched data processing module, which is connected with the protein nanopore chip in the chip capsule and detects and screens 4 pore channel signals on the protein nanopore chip.
Preferably, the shielding shell is provided with a window, and the real-time temperature and solution concentration readings of the internal display screen can be observed through the window.
Preferably, the shielding shell, the circuit module, the micro pretreatment tank, the dehydration condensation reaction tank and the chip capsule can be disassembled and assembled.
By adopting the utility model discloses a perfluor carboxylic acid on-spot quick detection device, nanopore analytical method can reach 0.1 pM's analysis scope, and linear range can reach 106And the accuracy is higher. Nanopore assays can yield accurate data in less than 10 minutes in reaction time, and nanopore devices require only 20,000 dollars, which is less expensive in time and cost. The utility model discloses fuse nanotechnology and perfluorocarboxylic acid detection technique, replace the mass spectrometry of traditional high consumption, low efficiency, high cost, low precision, provide the new method for the detection of perfluorocarboxylic acid pollutant. The utility model discloses to detect the instrument set in the suit box, easy operation is nimble, easily controls, has reduced the probability of misdetection, has strengthened the adaptability to complicated changeable environment, can apply to the field conveniently. The utility model utilizes the integration and development of the science and technology fields of nano materials, electricity, computers and the like to detect the single molecule in the water through the nanotechnology; the nanopore technology can directly display a single-molecule signal, can realize direct and high-sensitivity real-time online analysis, and constructs a complete and available perfluorocarboxylic acid pollutant detector and method.
Drawings
FIG. 1 is a drawing of a structure of a field perfluorocarboxylic acid detecting set of the on-site rapid perfluorocarboxylic acid detecting apparatus of the present invention.
Fig. 2 is a schematic diagram of the detection data transmission of the on-site rapid detection device for perfluorocarboxylic acid of the present invention.
Fig. 3 is a schematic structural diagram of the on-site rapid detection device for perfluorocarboxylic acid of the present invention.
FIG. 4 is a structural diagram of a micro pretreatment tank of an operation module of the rapid field perfluorocarboxylic acid detecting apparatus of the present invention.
Fig. 5 is a circuit structure diagram of the on-site rapid detection device for perfluorocarboxylic acid of the present invention.
FIG. 6 is a schematic view of the dehydration condensation reaction between the object to be detected and the probe of the device for rapidly detecting perfluorocarboxylic acid in situ of the present invention.
Fig. 7 is a diagram of detection signals of an example of the on-site rapid detection device for perfluorocarboxylic acid of the present invention.
Reference numerals:
101 liquid-transfering gun
102 pipette box
103 polypeptide probe reagent
104 electrolyte
105 micro pretreatment pool
106 chip capsule
107 centrifugal tube box
108 perfluorocarboxylic acid detector
109 connecting line
110 computer
201 matched data processing module
202 USB data line
203 assembled perfluorocarboxylic acid detector
204 button
205 view window
301 left groove
302 solution channel
303 middle groove
304 conductivity meter electrode
305 valve button
306 temperature control circulating pipeline
307 protein nanopore chip
308 display screen
309 channel electrode
401 filter screen
402 upper sieve plate
403 solid phase packing
404 lower sieve plate
405 opening a hole
Detailed Description
In order to more clearly describe the technical content of the present invention, the following further description is given with reference to specific embodiments.
In the technical solution of the present invention, the main protection of the device for rapidly detecting perfluorocarboxylic acid on site is the hardware structure and connection relationship thereof supporting the whole hardware function platform for realizing the corresponding function, and each of the functional modules and module units included therein can correspond to the specific hardware circuit in the actually known hardware device or integrated circuit structure, so that only the improvement of the specific hardware topology connection structure and the specific hardware circuit is involved, the improvement of the hardware part exists, and does not depend on the computer control software, and does not belong to the carrier for executing only the control software or the computer program, therefore, the application of any control software or computer program is not involved for solving the corresponding technical problem and obtaining the corresponding technical effect, that is, the present invention can solve the problem to be solved only by the improvement of the actually known hardware device or hardware circuit structure involved in these modules and units And achieve the corresponding technical result without the assistance of specific control software or computer programs to implement the corresponding functions.
The utility model discloses a this on-spot quick detection device of perfluorocarboxylic acid, including shielding shell, operating module and circuit module, operating module include left groove 301, well groove 303, right groove, accuse temperature circulating line 306 and passageway electrode 309, left groove 301 be equipped with miniature preliminary treatment pond 105, well groove 303 be equipped with the dehydration condensation reaction tank, right groove put chip capsule 106, accuse temperature circulating line 306 encircle right groove outside, control the temperature through resistance wire heating and control the temperature and keep the electrolyte temperature, operating module and circuit module all install inside the shielding shell, the inside position that corresponds with chip capsule 106 of shielding shell be provided with a needle, the needle puncture chip capsule 106 when closed shielding shell and make electrolyte flow out; the circuit modules are respectively connected with a channel electrode 309 and a temperature control circulating pipeline 306.
As the preferred embodiment of the present invention, the micro-pretreatment tank 105 comprises a protective film, a filter screen 401, a solid filler 403, an upper screen 402, a lower screen 404 and an opening 405, the protective film covers the top of the micro-pretreatment tank 105, the filter screen 401 is disposed above the interior of the micro-pretreatment tank 105, and filters suspended particles such as silt and other solid impurities in the sample to be tested, the solid filler 403 is disposed between the upper screen 402 and the lower screen 404, the right side of the micro-pretreatment tank 105 is disposed with the opening 405, and is disposed between the solid filler 403 and the lower screen 404, and the space below the lower screen 404 stores waste liquid.
As the preferred embodiment of the utility model, the middle groove 303 add polypeptide probe reagent and electrolyte, the bottom of middle groove 303 put conductivity meter electrode 304, conductivity meter electrode 304 link to each other with the circuit module, polypeptide probe reagent and determinand dehydration condensation, electrolyte dilute.
As the preferred embodiment of the present invention, the chip capsule 106 placed in the right groove is composed of a protein nanopore chip 307 and a capsule, the protein nanopore chip 307 is uniformly integrated with 4 protein nanopores, and the capsule contains electrolyte.
As a preferred embodiment of the present invention, the circuit module includes an upper half circuit structure and a lower half circuit structure, the upper half circuit structure is composed of two identical inverting operational amplifiers, an in-phase operational amplifier and a first power supply, the two identical inverting operational amplifiers are sequentially connected to the current input end, the in-phase operational amplifier is connected to the current output end, and the first power supply and the conductance meter electrode 304, the resistance wire of the temperature control circulation pipeline 306 and the channel electrode 309 are all connected in parallel and provide current;
the lower half circuit structure comprises catholyte equivalent resistance, nanopore equivalent resistance, anolyte equivalent resistance, a plurality of resistances, resistance box and second power supply, catholyte equivalent resistance, nanopore equivalent resistance and anolyte equivalent resistance establish ties in proper order, catholyte equivalent resistance's one end be connected with in-phase operational amplifier's normal phase input, anolyte equivalent resistance one end be connected with reverse phase operational amplifier's output, resistance box and second power supply establish ties to establish ties at nanopore equivalent resistance's both ends through the resistance.
As a preferred embodiment of the present invention, the device further comprises a data processing module 201 connected to the protein nanopore chip 307 in the chip capsule 106 for detecting 4 pore channel signals on the screening protein nanopore chip 307.
As a preferred embodiment of the present invention, the shielding housing is provided with a window 205, and the window 205 can be used to observe the real-time temperature and solution concentration indication of the internal display screen 308.
As the preferred embodiment of the present invention, the shielding case, the circuit module, the micro pre-treatment tank 105, the dehydration condensation reaction tank and the chip capsule 106 can be disassembled and assembled.
The utility model discloses an among the embodiment, on the basis of nanopore monomolecular detection technique, provide a perfluorocarboxylic acid on-spot short-term test instrument, thereby detect perfluoralkyl carboxylic acid pollutant and reach and improve the accuracy, reduce and detect purposes such as limit, reduce cost. The method has the function of analyzing the high-precision content of the perfluorocarboxylic acid by collecting samples (such as water samples of water sources) and simply pretreating, can reduce the detection limit of the perfluorocarboxylic acid, and provides a convenient and relatively economic perfluorocarboxylic acid detection method.
The perfluorocarboxylic acid detector consists of a shielding shell, an operation module and a circuit module.
The shielding shell is made of metal and mainly plays a role in shielding electromagnetic interference and mechanical vibration so as to stabilize detection signals inside the instrument. In order to prevent the electrolyte from volatilizing, the shell cover needs to be closed in the process of waiting for the chip to acquire signals.
A window 205 is arranged on the shielding shell, and an inspector can observe the readings on the display screen 308 through the window to obtain the real-time temperature and the solution concentration, so as to prevent the temperature abnormality from generating errors to the experiment (the experiment temperature is set to be (20 +/-0.2) DEG C).
A needle is arranged at the position, corresponding to the chip capsule, in the shielding shell cover and used for closing the shielding shell and simultaneously puncturing the chip capsule to enable electrolyte to flow out and uniformly mixing with a solution containing a structural substance to be detected.
The operation module is provided with a left tank, a middle tank and a right tank and a temperature control circulating pipeline 306, and the left tank 301 is used for installing a disposable micro pretreatment tank. The micro pretreatment tank is composed of a protective film, a filter screen 401, solid phase filler 403, an upper sieve plate 402, a lower sieve plate 404 and an opening 405. The protective film covers the top of the micro pretreatment tank; the filter screen is used for filtering suspended particles such as silt and other solid impurities in the sample to be detected; the solid-phase filler is positioned between the upper sieve plate and the lower sieve plate; the lower space of the lower sieve plate is used for storing waste liquid; the opening is arranged at the right side of the micro pretreatment tank. The solution to be measured after being not pretreated flows through the filter screen after being added into the micro pretreatment tank, and the solution to be measured after impurities and waste liquid are filtered is remained between the upper sieve plate and the lower sieve plate and flows out of the sieve plates.
The middle tank is used for adding the probe and the electrolyte. The probe and the pollutant molecules are dehydrated and condensed to form a probe-pollutant molecule structure to be detected, and the conductivity meter electrode 304 is arranged at the bottom of the middle tank.
The right slot is used for mounting the chip capsule. The chip capsule consists of a chip containing 4 protein nanopores and a capsule. The capsule contains 4M KCl electrolyte; 4 protein nanopores are uniformly arranged on the chip, and the diameter of each protein nanopore is 1 nm; the needle punctures the chip capsule after closing the shielding shell so as to lead the electrolyte to flow out and mix. The protein nanopores are integrated on the chip and are positioned at the cis side of the nanopores before the object to be detected passes through the nanopores. The circuit module provides-50 mV voltage, so that charged pollutant molecules pass through the protein nanopores to generate via electric signals, and the signals are transmitted to the notebook computer through the USB data lines.
The temperature control circulating pipeline surrounds the outside of the right tank to maintain the temperature of the electrolyte.
The left groove 301 is used for installing the disposable micro pretreatment tank 105, the middle groove 303 is sequentially added with the probe 103 and the electrolyte 104, the probe 103 and the object to be tested are subjected to dehydration condensation reaction, the electrolyte 104 is diluted to 0.2mM, and the right groove is used for installing the chip capsule 106 for experiment. The temperature control circulation pipeline 306 is heated by resistance wires to control the temperature so as to maintain the temperature of the solution at about 20 ℃.
The circuit module is shown in fig. 5, and the total power supply of the circuit module is continuously provided by the notebook computer connected with the USB connecting line. The circuit module is divided into an upper half circuit and a lower half circuit.
The upper half part of the circuit respectively provides current for the electrode detection electrolyte concentration of the conductivity meter, the resistance wire of the temperature control water circulation system and the channel electrode. The current input end is provided with two same inverting operational amplifiers to meet different requirements of channel electrode current and voltage and ensure the same current direction; the output end is provided with a non-inverting operational amplifier to ensure that the voltage and the current change to the original value by changing R1And R2And the resistance value is adjusted by the required magnification or reduction times.
The lower half part of the circuit consists of a catholyte equivalent resistance, a nanopore equivalent resistance, an anolyte equivalent resistance and a plurality of resistors R10－R12A resistance box and a power supply. The method is characterized in that the lower half part of the circuit applies a noise reduction module to suppress background ion current.
The matched data processing module is arranged in a notebook computer, automatically screens 4 pore channel signals on the protein nanopore chip to obtain high-quality characteristic signals, and compares the high-quality characteristic signals with data in a library to obtain the content of pollutants in a sample to be detected. The water samples included: river and lake water samples, water samples of water source places, water samples of reservoirs and the like.
The upper half part of the circuit is aligned with a middle tank 303, a right tank and a temperature-controlled water circulation system 306. The power supply of the main circuit is continuously provided by the notebook computer connected with the USB connecting line.
For the middle tank 303, the circuit supplies current to the middle tank, so that the accurate dynamic identification of the concentration of the solution in the electrode tank is ensured, and the error is reduced.
For the temperature-controlled water circulation system 306, the circuit supplies current to the temperature-controlled water circulation system, so that the heating wire can be heated normally.
For the right slot, because the requirements on current and voltage are different, the current provided by a computer is larger than the current required by a chip, and can generate larger influence on the experiment, two input ends are arrangedA same inverting operational amplifier (the inverting operational amplifier satisfies the relation Vout/Vin ═ R)2/R1) The current and voltage are reduced, and the current direction is ensured to be unchanged.
In order to ensure that the output current can be identified by a computer, a non-inverting operational amplifier is arranged at the output end (the non-inverting operational amplifier satisfies the relation that Vout/Vin is 1+ R1/R2) The voltage and the current are changed back to the original values, and the circuit is ensured to be stable; by varying R1And R2The particular numerical values are selected to achieve the desired magnification or reduction. Therefore, the voltage and the current are simply controlled, the electric energy is saved, and the space is saved.
The lower half part of the circuit consists of a catholyte equivalent resistance, a nanopore equivalent resistance, an anolyte equivalent resistance and a plurality of resistors R10－R12A resistance box and a power supply. The lower half part of the circuit applies a noise reduction module, so that the detection limit is reduced, and higher sensitivity is realized; the background ion current is suppressed; the noise reduction module technology is adopted, so that a tiny current signal is optimized, the influence of background noise is reduced, and the signal-to-noise ratio is greatly improved.
The water sample to be detected flows into the micro pretreatment tank 105 for extraction and purification, flows into the solution channel 302, enters the middle tank 303, forms a probe-pollutant molecule structure to be detected after dehydration condensation reaction with the probe, the structure to be detected passes through the nanopore under the action of an external electric field of the protein nanopore chip 307 in the right tank to generate a hole passing signal, the content of perfluorocarboxylic acid is obtained through matched software, and the perfluorocarboxylic acid content is displayed on the notebook computer 110. When the user uses the instrument, the instrument is connected with a notebook computer through a USB interface 109, a micro pretreatment pool is arranged in the left groove 301, and a protein nanopore chip is arranged in the right groove. The water sample to be detected is added into the micro pretreatment tank, and after the water sample is subjected to pretreatment extraction, the sample flows into the middle tank through the solution channel 302. The user adds the probe into the middle tank 303, and after calculating according to the solution concentration data on the right display screen 308, the electrolyte is accurately dropped to dilute the probe to 0.02mM, and then the valve button 305 is pressed to open the valve, so that the solution with the concentration flows into the protein nanopore chip. Closing the shielding shell of the detector, and puncturing the capsule to make the electrolyte flow into the right groove. After the full mixing, the electric signal is transmitted to a notebook computer through a USB data line, and the detection conditions of 4 pore channels on the chip are automatically analyzed by matching software, and the content of the perfluorocarboxylic acid in the water sample is displayed.
In a specific embodiment, the apparatus is connected to a notebook computer via a USB interface, the left groove 301 is a card groove of the micro pre-treatment tank 105, and the right groove is a card groove of the protein nanopore chip 307. After the assembly is finished, a water sample to be detected is added into the micro pretreatment tank, and the water sample to be detected flows into the middle tank 303 through the solution channel 302 after being pretreated and extracted.
After the extracted water sample to be detected flows into the middle tank 303, a probe is added, according to the solution concentration data on the right display screen 308, electrolyte is accurately dripped to dilute the probe to 0.02mM, and then the valve is opened by using the valve button 305, so that the solution with the concentration flows into the protein nanopore chip 307. The perfluorocarbon acid detector lid should be closed at this time (the top of the lid is aligned with the protein nanopore chip 307, which punctures the capsule when closed) and the electrolyte flows into the right well.
After the solutions are fully mixed, the electric signal is transmitted to the notebook computer 110 through the USB data line 109 under the transmission of the channel electrode (gold finger) 309, and the detection conditions of 4 nanopores on the chip are automatically analyzed by the matching software and compared with the data in the library, so as to obtain the content of the perfluorocarboxylic acid in the water sample.
Wherein, the volume of the micro pretreatment tank is 1.5cm multiplied by 1.5cm, and the micro pretreatment tank has the functions of absorbing and filtering a water sample to be detected and treating waste liquid. The filter screen 401 will filter suspended particles such as silt and other solid impurities in the liquid sample, and the filtrate flows between the two sieve plates 401 and 402 for solid phase extraction. The small size of the device has the advantages of easy carrying, easy installation, easy replacement and the like.
Further, the micro pre-treatment tank 105 and the protein nanopore chip 307 should be loaded into the left tank 301 and the right tank, respectively, before adding the sample, and the probe and the electrolyte should be manually added through the pipette gun 101, so as to increase the flexibility of operation.
The probe and the pollutant molecules are subjected to dehydration condensation to form a probe-pollutant molecule structure to be tested, and a current signal of the probe-pollutant molecule structure is easy to capture when passing through the hole, so that the risks of missing test and wrong test are reduced; in addition, due to the fact that the size of the object to be detected is increased, the staying time of the object in the hole is increased, signals are easy to detect, and the capture rate is improved.
In addition, the cover of the perfluorocarboxylic acid detector should be closed immediately after the liquid in the right groove flows into the chip groove stably, so that the volatilization of the electrolyte is reduced as much as possible.
Furthermore, before the sample is added, the protective filter 401 on the micro pretreatment tank needs to be uncovered, and the existence of the filter 401 protects the pretreatment tank from being infected, so that the quality guarantee time of the micro pretreatment tank is prolonged.
After the sample is added, the interfering material flows through the lower frit 404, is deposited below the lower frit 404, and the target is adsorbed in the solid phase filler 403. The target is rinsed with eluent and allowed to flow into the middle tank 303 through the opening 405.
The chip capsule is composed of a chip containing 4 protein nanopores and a capsule above the chip. The capsule contains 4M KCl electrolyte. The combination greatly avoids the concentration nonuniformity caused by the volatilization of the electrolyte, further prevents the concentration misdetection of pollutant molecules as far as possible, reduces the waste of space and simplifies the operation.
Preferably, 4 protein nanopores are uniformly arranged on the chip, and the diameter of each nanopore is 1 nm. And the electrolyte is mixed with the diluted solution containing the target after the capsule is punctured by the needle, and is positioned at the cis side of the nano-pores before the object to be detected passes through the pores. The circuit module provides-50 mV voltage for the electrolyte entering the middle tank 303, so that the charged target object passes through the nanopore, and the electrical signal of the via hole is transmitted to the computer.
During data processing, the matched software screens the signals of all the holes on the chip respectively, analyzes high-quality signals and detects the content of the perfluorocarboxylic acid through identification and classification.
The utility model discloses a full perfluor carboxylic acid on-spot short-term test instrument contains all instruments and notebook computer pack into in the open-air perfluor carboxylic acid detection suit box of customization. As shown in figure 1, the main tool of the utility model is a field perfluorocarboxylic acid detection kit, which has an upper layer and a lower layer. The instrument and its auxiliary tools include: two pipette tips 101, a pipette tip 102, six centrifuge tubes 107, three chip capsules 106, three micro pretreatment tanks 105, a bottle of polypeptide probe reagent 103, a bottle of 4MKCl electrolyte 104, a USB data line 109 and a perfluorocarboxylic acid detector 108.
The upper layer is provided with a perfluorocarboxylic acid detection related instrument which comprises 2 pipette guns 101, 1 pipette head 102, 6 centrifuge tubes 107, 3 chip capsules 106, 3 micro pretreatment tanks 105, 1 bottle of polypeptide probe reagent 103 and 1 bottle of 4M KCl electrolyte 104.
The lower layer is provided with a perfluorocarboxylic acid detector 108, a notebook computer 110 and a USB data line 109. The left side of the detector is provided with a USB connector for connecting a notebook computer to record and process experimental data.
The following is a specific embodiment of the present invention.
Example (b): c in water sample of Huangpu river6F11And (5) detecting COOH.
Referring to FIG. 3, the left tank 301 of the micro pre-treatment tank has a volume of about 1.5cm × 1.5cm × 1.5cm, is small, portable and fully functional, and is a key component in the process of detecting perfluorocarboxylic acid.
According to FIG. 4, this micro pre-treatment tank consists of: the device comprises a filter screen 401, an upper sieve plate 402, a solid filler 403, a lower sieve plate 404 and a collecting pipeline 405, wherein the collecting pipeline 405 is connected with a solution channel 302, the solution channel 302 is connected with a middle tank 303, and the middle tank 303 is a dehydration condensation reaction tank.
Before the micro pretreatment tank is used, a film covering the micro pretreatment tank is uncovered, then a liquid sample of Huangpu river water is added into the micro pretreatment tank, standing is carried out for a plurality of minutes, when the liquid sample completely flows through a filter screen 401, and the filter screen 401 is used for filtering suspended particles such as silt and other solid impurities in the liquid sample.
Then the liquid sample flows between the two sieve plates 401 and 402 to be extracted in a solid phase, the liquid sample required by the experiment is adsorbed on the solid phase packing 403 (the surface of the high-purity silica gel is bonded with aminopropyl NAX1), and the interference in the liquid flows to the lowest layer.
At this time, an appropriate amount of eluent (0.5mL of 0.5% ammonia-methanol solution) is added into the left tank 301 of the micro pretreatment tank, so that the extracted liquid sample flows into the solution channel 302 from the collection pipe 405 and further flows into the middle tank 303, and the perfluorocarboxylic acid compound (i.e., C) in the sample is completely treated6F11COOH) was extracted.
This process ensures that the valve to the right of the middle tank 303 is closed and liquid will not flow into the right tank.
The liquid-transferring gun 101 is used, the probe 103 is added into the middle tank 303, and is subjected to dehydration condensation with the object to be detected to form a probe-pollutant molecule structure to be detected, so that the object to be detected is electrified, the object to be detected is subjected to the action of an electric field at an orifice and is easily captured, and the capture rate is greatly increased; in addition, the dehydration condensation reaction can make the volume of the object to be detected become bigger, thereby the retention time of the object to be detected in the hole is increased, and the signal is easier to be detected.
Taking FIG. 6 as an example, the polypeptide probe R7A and a perfluorinated compound C6F11Compound C is generated after the COOH is dehydrated and condensed6F11COR7A。
After the reaction is sufficiently performed, the concentration displayed on the display screen 308 of the detector is about 0.2mM and the value is kept stable after the 4M KCl electrolyte 104 is added for dilution.
At the right slot, a chip capsule 307 is inserted, the capsule comprising two parts: chip part (there are four protein nanopore that the aperture is 1nm in the chip) and 4M KCl electrolyte part, and the space has the minor segment distance between two parts, punctures the capsule when the needle, and electrolyte 104 flows to the chip on, and the capsule film on upper strata can not touch electrolyte 104 yet, prevents to produce the influence to the experiment.
After the electrolyte 104 soaks the chip, the button 305 is pressed to open the valve, and the liquid flows into the right groove of the detector. The nano protein holes in the 3 chip capsules 106 in the field perfluorocarboxylic acid detection kit are different, and partial protein is mutated to improve the resolution of perfluorocarboxylic acid and reduce the detection limit by transforming the nano protein holes.
A temperature-controlled water circulation system 306 is laid around the right slot chip capsule 307 (the circuit principle of the temperature-controlled water circulation system 306 will be explained in the following circuit module part), and after the resistance wires are heated and controlled for a period of time, the temperature on the display screen 308 is (20 +/-0.2) ° c.
The data processing step is explained below.
As shown in fig. 2, in the data processing link, after the assembled perfluorocarboxylic acid detector 203 completely uploads experimental data to the notebook computer through the USB data line 202, the supporting software 201 automatically filters the electrical signals, searches for appropriate via hole signals, and performs classification and screening on each hole.
Firstly, obtaining screened primary processing data by making a uniform scatter diagram of the amplitude A and the standard deviation S of a required signal.
And secondly, classifying different via hole signal events by Python script codes in the software, analyzing information, searching for a good hollow hole signal as a standard signal, and further screening by using A and S of the standard signal as standards to obtain secondary processing data.
Thirdly, statistically fitting the secondary processing data through a built-in program to obtain a unimodal statistical chart and related data, and finally comparing the unimodal statistical chart with the data in the library to obtain the perfluorocarboxylic acid compound (C)6F11COOH) content.
The data processing mode can discard some signals with larger deviation, thereby improving the resolution of the signals. In addition, most data processing procedures are completed through automatic operation of Python and other built-in programs, the required manual operation is less, accidental manual operation errors can be reduced, and the method is more rapid, convenient and accurate.
The utility model discloses an operating procedure as follows:
a certain amount of liquid sample of a water source area is injected into a left groove 301, the liquid sample is filtered and extracted by a micro pretreatment tank, the liquid sample without interferents flows into a middle groove 303, a polypeptide probe reagent 103 is added for dehydration condensation reaction, the liquid sample is diluted to 0.2mM by 4M KCl electrolyte 104, a chip capsule 307 is inserted into a right groove, a needle is used for puncturing the part of the capsule, after the electrolyte 104 soaks the chip, a valve button 305 is pressed to open a valve, the liquid flows into a right groove of a detector, the resolution of the perfluorocarboxylic acid is improved and the detection limit is reduced by modifying nano protein holes in 3 chip capsules 106 in a field perfluorocarboxylic acid detection kit, and meanwhile, a temperature control water circulation system 306 is laid around the chip capsule 307 of the right groove to control the experiment temperature to be about 20 ℃ and then the experiment data is recorded.
After experimental data are completely uploaded to a notebook computer, the matched software 201 classifies and screens, a uniform scatter diagram is made according to required signals to obtain primary processing data, good hole signals are searched by Python script codes to serve as standard signals, further screening is carried out to obtain secondary processing data, finally, the secondary processing data are subjected to statistical fitting by built-in codes to obtain a single-peak statistical diagram and related data, and the single-peak statistical diagram and the related data are compared with data in a library to obtain the content of the perfluorocarboxylic acid.
The utility model has the characteristics of as follows:
1. the perfluorocarboxylic acid detector comprises a metal shielding shell, a micro pretreatment tank, a protein nanopore detection chip integrated with a protein nanopore and an electrolyte, a protein nanopore detection circuit and a temperature control device.
2. The detector adopts a detection method based on protein nanopores to detect the accurate content of perfluorocarboxylic acid pollutants. Compared with the traditional mass spectrometry, the detection method greatly improves the resolution efficiency of the perfluorocarboxylic acid and reduces the detection limit while ensuring the accurate identification and statistics of the quantity of the perfluorocarboxylic acid.
3. The resolution of the perfluorocarboxylic acid can be further improved by modifying the protein nanopore (mutating partial protein).
4. The micro pretreatment tank integrates the filtering step and the solid-phase extraction step, and a solid-phase extraction column is not needed, so that the micro pretreatment tank is more convenient and simpler.
5. The noise reduction module optimizes a tiny current signal, reduces the influence of background noise and greatly improves the signal-to-noise ratio.
6. The length of the substance to be detected is increased by combining the substance to be detected with the probe, so that the residence time of the substance to be detected in the hole is prolonged, and the capture rate is improved.
7. The power supply is provided by the notebook computer, and the operational amplifier is used for combining the protein nanopore detection circuit with circuits required by other devices, so that the design of the device is simpler and clearer.
8. The data processing method taking the automatic operation of the built-in program as the main part and the manual operation as the auxiliary part can reduce accidental manual operation errors, and is more rapid, convenient and accurate.
9. The instrument adopts multi-pore channel detection, is mutually independent, reduces the probability of sample pollution and shortens the detection time of perfluorocarboxylic acid pollutants.
10. The instrument can be made into a portable version and is suitable for different occasions.
Each part of the instrument is flexible to assemble, can be made into a portable version, is suitable for different occasions, and improves the flexibility. The utility model discloses utilize the integration and the development in the scientific and technological field of nano-material, electricity, computer, have huge development potential and practical value in the aspect of water resource environmental monitoring.
By adopting the utility model discloses a perfluor carboxylic acid on-spot quick detection device, nanopore analytical method can reach 0.1 pM's analysis scope, and linear range can reach 106And the accuracy is higher. Nanopore assays can yield accurate data in less than 10 minutes in reaction time, and nanopore devices require only 20,000 dollars, which is less expensive in time and cost. The utility model discloses fuse nanotechnology and perfluorocarboxylic acid detection technique, replace the mass spectrometry of traditional high consumption, low efficiency, high cost, low precision, provide the new method for the detection of perfluorocarboxylic acid pollutant. The utility model discloses to detect the instrument set in the suit box, easy operation is nimble, easily controls, has reduced the probability of misdetection, has strengthened the adaptability to complicated changeable environment, can apply to the field conveniently. The utility model utilizes the integration and development of the science and technology fields of nano materials, electricity, computers and the like to detect the single molecule in the water through the nanotechnology; the nanopore technology can directly display a single-molecule signal, can realize direct and high-sensitivity real-time online analysis, and constructs complete and available perfluorocarboxylic acidAcid contaminant detector and method.
In this specification, the invention has been described with reference to specific embodiments thereof. It will, however, be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention. The specification and drawings are, accordingly, to be regarded in an illustrative rather than a restrictive sense.
Claims (8)
1. The on-site rapid detection device for the perfluorocarboxylic acid is characterized by comprising a shielding shell, an operation module and a circuit module, the operation module comprises a left groove (301), a middle groove (303), a right groove, a temperature control circulating pipeline (306) and a channel electrode (309), the left groove (301) is provided with a micro pretreatment tank (105), the middle groove (303) is provided with a dehydration condensation reaction tank, the right groove is provided with a chip capsule (106), the temperature control circulating pipeline (306) surrounds the outside of the right groove, the temperature of the electrolyte is kept by heating and controlling the temperature through a resistance wire, the operation module and the circuit module are both arranged in the shielding shell, a needle is arranged at the position corresponding to the chip capsule (106) in the shielding shell, the needle punctures the chip capsule (106) when closing the shielding shell so as to lead the electrolyte to flow out; the circuit module is respectively connected with the channel electrode (309) and the temperature control circulating pipeline (306).
2. The on-site rapid detection device for perfluorocarboxylic acid as claimed in claim 1, wherein the micro pretreatment tank (105) comprises a protective film, a filter screen (401), solid phase filler (403), an upper sieve plate (402), a lower sieve plate (404) and an opening (405), the protective film covers the top of the micro pretreatment tank (105), the filter screen (401) is arranged above the inside of the micro pretreatment tank (105) to filter silt in a sample to be detected, the solid phase filler (403) is arranged between the upper sieve plate (402) and the lower sieve plate (404), the opening (405) is arranged on the right side of the micro pretreatment tank (105) and is arranged between the solid phase filler (403) and the lower sieve plate (404), and the space below the lower sieve plate (404) is used for storing waste liquid.
3. The on-site rapid detection device for perfluorocarboxylic acid as claimed in claim 1, wherein the middle tank (303) is filled with a polypeptide probe reagent and an electrolyte, the bottom of the middle tank (303) is provided with a conductivity meter electrode (304), the conductivity meter electrode (304) is connected with a circuit module, the polypeptide probe reagent is subjected to dehydration condensation with an object to be detected, and the electrolyte is diluted.
4. The on-site rapid detection device for perfluorocarboxylic acid as claimed in claim 1, wherein the chip capsule (106) placed in the right tank comprises a protein nanopore chip (307) and a capsule, wherein 4 protein nanopores are uniformly integrated in the protein nanopore chip (307), and the capsule contains an electrolyte.
5. The on-site rapid detection device for perfluorocarboxylic acid as claimed in claim 1, wherein the circuit module comprises an upper half circuit structure and a lower half circuit structure, the upper half circuit structure comprises two identical inverting operational amplifiers, an in-phase operational amplifier and a first power supply, the two identical inverting operational amplifiers are sequentially connected with a current input end, the in-phase operational amplifier is connected with a current output end, and the first power supply, the conductivity meter electrode (304), the resistance wire of the temperature control circulation pipeline (306) and the channel electrode (309) are connected in parallel and provide current;
the lower half circuit structure comprises catholyte equivalent resistance, nanopore equivalent resistance, anolyte equivalent resistance, a plurality of resistances, resistance box and second power supply, catholyte equivalent resistance, nanopore equivalent resistance and anolyte equivalent resistance establish ties in proper order, catholyte equivalent resistance's one end be connected with in-phase operational amplifier's normal phase input, anolyte equivalent resistance one end be connected with reverse phase operational amplifier's output, resistance box and second power supply establish ties to establish ties at nanopore equivalent resistance's both ends through the resistance.
6. The on-site rapid detection device for perfluorocarboxylic acid as claimed in claim 1, wherein the device further comprises a data processing module (201) connected to the protein nanopore chip (307) in the chip capsule (106) for detecting 4 pore channel signals on the screening protein nanopore chip (307).
7. The apparatus for rapidly detecting perfluorocarboxylic acid in situ according to claim 1, wherein said shielding housing has a window (205), and said window (205) allows real-time temperature and solution concentration indication of the internal display screen (308) to be viewed.
8. The on-site rapid detection device for perfluorocarboxylic acid as claimed in claim 1, wherein the shielding housing, the circuit module, the micro pretreatment tank (105), the dehydration condensation reaction tank and the chip capsule (106) are all detachably assembled.
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| CN202120524066.6U CN214668750U (en) | 2021-03-12 | 2021-03-12 | On-spot quick detection device of perfluor carboxylic acid |
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| CN202120524066.6U CN214668750U (en) | 2021-03-12 | 2021-03-12 | On-spot quick detection device of perfluor carboxylic acid |
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