CN116183704B - Coaxial integrated implantable optical fuel sensor and method for detecting persistent organic pollutants - Google Patents
Coaxial integrated implantable optical fuel sensor and method for detecting persistent organic pollutants Download PDFInfo
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Abstract
本发明公开了一种同轴集成的植入式光燃料传感器，包括光阳极、生物阴极和燃料，所述的光阳极是以导光光纤为基底，在其一端依次修饰金层和碳纳米管以及Ag2S‑Bi2S3异质结所得；所述生物阴极是以玻璃毛细管为基底，在其一端修饰金层后，再继续修饰用于特异性识别目标物的核酸适配体，然后在该修饰端的端口处用全氟磺酸溶液固化形成质子交换膜所得；所述燃料是抗坏血酸溶液；所述同轴是将光阳极插入生物阴极内形成集成结构。本发明可以用于在持久性有机污染物方面的检测应用，解决了单独植入多个电极以及光源到复杂环境造成的灵敏度较低、选择性较差、易被污染、难以实现原位检测等问题。The present invention discloses a coaxial integrated implantable light fuel sensor, comprising a photoanode, a biocathode and a fuel, wherein the photoanode is based on a light-guiding optical fiber, and a gold layer, a carbon nanotube and an Ag2S - Bi2S3 heterojunction are sequentially modified at one end of the photoanode ; the biocathode is based on a glass capillary, and after a gold layer is modified at one end, a nucleic acid aptamer for specific identification of a target is further modified, and then a perfluorosulfonic acid solution is used to solidify the proton exchange membrane at the port of the modified end; the fuel is an ascorbic acid solution; the coaxial structure is formed by inserting the photoanode into the biocathode. The present invention can be used for the detection of persistent organic pollutants, and solves the problems of low sensitivity, poor selectivity, easy contamination, and difficulty in in-situ detection caused by the single implantation of multiple electrodes and light sources in a complex environment.
Description
Technical Field
The invention belongs to the field of photoelectrochemistry sensing, and particularly relates to a coaxial integrated implantable optical fuel sensor, a preparation method thereof and detection application thereof in the aspect of persistent organic pollutants.
Background
Persistent organic pollutants refer to synthetic chemicals with high toxicity, persistence, bioaccumulation and long distance mobility, which are ubiquitous in the environment, and have become a major environmental pollution problem of global concern. Leakage of persistent organic pollutants into the environment can be bioaccumulated and bio-amplified by the food chain, ultimately causing serious adverse effects on human health, such as endocrine disorders, immune and reproductive system dysfunction, developmental neurotoxicity, and certain cancers. Thus, there is an urgent need for an analytical method for rapid, sensitive, portable and on-site detection of persistent organic pollutants, which is a critical step in assessing their environmental risk. Fish, an important component of the human diet, can accumulate persistent organic pollutants from dietary sources and gill membranes, resulting in higher pollutant enrichment in their tissues than in surrounding water, and are the primary source of persistent organic pollutants accumulated by humans. Therefore, in-situ quantitative detection of persistent organic pollutants in fish is of great importance for the comprehensive assessment of the harm of persistent organic pollutants to the ecological environment and human health.
Conventional techniques for analysis of contaminants in animal samples typically require destruction or killing of organisms, are not only unscrupulous to the animal, are detrimental to endangered species, but also do not reflect the actual accumulation and change of persistent organic contaminants in the living body. Although solid-phase microextraction technology can realize in-situ sampling in living bodies, the follow-up needs complex elution steps and large-scale instruments such as high performance liquid chromatography are required for sample analysis, so that on-site monitoring and timely feedback of target pollutants are difficult to realize. In various in vivo and in situ analysis techniques, electrochemical sensing has been widely used with its advantages of high spatial-temporal resolution, simplicity of equipment, etc. Photoelectrochemical sensors, which are evolutionary products of electrochemical analysis, not only inherit the above-mentioned advantages, but also have higher sensitivity due to the separation of the photoexcitation signal from the electrical detection signal. In addition, the self-powered photoelectrochemical sensor formed by the photo-fuel cell with only the anode and the cathode can work without an external power supply, so that the portability of the equipment and the detection with low cost are easier to realize. However, the existing photoelectrochemical living body sensor basically needs to be implanted with a separated three-electrode system comprising a photo-anode, a reference electrode and a counter electrode, which easily causes three problems that 1) biological macromolecules in a complex living body environment cause biological pollution to the three electrodes, electroactive small molecules in the living body easily interfere with the photo-anode, and meanwhile, photoactive materials on the photo-anode can cause biological toxicity to the living body, 2) the distance between implanted electrodes in a freely movable animal body cannot be accurately controlled, so that the detection precision is affected, and 3) a plurality of electrodes and additional light sources are required to be implanted into the living body for multiple times, so that great mechanical damage is caused to the living body.
Disclosure of Invention
The invention aims to solve the technical problems of low sensitivity, poor selectivity, easy pollution, difficult realization of in-situ detection and the like caused by independently implanting a plurality of electrodes and light sources into a complex environment.
The invention adopts the technical proposal for solving the problems that:
the coaxial integrated implantable optical fuel sensor comprises an optical anode, a biological cathode and fuel, wherein the optical anode is obtained by taking a light guide optical fiber as a substrate, sequentially modifying a gold layer, a carbon nano tube and an Ag 2S-Bi2S3 heterojunction at one end of the optical anode, the biological cathode is obtained by taking a glass capillary as a substrate, continuously modifying a nucleic acid aptamer for specifically identifying a target object after the gold layer is modified at one end of the biological cathode, and then solidifying the nucleic acid aptamer at the end of the biological cathode by using a perfluorosulfonic acid solution to form a proton exchange membrane, and the fuel is an ascorbic acid solution.
According to the scheme, the fuel is injected into the biocathode, the photo-anode is inserted into the biocathode to be contacted with the fuel, and the photo-anode and the biocathode are coaxial.
According to the above scheme, the carbon nanotubes may be multi-wall carbon nanotubes or single-wall carbon nanotubes.
The preparation method of the coaxial integrated implantable optical fuel sensor mainly comprises the following steps:
s1, selecting a glass capillary tube and a light guide optical fiber, wherein the inner diameter of the glass capillary tube is larger than the diameter of the light guide optical fiber;
S21, modifying a gold layer at one end of the glass capillary tube by adopting a seed-mediated growth method, then modifying a nucleic acid aptamer capable of specifically recognizing a target object on the surface of the gold layer through gold sulfide bonds, and closing an active site by using a 6-mercapto-1-hexanol (MCH) solution to obtain a glass capillary tube/gold layer/nucleic acid aptamer electrode;
s22, injecting perfluorinated resin solution into the modified end of the glass capillary/gold layer/nucleic acid aptamer electrode, and forming a layer of proton exchange membrane at the port of the modified end of the electrode after drying to obtain a biological cathode;
S31, modifying a gold layer at one end of the light guide fiber in the S1 by adopting a seed-mediated growth method, and then modifying a multiwall carbon nanotube (MWNT) on the surface of the gold layer by adopting a layer-by-layer self-assembly method to obtain a fiber/gold layer/MWNT electrode;
S32, utilizing a continuous ion layer to adsorb and modify an Ag 2S-Bi2S3 heterojunction with high photoelectric conversion efficiency at the modification end of the optical fiber/gold layer/MWNT electrode, and constructing to obtain a photo-anode;
S4, filling the fuel ascorbic acid solution into the biological cathode obtained in the S22, and inserting the modified end of the photoanode obtained in the S32 into the biological cathode to contact with fuel, so that the coaxial integrated implantable optical fuel sensor is obtained.
According to the scheme, the diameter of the transparent light guide optical fiber is preferably 100-200 mu m, the length of the modified end is preferably 2-3 cm, the inner diameter and the outer diameter of the glass capillary are preferably 250-350 mu m and 350-450 mu m respectively, and the length of the modified end is preferably 1.5-2.5 cm. Further, the glass capillary tube modified end comprises a straight tube section and a necking section (drawn by a drawing instrument) positioned at one end of the straight tube section, and the diameter of the tip end of the necking section is preferably 35-45 mu m.
According to the scheme, the method for growing the gold layer in the S21 comprises the steps of soaking one end of a glass capillary tube in a dopamine solution for 0.5-1.5 h, washing and drying, soaking the glass capillary tube in a gold seed for 10-13 h, and finally standing in a mixed solution of hydroxylamine hydrochloride and chloroauric acid to grow the gold layer, washing and drying. The concentration of the dopamine solution is within the range of 1-2 mg/mL, the gold seeds refer to aqueous solutions containing gold nanoparticles, the concentration is preferably within the range of 50-100 mug/mL, and in the mixed solution of hydroxylamine hydrochloride and chloroauric acid, the concentration of each of the hydroxylamine hydrochloride and the chloroauric acid is preferably within the range of 0.5-1.5 mM and 0.03-0.07 wt%, and the mixture is kept stand for 3-5 min for growth.
According to the scheme, the method for modifying the aptamer through gold sulfide bonds in S21 comprises the steps of firstly dissolving a thiolated aptamer in 5-20 mM PBS buffer solution (pH 7.0-7.5) with the concentration of 6-10 mu M, then adding tris (2-carboxyethyl) phosphine (TCEP) aqueous solution to activate the aptamer for 1-3 hours (the concentration of TCEP in the aptamer solution is 0.2-1 mM) to obtain the aptamer solution, then placing one end of a glass capillary with a gold layer growing on the aptamer solution, incubating the end for 12-20 hours at 4 ℃, taking out the end, then washing the end with the PBS buffer solution, finally, placing the end in 0.5-2 mM 6-mercapto-1-hexanol (MCH) aqueous solution for sealing for 1-3 hours, and then taking out the end and washing the end with the PBS buffer solution to obtain the glass capillary/gold layer/nucleic acid aptamer electrode.
According to the scheme, the specific operation method of the S22 is that a perfluorinated sulfonic acid resin solution (Nafion) is injected into a modified end port of a capillary glass tube/a gold layer/a nucleic acid aptamer electrode, and then the modified end port is solidified at room temperature to form a proton exchange membrane. The concentration of the Nafion solution is in the range of 0.4-0.6wt%, the injection volume is in the range of 0.04-0.06 mu L, and the end port curing at the modified end can be realized to form the proton exchange membrane.
According to the scheme, the method for growing the gold layer in the S31 comprises the steps of soaking a clean light guide optical fiber in 1-2 mg/mL of dopamine solution for 1.5-2.5 h, washing and drying, then adopting acetone soaking treatment for 2-4S to remove a polydopamine layer and an optical fiber cladding layer with the front end of 0.7-0.9 cm of the optical fiber so that the optical fiber can transmit light at the front end, washing and drying, soaking the end with 1.5-2.5 cm in gold seeds for 3-5 h, standing in a mixed solution of hydroxylamine hydrochloride and chloroauric acid for 3-5 min, washing and drying to obtain the optical fiber with the front end of 0.7-0.9 cm of which the gold layer does not grow. The gold seed is an aqueous solution containing gold nanoparticles, the concentration of the aqueous solution is preferably in the range of 50-100 mu g/mL, and the concentration of each of hydroxylamine hydrochloride and chloroauric acid in a mixed solution of the hydroxylamine hydrochloride and chloroauric acid is preferably in the range of 0.5-1.5 mM and 0.03-0.07 wt%.
In S31 and S21, after the gold layer grows on the light guide fiber and the glass capillary, the resistance is 10-20Ω.
According to the above scheme, in S31 and S32, the gold layer is not completely overlapped with the carbon nanotube, but is partially overlapped at the modified end, the modified region of the carbon nanotube is closer to (or extends to) the port direction of the optical fiber modified end than the modified region of the gold layer, and the modified region of the carbon nanotube is larger than the modified region of the gold layer, i.e., the modified region of the gold layer does not extend to the modified end port, a small distance (e.g., 0.7-0.9 cm) exists from the modified end port, and the modified region of the carbon nanotube extends to the modified end port, and the modified region of the carbon nanotube includes the modified region of the gold layer and the region of the optical fiber front end where the gold layer is not modified, and the modified region of the Ag 2S-Bi2S3 heterojunction is substantially overlapped with the modified region of the carbon nanotube. Specifically, the part 0.7-0.9 cm of the forefront end of the optical fiber modified end is not provided with a modified gold layer, but the carbon nano tube is modified, and the modified region of the carbon nano tube comprises a gold layer modified region and the part 0.7-0.9 cm of the optical fiber modified front end is not provided with a modified gold layer.
According to the scheme, the method for modifying the carbon nano tube by the middle layer self-assembly method in the S31 comprises the steps of placing an optical fiber after growing a gold layer in a polydiallyl dimethyl ammonium chloride (PDDA) aqueous solution for adsorption, soaking and washing with water, then placing the optical fiber in a carboxylated carbon nano tube aqueous solution for adsorption, wherein the method is one cycle in the S31, washing and drying the optical fiber after one cycle, and then carrying out the next cycle to realize the modification of the carbon nano tube. The cycle times range is 3-5 times, the concentration of PDDA is 0.5-1.5wt%, the adsorption time is 4-6 min, the concentration of carboxylated carbon nanotube aqueous solution is 0.4-0.6mg/mL, and the adsorption time is 4-6 min respectively.
According to the scheme, the method for adsorbing and modifying the Ag 2S-Bi2S3 heterojunction on the optical fiber/gold layer/MWNT electrode by utilizing the continuous ion layer in the S32 comprises the steps of placing the modified end of the optical fiber/gold layer/MWNT electrode in a 0.08-0.12M AgNO 3 aqueous solution for 25-35 min in a dark environment, continuously soaking in a 0.1-0.14M Na 2 S solution for 25-35 min after water soaking, washing and drying, then respectively soaking in 8-12 mM Bi (NO 3)3 solution and 8-12 mM Na 2 S solution for 8-12 min, washing and drying, and adsorbing Bi 2S3 in one cycle, wherein the cycle number of adsorbing Bi 2S3 is 1-3.
According to the scheme, in S4, the concentration of the fuel ascorbic acid solution is 20-100 mM, and the filling height in the biological cathode is higher than that of the photoanode modified end.
According to the scheme, the target object is a persistent organic pollutant, the invention takes 3,3', 4' -tetrachlorobiphenyl (PCB 77) as an example, the Aptamer capable of specifically recognizing 3,3', 4' -tetrachlorobiphenyl (PCB 77) is SH-Aptamer, and the sequence is 5'-SH- (CH 2)6 -GGC-GGG-GCT-ACG-AAG-TAG-TGA-TTT-TTT-CCG-ATG-GCC-CGT-G-3'. If other pollutant is selected as the target object to be detected, the corresponding molecule capable of specifically recognizing can be selected, and only the recognition molecule contains amino or mercapto and other groups capable of being modified to a gold layer is needed.
The application of the coaxial integrated implanted optical fuel sensor in detecting 3,3', 4' -tetrachlorobiphenyl (PCB 77) comprises inserting the coaxial integrated implanted optical fuel sensor into a PCB77 solution, irradiating a non-modified end of a photo-anode with a laser source, exciting the modified Ag 2S-Bi2S3 to generate photo-generated electrons along with the transmission of optical fibers to the modified end of the photo-anode, transmitting the electrons to a biological cathode through an external circuit to form an open-circuit voltage, blocking the transmission of electrons after a target object is identified to the biological cathode through an adapter to reduce the open-circuit potential, connecting the biological cathode and the photo-anode with wires at two ends of a potentiometer through a gold layer with surface modification, measuring the change of the open-circuit voltage along with the concentration of the PCB77, and measuring the content of the PCB77 in a to-be-detected object by adopting a standard curve method.
According to the scheme, the sample to be tested can be living bodies such as fish, mice, plants and the like, and can also be solutions such as blood, urine and the like.
According to the scheme, the potentiometer can be an electrochemical workstation or a portable potentiometer. The portable potentiometer may be replaced with a portable pH meter that can take a potential reading.
The invention also provides a coaxial integrated implantable optical fuel sensor system, which comprises the coaxial integrated implantable optical fuel sensor, a light source and a potentiometer, wherein the coaxial integrated implantable optical fuel sensor is used for being inserted into an object to be detected, the light source and a photoanode of the sensor can be connected through a base optical fiber of the photoanode, and a biological cathode of the sensor and a gold layer of the photoanode are respectively and electrically connected with two ends of the potentiometer through thin copper wires. The wavelength of the light source is in the visible-near infrared wavelength range capable of exciting the Ag 2S-Bi2S3 material.
The detection principle of the invention is that the optical active material Ag 2S-Bi2S3 with the surface modified by the optical fiber is excited by light transmitted along the optical fiber (a laser is connected with the unmodified end of the optical fiber) to generate electron-hole pairs. Because of the band matching of Ag 2 S and Bi 2S3, the excited electrons in Bi 2S3 are transported to Ag 2 S, which has a relatively negative valence band energy level, then to the carbon nanotubes, then to the fiber/gold layer, and finally to the glass capillary/gold layer/aptamer bioanion through an external circuit, thereby generating electrical energy (open circuit potential). The ascorbic acid fuel in the glass capillary is used to fill the photogenerated holes of Bi 2S3 to promote the separation of electron-hole pairs. When the target PCB77 recognizes that the aptamer-PCB 77 complex with poor conductivity is formed on the surface of the biocathode through interaction with the aptamer, separation of hole-electron pairs is blocked, OCP signals are reduced, and therefore detection of the PCB77 is achieved. The gold layer is opaque, so that the gold layer does not grow at the forefront end of the optical fiber after acetone treatment, but the carbon nano tube with better light transmittance is modified, and the light transmitted by the optical fiber can be ensured to irradiate the Ag 2S-Bi2S3 at the outmost layer to realize material excitation. The electron transfer between the cathode and the anode is not affected after the proton exchange membrane is modified by the tip of the biological cathode, and meanwhile, the photoanode hidden in the cathode can avoid the influence on the selectivity of the photoanode due to the contact with complex biological environment because the proton membrane can only pass through protons and electrons.
Compared with the prior art, the invention has the beneficial effects that:
1. The coaxial integrated implantable photo-fuel sensor prepared by the invention has the advantages that the photo-anode is hidden in the biological cathode, the distance between the photo-anode and the biological cathode is fixed and shortened, the biological pollution of the photo-anode is reduced, and the sensing sensitivity and accuracy are improved;
2. the coaxial integrated implantable optical fuel sensor prepared by the invention can eliminate the interference of electroactive small molecules on the optical anode in complex living environment or solution environment and overcome the possible biotoxicity of the photoactive material;
3. The coaxial integrated implantable optical fuel sensor prepared by the invention reduces the damage caused by additionally inserting a reference electrode, a counter electrode and a light source into a living body, and greatly reduces the mechanical damage to living tissues;
4. The coaxial integrated implanted optical fuel sensor prepared by the invention can be applied to in-situ monitoring of the bioaccumulation level of the PCB77 in living bodies such as fish brain, and the fluctuation of the PCB77 in the body can be directly reflected by a handheld potentiometer on site, thus providing an important technical breakthrough for in-situ monitoring technology of living bodies.
In conclusion, the coaxial integrated implantable optical fuel sensor provided by the invention realizes rapid in-situ detection of persistent organic pollutants in living bodies by adopting the portable potentiometer on site, has the advantages of high sensitivity, good pollution resistance, excellent biocompatibility, low biotoxicity, small implantation damage and the like, is low in cost, can work under the condition of no external voltage, has the performance of portability and low cost, and is suitable for on-site detection of various targets.
Drawings
FIG. 1 is a schematic illustration OF a process for preparing a photoanode OF the present invention, wherein Optical Fiber (OF) represents an Optical fiber, PDA is polydopamine, acetone is acetone, remove cladding represents a clad removal, and AuNPs seeds represent gold species.
FIG. 2 is a schematic diagram showing a preparation process of the biocathode of the invention, wherein GLASS CAPILLARY represents a glass capillary, au-decorated represents a modified gold layer, PCB77 aptamer represents a PCB77 aptamer, and MCH is mercapto hexanol.
FIG. 3 is a linear relationship diagram of application example 1;
FIG. 4 is a schematic view of the living body detection of the coaxial integrated implantable optical fuel sensor of application example 2;
fig. 5 is a graph showing the results of a test of concentration of enriched contaminants in fish brains of application example 2, which were exposed to different concentrations of PCB77 in the contaminant solution for different times.
FIG. 6 is a graph comparing the results of the test of application example 2 using the sensor we constructed and gas chromatography to determine the concentration of PCB77 in fish brains after 6 days of exposure to PCB77 at different concentrations.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the invention further, but are not to be construed as limiting the invention.
In the following embodiments, after the gold layer is grown on the light guide fiber and the glass capillary, the resistance is 10 to 20 Ω.
Examples
A preparation method of a coaxial integrated implantable optical fuel sensor comprises the following specific steps:
s11, drawing a capillary with the inner diameter of 300 mu M and the outer diameter of 400 mu M by using a drawing instrument to obtain a conical glass capillary with the tip end diameter of 40 mu M, dissolving a nucleic acid Aptamer SH-Aptamer capable of specifically recognizing a target object PCB77 in a 10mM PBS (pH=7.4) solution to obtain an 8 mu M Aptamer solution, and adding 0.5mM TCEP activated Aptamer for 2 hours;
S12, soaking the tip end (about 2cm long) of a capillary glass tube in 1.5mg/mL dopamine solution for 1h, washing and drying, soaking in gold seeds for 12h, finally standing and growing in a mixed solution of 1mM hydroxylamine hydrochloride and 0.05wt% chloroauric acid for 4min, washing and drying, then placing in an aptamer solution obtained in S11, incubating for 16h at 4 ℃, taking out, washing with a 10mM PBS (pH=7.4) buffer solution, sealing in a 1mM MCH solution for 2h, taking out, and washing with a 10mM PBS (pH=7.4) buffer solution again to obtain the capillary glass tube/gold layer/nucleic acid aptamer electrode;
S13, injecting 0.05 mu L of 0.5% Nafion 117 perfluorinated resin solution into the tip of a capillary glass tube/gold layer/nucleic acid aptamer electrode (namely a necking section), and solidifying the tip port at room temperature to form a Nafion 117 membrane, thereby obtaining a biological cathode;
S21, soaking the front end (the front end is about 2cm long) of a transparent light guide optical fiber with the length of 7cm and the diameter of 125 mu m in 1.5mg/mL of dopamine solution, washing and drying, adopting acetone to treat for 3s to remove a polydopamine layer and an optical fiber cladding layer at the front end (0.8 cm) of the optical fiber so that the optical fiber can transmit light at the front end, washing and drying, soaking in gold seeds for 4h, finally standing and growing in a mixed solution of 1mM hydroxylamine hydrochloride and 0.05% chloroauric acid for 4min, washing and drying to obtain an optical fiber with a gold layer at the front end, wherein the longitudinal length of a gold layer modification region of the optical fiber is about 1.7cm, and the distance between the gold layer modification region and a port of the optical fiber modification end is about 0.8cm;
S22, adsorbing the front end of the optical fiber obtained in the S21 in a solution containing 1wt% of PDDA for 5min, soaking in water, and then adsorbing in a carboxylated MWNT solution of 0.5mg/mL for 5min, wherein the adsorption is one cycle, the total number of cycles is 4, washing and drying are carried out, an optical fiber/gold layer/MWNT electrode is obtained, the part of the front end of the optical fiber, which is 0.8cm in length, is not provided with a modified gold layer, but is modified by carbon nano tubes, and the longitudinal length of a carbon nano tube modification area is about 2.5cm;
S23, soaking the modified end of the optical fiber/gold layer/MWNT electrode in 0.1M AgNO 3 solution for 30min in dark environment, continuously soaking in 0.12M Na 2 S solution for 30min after soaking in water, washing and drying, and then sequentially soaking in 10mM Bi (NO 3)3 solution and 10mM Na 2 S solution for 10min respectively, wherein the cycle is that of adsorbing Bi 2S3, and the cycle is two times, and washing and drying are carried out, so that a photoanode is obtained;
S3, filling 'fuel' ascorbic acid (50 mM) into the biological cathode obtained in the step S13, inserting the photoanode modified end prepared in the step S23 into the modified end of the biological cathode, wherein the height of an ascorbic acid solution is higher than that of the photoanode modified end, so that the coaxial integrated implantable optical fuel sensor is obtained and can be used for tracking and detecting persistent organic pollutants in vivo.
Application example 1
The coaxial integrated implantable photo-fuel sensor prepared by the example was used to detect PCB77 in the buffer solution. The open circuit potential is measured by using a 650nm laser pen as a light source and a portable pH meter, the coaxial integrated implanted optical fuel sensor is inserted into a buffer solution containing PCB77 with different concentrations, the laser pen is connected with the non-modified end of the photo anode, the biological cathode and the photo anode are respectively connected with the two ends of the pH meter through copper wires, and then the open circuit voltage is measured, so that the response signals of the coaxial integrated implanted optical fuel sensor to the PCB77 with the series concentrations are shown in the table 1.
Table 1PCB77 test results
As can be seen from analysis of the data in Table 1, the response of the implanted optical fuel sensor to the PCB77 series concentration gradually decreases with the increase of the concentration, and the linear fitting finds that the open-circuit potential variation value delta OCP (the difference between the OCP of the target object and the OCP of the background) and the logarithm of the PCB77 concentration are in a linear relation (figure 3), and the regression equation is delta OCP=22.6+12.21 lgC (R 2 =0.998) (delta OCP: mV; C: pg/mL), the linear range is 0-10000 pg/mL, and the detection sensitivity is 2.8fg/mL, so that the practical detection requirement can be met.
Application example 2
The coaxial integrated implantable optical fuel sensor prepared by the embodiment is adopted to carry out in-situ monitoring on the PCB77 enriched in the fish brain, and the specific process is as follows:
The fish were placed in aerated aquariums containing dechlorinated tap water for two weeks to accommodate feed prior to in vivo testing. 36 grass carp were divided into 4 groups (9 fish per 50L aquarium (40L water)), and raised in 0 (control group), 0.1, 1, 10ng/mL PCB77 water for 3, 6, 9 days, respectively. To keep the concentration of PCB77 in the water stable, two thirds of the contaminated water was replaced every 12 hours, and the water quality (pH 6.8.+ -. 0.2, dissolved oxygen 7.0.+ -. 0.3mg/L, temperature 25.+ -. 0.7 ℃) was monitored daily. At the end of each exposure interval, 3 fish were removed from each aquarium for photoelectrochemical testing of the in vivo PCB 77.
In vivo analysis fish were first anesthetized with 0.03% eugenol until vertical balance was lost. The head was then pierced with a 26-gauge needle at the midpoint of both eyes along the axis of the body of the fish, inserted about 7mm to penetrate the skull, after which the needle was removed and the integrated sensor was inserted about 1.7cm into the hole to penetrate the entire brain. Meanwhile, a 650nm laser pen is used as an excitation source, the laser pen is connected with the non-modified end of the photo-anode, and the bio-cathode and the photo-anode are respectively connected with two ends of the pH meter through gold layers on the surfaces of the bio-cathode and the photo-anode by copper wires. Finally, the fish were placed in fresh water to restore vertical equilibrium while the OCP response was detected by a pH meter.
The concentration of PCB77 in brains of fish exposed to different concentrations of PCB77 and different times was monitored (as in fig. 5), and the results showed that the OCP signal of the sensor in the brains of the control group (no PCB77 exposure) remained essentially unchanged throughout the experiment, indicating that the sensor background was stable, and that the accumulation of PCB77 in the brains was positively correlated with exposure dose and exposure time, confirming that the constructed photo-fuel microsensor could directly track the bioaccumulation level of persistent organic pollutants in vivo. Finally, the concentration of the PCB77 in the fish brain is detected by adopting a gas chromatography method, and the obtained result is very similar to the detection result of the prepared microsensor (as shown in figure 6), so that the photo-fuel sensor has higher reliability.
Variations and modifications to the above would be obvious to persons skilled in the art to which the invention pertains from the foregoing description and teachings. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not constitute any limitation on the scope of the present invention.
Claims (10)
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