CN115058888A - Fe-N-C nano enzyme in-situ modified carbon fiber and preparation method thereof - Google Patents
Fe-N-C nano enzyme in-situ modified carbon fiber and preparation method thereof Download PDFInfo
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
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Abstract
The invention relates to a Fe-N-C nano enzyme in-situ modified carbon fiber and a preparation method thereof. The invention takes the carbon fiber as a substrate material, grafts the benzenesulfonic acid group on the surface of the carbon fiber through diazotization grafting reaction, improves the dispersibility of the carbon fiber in a water phase, can promote the close wrapping of the m-diphenylamine polymer by utilizing the electrostatic action, and effectively enhances the adhesive force of the synthetic material on the carbon fiber. Further passing through N in m-phenylenediamine and metal ion Fe 3+ By high temperature pyrolysis of Fe 3+ Covalently bonded with N atom on the surface of carbon fiber to form stableAnd determining the monoatomic structure to obtain the Fe-N-C nanoenzyme in-situ modified carbon fiber. The method improves the charge transfer speed of the surface of the carbon fiber, reduces the overpotential when the carbon fiber is used for detecting the cranial nerve chemical substances, and improves the catalytic activity, thereby realizing the high-sensitivity detection of the cranial nerve chemical substances.
Description
Technical Field
The invention belongs to the technical field of nano material synthesis, and particularly relates to Fe-N-C nano enzyme in-situ modified carbon fiber and a preparation method thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
At present, many nanoenzymes are composed of metals and metal oxides, because the metal active centers can simply mimic the catalytic electronic redox processes of natural enzymes. Research shows that the overpotential of the electrode reaction of the target object can be greatly reduced by utilizing the excellent catalytic activity and selectivity of the Fe-based nanoenzyme, the interference of other substances in the body is effectively eliminated, and the huge potential of the nanoenzyme in the in-vivo detection is shown.
The in vivo analysis of brain neurochemicals by using the implanted electrochemical biosensor is an important way for researching brain function and brain activity mapping. And carbon fiber is an ideal electrode material in a microelectrode system for in situ electrochemical analysis of a living body. In general, in a carbon fiber microelectrode, dip (drop) coating is a conventionally employed method for modifying an electrode, and thus it is difficult to achieve precise spatial control, resulting in poor reproducibility. At present, relevant reports that nano enzyme is synthesized firstly and then is decorated on a working electrode have relatively complex steps; furthermore, the modification process may affect the activity of the catalyst, and the weak interaction between the catalyst and the carbon fibers may not ensure the mechanical stability of the electrode. Many neurodegenerative diseases (such as Alzheimer's disease and Parkinson's disease) have long pathological processes, and the need for long-term monitoring puts higher requirements on the stability of the device. Therefore, it is necessary to search for a more efficient and convenient modification or synthesis method, improve the catalytic activity and adhesion of the nanoenzyme on the surface of the carbon fiber microelectrode, and construct a robust electrode/brain catalytic interface, thereby effectively improving the sensitivity, selectivity, time resolution and stability of the detection of the neurochemical substances in vivo.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide the Fe-N-C nanoenzyme in-situ modified carbon fiber and the preparation method thereof, and the carbon fiber is directly prepared into a carbon fiber microelectrode for sensitive detection of representative cranial nerve chemical substances, namely hydrogen peroxide and Dopamine (DA).The invention takes the carbon fiber as a substrate material, grafts the benzenesulfonic acid group on the surface of the carbon fiber through diazotization grafting reaction, improves the dispersibility of the carbon fiber in a water phase, can promote the close wrapping of the m-diphenylamine polymer by utilizing the electrostatic action, and effectively enhances the adhesive force of the synthetic material on the carbon fiber. Further passing through N in m-phenylenediamine and metal ion Fe 3+ By high temperature pyrolysis of Fe 3+ And the carbon fiber and N atoms are subjected to covalent bonding on the surface of the carbon fiber to form a stable monoatomic structure, so that the Fe-N-C nanoenzyme in-situ modified carbon fiber (Fe-N-C/CF) is obtained. The method improves the charge transfer speed of the surface of the carbon fiber, reduces the overpotential when the carbon fiber is used for detecting the cranial nerve chemical substances, and improves the catalytic activity, thereby realizing the high-sensitivity detection of the cranial nerve chemical substances.
In order to achieve the above technical effects, the present application provides the following technical solutions:
the invention provides a preparation method of Fe-N-C nano-enzyme in-situ modified carbon fiber. The method comprises the following steps:
(1) dissolving sulfanilic acid in ultrapure water, and slowly and sequentially dropwise adding pre-cooled NaOH solution, HCl solution and NaNO in ice water bath 2 Dispersing the pretreated carbon fibers into the solution, maintaining the low temperature for reaction, adding reducing Fe powder into the solution after the reaction, and stirring to obtain grafted carbon fibers;
(2) dissolving m-phenylenediamine in ultrapure water, adding concentrated hydrochloric acid, and then adding the grafted carbon fiber into the solution; slowly dropwise adding precooled ammonium persulfate and FeCl in sequence 3 A solution; controlling the temperature for a period of time at low temperature, and then heating for reaction; taking out, rotary steaming and drying at normal temperature; supplementing FeCl 3 Rotary steaming and drying;
(3) and (3) placing the product obtained in the step (2) in a tube furnace, performing first high-temperature pyrolysis in an argon atmosphere, then performing acid washing, filtering, washing, drying, and performing second high-temperature pyrolysis after drying to obtain the Fe-N-C nanoenzyme in-situ modified carbon fiber.
Further, the pretreatment process of the carbon fiber comprises the following steps: the carbon fiber is desized, soaked in acetone solution for 24h, then ultrasonically treated and cleaned in ultrapure water for three times, and then dried in a vacuum drying oven.
Further, in the step (1), the using amount of sulfanilic acid is 0.5-1 mmol; the concentration of the NaOH solution is 1M, and the volume of the NaOH solution is 0.5-1 mL; the concentration of the HCl solution is 1M, and the volume of the HCl solution is 3-5 mL; NaNO 2 The concentration of the solution is 1M, and the volume of the solution is 0.5-1 mL.
Furthermore, in the step (1), the amount of the pretreated carbon fibers is 0.02-0.2 g.
Further, in the step (1), the low temperature is 0-3 ℃, and the reaction time is 1 h.
Furthermore, in the step (1), the using amount of the reducing Fe powder is 0.1-0.2 g.
Further, in the step (2), the using amount of the m-phenylenediamine is 1-2 g; the concentration of the concentrated hydrochloric acid is 36% -38%, and the volume of the concentrated hydrochloric acid is 3-6 mL; the concentration of ammonium persulfate is 2M, and the volume of ammonium persulfate is 10-20 mL; FeCl 3 The concentration of the solution is 1M, and the volume of the solution is 3-8 mL.
Further, in the step (2), the temperature is controlled at the low temperature of 0-3 ℃, after 8 hours, the temperature is raised to 7-8 ℃, and the reaction time is 12 hours.
Further, the rotary evaporation conditions are as follows: starting at 60 ℃ and controlling the temperature at 80 ℃ to a vacuum degree of-0.08 MPa. Drying at normal temperature: drying in a vacuum drying oven at 100 deg.C for 12 hr under normal pressure.
Further, in the step (2), FeCl is added 3 The dosage of the solution (1M) is 1-10 mL.
Further, in the step (3), the temperature is 850-1000 ℃ and the time is 1h during the first high-temperature pyrolysis; the temperature of the second high-temperature pyrolysis is 850-1000 ℃, and the time is 3 h.
Further, in the step (3), after the temperature of the tube furnace is reduced after the first high-temperature pyrolysis, the tube furnace is taken out for acid washing, and the acid washing is carried out for 8 hours at 80 ℃ to remove inactive and unstable compounds (such as Fe) 3 C and FeS, etc.).
The invention provides a Fe-N-C nano enzyme in-situ modified carbon fiber prepared by the preparation method.
The second aspect of the invention provides application of the Fe-N-C nano-enzyme in-situ modified carbon fiber in brain neurochemical analysis and detection.
The invention has the beneficial effects that:
the invention adopts diazotization grafting reaction, m-phenylenediamine polymerization reaction and Fe 3+ A series of reactions such as anchoring, high-temperature pyrolysis and the like, and Fe-N-C nano enzyme is synthesized on the carbon fiber in situ. Making it into carbon fiber microelectrode, and utilizing inherent enzyme-like activity of Fe-N-C nanoenzyme to implement representative cranial nerve chemical substance H 2 O 2 And DA, reducing the overpotential of the reaction, and Fe-N-C/CF microelectrode pair H 2 O 2 And DA have good current response and stability, and the electrode material has great potential in vivo analysis.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a schematic diagram of the synthesis of Fe-N-C/CF.
In FIG. 2, a and b are SEM images of CF and Fe-N-C/CF, respectively, and C, d, e and f are element distribution diagrams of C, N, O, Fe in Fe-N-C/CF, respectively.
In FIG. 3, A is CF, CF-Ph-SO 3 XRD spectra of H and Fe-N-C/CF; B. c, D, E are fine spectra of different elements (B is C1s, C is O1s, D is N1s, E is Fe 2 p).
FIG. 4 shows an electrochemical AC impedance spectrum (wherein a is CF and b is CF-Ph-SO) 3 H and C are Fe-N-C/CF).
FIG. 5A is a pair of Fe-N-C/CF microelectrodes (inset) not containing H (a) 2 O 2 And (b) contains 5mM H 2 O 2 A CV curve of (d); b is (a) CF microelectrode and (B) Fe-N-C/CF microelectrode, 0.5mM H is continuously dripped into aCSF 2 O 2 Current response of (d); c is Fe-N-C/CF microelectrode pair (a) saturated N 2 Air, (c) saturated oxygen CV curve.
FIG. 6A shows a pair of Fe-N-C/CF microelectrodes comprisingVarying concentrations (0,2,5,10,20mM) of H 2 O 2 A CV curve of (a); b is the CA curve of the Fe-N-C/CF microelectrode under different voltages (0.2,0.15,0.1,0, -0.05, -0.1, -0.2, -0.3V); c is Fe-N-C/CF microelectrode for the successive addition of different concentrations of H to aCSF 2 O 2 Current response curve of (D) current and H 2 O 2 Corresponding curve of concentration.
FIG. 7, A is a CV curve of CF and (B) Fe-N-C/CF microelectrodes at (a) without DA and (B) with 20 μ M DA of aCSF.
FIG. 8, A is a CV curve of Fe-N-C/CF microelectrodes against DA at various concentrations (0,1,5, 10. mu.M); b is the CA curve of the Fe-N-C/CF microelectrode at different voltages (0.3,0.2,0.15,0.1,0.05, 0V); c is the current response curve of the Fe-N-C/CF microelectrode to the continuous addition of DA of different concentrations and D is the corresponding curve of the current and the DA concentration.
FIG. 9, panel A is a regional mini-perfusion of Fe-N-C/CF microelectrodes recorded in the right cortex of anesthetized rats containing 10mM H 2 O 2 The current response of aCSF (applied voltage: -0.1V vs Ag/AgCl); b is the high K of local micro-perfusion recorded by the Fe-N-C/CF microelectrode in the volt gap of the anesthetized rat + Current response of stimulated DA (applied voltage: 0.2V vs Ag/AgCl).
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
Example 1
(1) Desizing directly purchased carbon fibers, soaking the carbon fibers in an acetone solution for 24 hours, then ultrasonically treating and cleaning the carbon fibers in ultrapure water, washing the carbon fibers for three times, and drying the carbon fibers in a vacuum drying oven
(2) Diazotizing grafted benzenesulfonic acid on the surface of carbon fiber: weighing sulfanilic acid (1mmol) in a clean beaker, dissolving with 10mL of ultrapure water, and slowly and sequentially dropwise adding pre-cooled NaOH solution (1M,1mL), HCl solution (1M,5mL) and NaNO in an ice water bath 2 Solution (1M,1mL),and dispersing 0.2g of the pretreated carbon fiber into the solution, maintaining the temperature at 0 ℃, reacting for 1h, adding 0.1-0.2 g of weighed reductive Fe powder into the solution, stirring, reducing the diazonium salt to generate free radicals, and grafting the benzenesulfonic acid group onto the surface of the carbon fiber (as shown in figure 1).
(3) Production of poly (m-phenylenediamine) on the surface of carbon fibers: 1g of m-phenylenediamine was weighed out and dissolved in 20mL of ultrapure water for 20 minutes, and 3mL of 38% concentrated hydrochloric acid was transferred to the solution, followed by transferring the grafted carbon fiber to the solution. Precooled 20mL ammonium persulfate (2M) and 8mL FeCl were slowly added dropwise in sequence 3 Solution (1M). Because the reaction is exothermic, the temperature is controlled at 0 ℃ initially, and after 8h, the temperature is raised to 8 ℃ again, and the reaction time is 12 h. Taking out and transferring to an eggplant-shaped bottle for rotary steaming. The temperature is controlled at 80 ℃ and is controlled at 60 ℃ and the vacuum degree of-0.08 MPa. Subsequently, drying was carried out in a vacuum drying oven at 100 ℃ for about 12 hours under normal pressure. Supplementing FeCl 3 And (5) carrying out rotary evaporation on 1-10 mL of the solution (1M), and drying.
(4) High-temperature calcination: placing the quartz boat containing the material in the center of a tube furnace, introducing high-purity argon for 30min in advance, setting up a temperature raising and reducing program, performing first high-temperature pyrolysis at 1000 ℃ for 1h under the protection of high-purity argon, taking out the quartz boat after the temperature of the tube furnace is reduced, pickling, and removing inactive and unstable compounds (such as Fe) at 80 ℃ for 8h 3 C and FeS, etc.). And filtering and washing after the reaction is finished. Drying, and performing second high-temperature pyrolysis under the same conditions and steps as the first pyrolysis at 1000 ℃ for 3h to obtain Fe-N-C/CF.
Characterization of materials
(1) Scanning Electron Microscope (SEM): a plurality of unmodified carbon fibers and Fe-N-C/CF are adhered on a sample carrying table by conductive adhesive, sample introduction, vacuum pumping and emission acceleration voltage of 20KV are carried out, and the microscopic characterization of the material surface is carried out.
(2) X-ray diffraction (XRD): the analysis was performed using an automatic RINT 2500X-ray diffractometer (Rigaku) using Cu K alpha radiation. The data acquisition adopts a 0.02 degree/2 theta step scanning mode, the speed is 1 degree/min < -1 >, and the step length is 0.02 degree (2 theta).
(3) X-ray photoelectron spectrometer (XPS): the test was performed using Thermo Fisher ESCALAB XI + from siemens, with Al K alpha radiation (1486.6eV), fixing the material on Al tape.
As can be seen from SEM (FIG. 2), the in-situ synthesis of Fe-N-C nanoenzyme on carbon fiber was successful, and C, N, O, Fe distribution on the surface of Fe-N-C/CF was relatively uniform.
XRD (fig. 3) showed that the carbon had amorphous properties and no peaks of Fe-based nanoparticles were detected.
The chemical composition and atomic configuration information of Fe-N-C/CF were analyzed by XPS. From the XPS survey spectrum (FIG. 3B), it can be seen that C, N, Fe, and O elements are present in Fe-N-C/CF, consistent with the results of the element profile in the SEM. As can be seen from the spectrum of C1s (FIG. 3C), sp is indicated 2 Hybrid graphitic carbon is the main configuration of the synthetic nanoenzymes. The presence of C-OH in the O1s spectrum (FIG. 3D) can improve the wettability of the surface, which is beneficial to the detection of neurochemical substances. The spectrum of N1s (FIG. 3E) and the spectrum of Fe 2p (FIG. 3F) show that pyridine N and pyrrole N provide coordination sites for Fe to form an Fe-N structure, which is probably the catalytic origin of the synthesized Fe-N-C/CF.
Example 3 preparation of carbon fiber microelectrodes
Fe-N-C/CF and copper wires (diameter 100 mu m, length 10cm) are connected by conductive silver adhesive, after the conductive silver adhesive is dried, one end of a carbon fiber is penetrated from one end of a glass electrode to reach the middle part (external diameter: 1.5mm, internal diameter: 1.10mm, length 10cm) of the glass electrode, another carbon fiber adhered with the copper wires is penetrated from the other end, the copper wires at the two ends of the glass electrode are fixed, and the capillary glass tube penetrated with the carbon fibers is drawn into two parts by a microelectrode drawing instrument. Pulling a 1mL syringe into a thin tube with a sufficiently slender front end by firing an alcohol lamp, sucking the single-component room-temperature vulcanized silicone rubber by using the syringe, entering the syringe from the tail end of the drawn glass electrode under a microscope, sealing the tip, and naturally drying at room temperature. Under a microscope, the carbon fibers of the tip were cut to 300 μm.
Example 4
Electrochemical measurements a conventional three-electrode system was used using a CHI760E electrochemical workstation, including a prepared carbon fiber microelectrode (Fe-N-C/CF microelectrode) as the working electrode, an Ag/AgCl (saturated potassium chloride) reference electrode and a platinum wire counter electrode.
Performing electrochemical performance characterization on the prepared Fe-N-C/CF microelectrode: alternating current impedance (EIS) test is carried out on the carbon fiber microelectrode before and after modification in a KCl solution containing 5mM [ Fe (CN)6]3-/4-, and the influence of the modification process on the surface charge transfer rate of the carbon fiber microelectrode is researched.
The prepared Fe-N-C/CF microelectrode is subjected to electrocatalytic performance test by Cyclic Voltammetry (CV) and Chronoamperometry (CA) to research the electrochemical behaviors of small molecule metabolites, namely hydrogen peroxide and dopamine on the Fe-N-C/CF microelectrode.
From the electrochemical ac impedance spectrum (fig. 4), it can be observed that the electrode process is mainly controlled by the charge transfer process (electrochemical reaction step), and the impedance caused by the diffusion process is negligible. The charge transfer resistance of the Fe-N-C/CF microelectrode is far lower than that of an unmodified carbon fiber microelectrode and that of a carbon fiber microelectrode grafted with a benzenesulfonic acid group, so that the Fe-N-C/CF microelectrode has good conductivity. Research on the application of CF microelectrode and Fe-N-C/CF microelectrode to H in artificial cerebrospinal fluid (aCSF) by adopting CV and CA 2 O 2 Electrocatalytic performance of. As can be seen from FIGS. 5A and 5B, the Fe-N-C/CF microelectrodes exhibited higher performance against HPRR and had higher peak potentials ca.0.25V (vs. Ag/AgCl) against HPRR. FIG. 5C is a CV curve comparison of Fe-N-C/CF microelectrode pairs ORR. It was observed that the onset of ORR was ca. -0.25V (vs. Ag/AgCl), which is significantly more negative than the onset of HPRR. Therefore, O can be excluded by controlling the potential to be distinguished from ORR to some extent 2 The interference of (3) improves the selectivity of the Fe-N-C/CF microelectrode on HPRR detection.
. As shown in FIG. 6A, we investigated the effect of hydrogen peroxide at various concentrations on the electrocatalytic activity of Fe-N-C/CF microelectrodes, and the results showed that Fe-N-C/CF microelectrodes have good electrocatalytic activity on HPRR. The applied potential is optimized through a CA test, and the-0.1V is selected to detect H in consideration of the magnitude of current response and the interference problem of noise 2 O 2 The optimum potential of the time.
FIG. 6C shows the optimum voltage at-0.1V (vs Ag/AgCl)Fe-N-C/CF microelectrodes for the purpose of on N 2 Continuous addition of different concentrations of H to saturated aCSF 2 O 2 Typical current-time curves. FIG. 6D shows the current vs. H 2 O 2 The concentration of (b) shows a good linear relationship, the linear equation between current and concentration is y (na) -0.7307c (mM) -0.8346 in the concentration range of 10 μ M to 1.34mM, the linear equation between current and concentration is y (na) -0.4261c (mM) -1.2143 in the concentration range of 1.34mM to 3.84mM, and the detection limit is 8.8 μ M.
. From FIG. 7, it can be seen that in the presence of DA, a significant redox peak is shown on the Fe-N-C/CF microelectrode, and the overpotential of the anode is greatly reduced (the anode peak potential is ca.0.0V (vs Ag/AgCl), and the response current after multiple cycles is not significantly reduced, which indicates that the synthesized Fe-N-C/CF has a good catalytic effect on the redox reaction of DA, and can effectively inhibit the electropolymerization of dopamine and its oxidation products, and shows good anti-pollution performance.
As shown in FIG. 8A, the results of our evaluation of the effect of different concentrations of DA on the electrocatalytic activity of Fe-N-C/CF microelectrodes using CV again indicate that Fe-N-C/CF microelectrodes have good electrocatalytic activity on DA. The applied potential is optimized through a CA test, and 0.2V is selected as the optimal potential when the DA is detected in consideration of the magnitude of current response and the interference problem of noise.
FIG. 8C shows the Fe-N-C/CF microelectrode vs. the voltage at N at the optimum of 0.2V (vs Ag/AgCl) 2 A typical current-time curve of different concentrations of DA was continuously added to saturated aCSF. FIG. 8D shows that the current and the DA concentration exhibit a good linear relationship, the detection range is 0.5 μ M to 577 μ M, and the detection limit is 0.22 μ M.
Example 5
(1) Preparation: the experimental animals are male Sprague-Dawley pure-breed rats (350-400 g), and are fed with free drinking water in a natural illumination period under the room temperature condition, and all animal experimental processes conform to animal feeding and experimental regulations of national center for Nano science. The rat is anesthetized by hydration chloral intraperitoneal injection (345mg/kg, ip), the head of the rat is fixed on a stereo positioning instrument, when the rat is fixed, the incisors of the mouse are firstly clamped on the incisor clamp of the adapter, the cross bar of the incisor clamp is lightly pressed, the height and the front and the back of the adapter are adjusted, so that the ear bars can conveniently enter the external auditory canal of the mouse, and the position of the incisor bar of the positioning instrument is adjusted to be lower than the horizontal line by 3.3 +/-0.4, namely the horizontal position of the skull is reached. The left hand holds up the mouse head, inserts the left side ear pole in the mouse duct, adjusts left and right side ear pole and makes the animal head keep in U type open-ended central point and put, locks fixed one side ear pole earlier, and the opposite side ear pole of later screwing makes the animal head can not rock, screws the incisor clamp screw simultaneously. Checking whether the fixation is successful: the middle of the nose, the head and the tail were not moved and the brain was visually observed. Hair at the site requiring surgery is removed with depilatory cream or razor. Then, the skin of the mouse head was cut with a scalpel, the cranium was opened, and the pia mater was removed.
(2) Living body assay H 2 O 2 . According to the previous literature reports [28,29] The Fe-N-C/CF microelectrode was inserted into the right cortex (AP ═ 3mm, L ═ 2mm, V ═ 1mm), the prepared miniature Ag/AgCl reference electrode was placed in the cerebral dura mater, and a platinum wire was used as a counter electrode inserted into the subcutaneous tissue of the brain. Through a silica capillary (L ═ 4cm,50 μm i.d.,375 μm o.d.), will contain 10mM H 2 O 2 The exogenous aCSF of (a) is microinjected into the local area of the brain where the microelectrode is implanted through the silica capillaries. The capillaries were implanted in the right cortex, parallel to the Fe-N-C/CF microelectrodes. The electrodes were fixed to the skull using acrylic dental cement. All local microinfusion was performed in the right cortex of rats. Due to the excellent catalytic activity of the Fe-N-C nanoenzyme on hydrogen peroxide, the sensitive detection of the hydrogen peroxide in vivo can be directly realized at a lower potential.
(3) And detecting the DA in vivo. Inserting the Fe-N-C/CF microelectrode into an volt gap (AP is 3mm, L is 2mm, and V is 1mm), placing the prepared miniature Ag/AgCl reference electrode into cerebral dura mater, and using a platinum wire as a counter electrode inserted into cerebral subcutaneous tissue. To stimulate DA release, 3M high K concentration was applied via silica capillaries (4 cm long, 50 μ M i.d.,375 μ M o.d.) + The exogenous aCSF is microinjected into the local area of the brain where the microelectrode is implanted through the silica capillary [32] Planting capillary tubesThe lodging is a threshold, parallel to the Fe-N-C/CF microelectrode. The electrodes were fixed to the skull using acrylic dental cement. DA was detected at a potential of 0.2V.
To verify that the Fe-N-C/CF microelectrode can be used for detecting H in vivo in real time 2 O 2 Content variation, Fe-N-C/CF microelectrodes were implanted in the right cortex of rats, the prepared miniature Ag/AgCl reference electrode was placed in the cerebral dura mater, and platinum wire was used as a counter electrode inserted into the subcutaneous tissue of the brain. Monitoring of H in rat brain by continuous microinjection of exogenous aCSF containing 10mM at optimal voltage 2 O 2 A change in (c). Continuous micro-perfusion was started around 240s while amperometrically recording the current response of the implanted Fe-N-C/CF microelectrodes. As a result, as shown in FIG. 9A, the baseline was relatively flat before the start of continuous micro-perfusion, and stopped after about 50s after the start of continuous micro-perfusion, and the current slowly reached a steady state again, indicating that the Fe-N-C/CF microelectrode was in vivo against H 2 O 2 Also has better response, and the sensing platform of the Fe-N-C/CF microelectrode can be used for the selective monitoring of hydrogen peroxide in vivo.
In order to verify that the Fe-N-C/CF microelectrode can be used for detecting the change of the DA content of a living body in real time, the Fe-N-C/CF microelectrode is implanted into a rat volt gap, and the change of the DA in the rat brain is monitored by continuously micro-perfusing exogenous aCSF with high K +. Beginning to perform micro-perfusion within about 125s, and simultaneously recording the current response of the implanted Fe-N-C/CF microelectrode by an ampere method; as a result, as shown in FIG. 9B, the baseline was relatively flat before the start of the micro-perfusion, and after the micro-perfusion was stopped, the current became large and slowly reached a plateau again, indicating that the Fe-N-C/CF microelectrode also responded well to DA in vivo.
Through diazotization grafting reaction, m-phenylenediamine polymerization reaction and Fe 3+ The Fe-N-C nano enzyme is synthesized in situ on the carbon fiber through a series of reactions such as anchoring, high-temperature pyrolysis and the like, and a series of characteristics such as SEM, XRD, XPS and the like prove that the Fe-N-C nano enzyme is successfully prepared. The carbon fiber microelectrode is prepared by using Fe-N-C nanoenzyme inherent enzyme-like activity to realize the representative cranial nerve chemical substance H 2 O 2 And the sensitive detection of DA reduces the reactionPotential, Fe-N-C/CF microelectrode pairs H 2 O 2 And DA have good current response and stability. In vivo experiments are carried out in the brain of the rat, and the preliminary verification proves that the prepared Fe-N-C/CF microelectrode can detect H in vivo 2 O 2 And changes in DA content. The great potential of the electrode material in vivo analysis is proved.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made to the present application by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A preparation method of Fe-N-C nano-enzyme in-situ modified carbon fiber is characterized by comprising the following steps:
(1) dissolving sulfanilic acid in ultrapure water, and slowly and sequentially dropwise adding pre-cooled NaOH solution, HCl solution and NaNO in ice water bath 2 Dispersing the pretreated carbon fibers into the solution, maintaining the low temperature for reaction, adding reducing Fe powder into the solution after the reaction, and stirring to obtain grafted carbon fibers;
(2) dissolving m-phenylenediamine in ultrapure water, adding concentrated hydrochloric acid, and then adding the grafted carbon fiber into the solution; slowly dropwise adding precooled ammonium persulfate and FeCl in sequence 3 A solution; controlling the temperature for a period of time at low temperature, and then heating for reaction; taking out, rotary steaming and drying at normal temperature; supplementing FeCl 3 Solution, rotary steaming and drying;
(3) and (3) placing the product obtained in the step (2) in a tube furnace, performing first high-temperature pyrolysis in an argon atmosphere, then performing acid washing, filtering, washing, drying, and performing second high-temperature pyrolysis after drying to obtain the Fe-N-C nanoenzyme in-situ modified carbon fiber.
2. The preparation method according to claim 1, wherein the pretreatment process of the carbon fiber is: the carbon fiber is desized, soaked in acetone solution for 24h, then ultrasonically treated and cleaned in ultrapure water for three times, and then dried in a vacuum drying oven.
3. The preparation method according to claim 1, wherein in the step (1), the sulfanilic acid is used in an amount of 0.5 to 1 mmol; the concentration of the NaOH solution is 1M, and the volume of the NaOH solution is 0.5-1 mL; the concentration of the HCl solution is 1M, and the volume of the HCl solution is 3-5 mL; NaNO 2 The concentration of the solution is 1M, and the volume is 0.5-1 mL; the dosage of the pretreated carbon fiber is 0.02-0.2 g.
4. The preparation method according to claim 1, wherein in the step (1), the low temperature is 0-3 ℃ and the reaction time is 1 h.
5. The method according to claim 1, wherein the amount of the reducible Fe powder used in step (1) is 0.1 to 0.2 g.
6. The method according to claim 1, wherein in the step (2), the amount of m-phenylenediamine is 1 to 2 g; the concentration and volume of the concentrated hydrochloric acid are 3-6 mL; the concentration of ammonium persulfate is 2M, and the volume of the ammonium persulfate is 10-20 mL; FeCl 3 The concentration of the solution is 1M, and the volume of the solution is 3-8 mL.
7. The preparation method according to claim 1, wherein in the step (2), the temperature is controlled at a low temperature of 0-3 ℃, after 8 hours, the temperature is raised to 7-8 ℃, and the reaction time is 12 hours; the rotary evaporation conditions are as follows: the temperature is controlled at 80 ℃ from 60 ℃ and the vacuum degree of-0.08 MPa; drying at normal temperature: drying in a vacuum drying oven at normal pressure for 12h at 100 ℃; in the step (2), FeCl is added 3 The volume of the solution is 1-10 mL.
8. The preparation method according to claim 1, wherein in the step (3), the temperature is 850-1000 ℃ for 1h during the first high-temperature pyrolysis; the temperature of the second high-temperature pyrolysis is 850-1000 ℃, and the time is 3 hours;
or, in the step (3), after the temperature of the tubular furnace is reduced after the first high-temperature pyrolysis, taking out the tubular furnace for pickling at 80 ℃ for 8 hours.
9. The Fe-N-C nanoenzyme in-situ modified carbon fiber prepared by the preparation method of any one of the preceding claims.
10. The use of the Fe-N-C nanoenzyme in-situ modified carbon fiber of claim 9 in the analysis and detection of brain neurochemicals.
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