CN110161094A - The method of free radical is quickly detected based on electrochemical sensor - Google Patents

The method of free radical is quickly detected based on electrochemical sensor Download PDF

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CN110161094A
CN110161094A CN201910599998.4A CN201910599998A CN110161094A CN 110161094 A CN110161094 A CN 110161094A CN 201910599998 A CN201910599998 A CN 201910599998A CN 110161094 A CN110161094 A CN 110161094A
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electrode
carboxylated
free radical
nps
ssdna
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CN110161094B (en
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孙冲
王道营
张牧焓
徐为民
邹烨
李鹏鹏
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Jiangsu Academy of Agricultural Sciences
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3278Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles

Abstract

The invention discloses a kind of methods that free radical is quickly detected based on electrochemical sensor, comprising the following steps: step 1 prepares carboxylated g-C3N4Nanoparticle;Step 2 constructs electrochemical sensor, and ssDNA/carboxylated-g-C is made3N4NPs/CS electrode;Step 3 establishes detection·The standard curve of OH free radical, prepares various concentration·OH free-atom aqueous solution, wherein by ssDNA/carboxylated-g-C3N4NPs/CS electrode is working electrode, uses methylene blue as signaling molecule;Step 4 is extracted in meat·OH free radical, utilizes ssDNA/carboxylated-g-C3N4NPs/CS electrode detects it.The method of the present invention is quick, high sensitivity, and selectivity is good, and the concentration of hydroxyl radical free radical is effectively detected.

Description

The method of free radical is quickly detected based on electrochemical sensor
Technical field
The present invention relates to a kind of meat quality detection methods.It is more particularly related to which a kind of passed based on electrochemistry The method that sensor quickly detects free radical.
Background technique
Active oxygen includes ultra-oxygen anion free radical (O2 ·-), singlet oxygen free radicals (1O2), 1,1- diphenyl -2-, three nitre Base phenylhydrazine free radical (DPPH·), hydroxyl radical free radical (·OH) etc., since its chemical activity is higher, cytodestructive can be caused Chain reaction.In active oxygen,·OH free radical is considered as most active and most harmful free radical, it and many substances such as sugar, Amino acid, phosphatide, nucleic acid and organic acid etc. react.These reactions can cause the peroxidating of lipid and protein, cause The loss of some essential amino acids, and generate some noxious materials.In addition, high concentration·Oxidative stress caused by OH free radical It can make cell mutation, apoptosis, lead to many diseases, such as hypertension, artery sclerosis, diabetes, cataract, arthritis, cancer. Therefore, in meat·The quantitative detection of OH free radical is very necessary.Currently, capillary electrophoresis, gas chromatography-mass spectrography, Liquid chromatography, chemoluminescence method, fluorescence and colorimetric method etc. are applied to detect·OH free radical.However, these methods it is time-consuming, It is cumbersome, and the instrument operator of profession is needed, it can not be widely applied in actual production.
Summary of the invention
It is an object of the invention to solve at least the above problems, and provide the advantages of at least will be described later.
It is a still further object of the present invention to provide a kind of method that free radical is quickly detected based on electrochemical sensor, energy The concentration of hydroxyl radical free radical is enough effectively detected, construction method is quick, and high sensitivity, selectivity are good, is not necessarily to preprocessing process;This Inventing the electrochemical sensor has good anti-interference to other active oxygen radicals.
In order to realize these purposes and other advantages according to the present invention, provide a kind of quick based on electrochemical sensor The method for detecting free radical, comprising the following steps:
Step 1 prepares carboxylated g-C3N4Nanoparticle, melamine and NaCl and KCl pulverize last calcining 4h, Salt frit is made;The salt frit is by grinding, desalting, and after being centrifuged and dialysing, solution obtained is lyophilized spare;
Step 2 constructs electrochemical sensor, carboxylated g-C prepared by the step 13N4Nanoparticle and chitosan It is fixed on glass-carbon electrode and carboxylated g-C is made3N4NPs/CS electrode later modifies ssDNA in carboxylated g-C3N4NPs/CS On electrode, ssDNA/carboxylated-g-C is made3N4NPs/CS electrode;
Step 3 establishes detection·The standard curve of OH free radical, prepares various concentration·OH free-atom aqueous solution, wherein will ssDNA/carboxylated-g-C3N4NPs/CS electrode is working electrode, uses methylene blue as signaling molecule;
Step 4 is extracted in meat·OH free radical, utilizes ssDNA/carboxylated-g-C3N4NPs/CS electrode pair It is detected.
Preferably, the specific steps of electrochemical sensor are constructed in the step 2 are as follows:
1) glass-carbon electrode pre-treatment;Glass-carbon electrode is successively polished to mirror surface with the alumina powder of 0.3 μm and 0.05 μm, Then dehydrated alcohol and ultrapure water successively ultrasound 30s are used, and is dried up at room temperature with pure nitrogen gas;
2) carboxylated g-C is prepared3N4NPs/CS electrode;Take the carboxylated g-C of 3mg/mL3N45 μ L of nano-particle solution is dripped to On electrode, at room temperature after natural drying, it is added dropwise on 1% chitosan solution to electrode of 5 μ L, naturally dry, makes carboxyl at room temperature Change g-C3N4NPs is fixed on electrode surface;
3) ssDNA/g-C is prepared3N4NPs/CS electrode;First carboxylated-g- is handled with EDC/NHS solution C3N4NPs/CS electrode, activated carboxyl, then, by carboxylated-g-C3N44 μM of 5 μ of ssDNA solution of NPs/CS electrode After L handles 40min, unbonded ssDNA is fallen with ultrapure water, electrode can obtain ssDNA/ after natural drying at room temperature carboxylated-g-C3N4NPs/CS electrode.
Preferably, the preparation method of standard solution described in the step 3 are as follows: generated using Fenton's reaction·OH is free Base, wherein the molar concentration rate of ferrous sulfate and hydrogen peroxide is 1:6, pH 3.5;With the ferrous sulfate of brand-new and the mistake of brand-new The OH free-atom aqueous solution of hydrogen oxide configuration various concentration.
Preferably, carboxylated g-C described in the step 13N4The preparation step of nanoparticle specifically: claim in proportion After taking melamine, NaCl and KCl mixed grinding uniform, powder is placed in 670 DEG C of calcining 4h, heating rate 10 in Muffle furnace ℃/min;After being cooled to room temperature, the salt frit of glassy yellow can be obtained;Salt frit is ground into uniform powder later, then with dilute Hydrochloric acid removes the salt in product, and product is re-dispersed into ultrapure water and is centrifuged again, removes big nitridation carbon particle by centrifugation; Supernatant is collected, is dialysed in ultrapure water with the bag filter that molecular weight is 500 to remove remaining Na+, K+, Cl-;Finally, by saturating Solution freeze-drying after analysis, can obtain carboxylated g-C3N4Nanoparticle.
Preferably, the ratio of melamine, NaCl and KCl are 4:1:1.2-1.3.
Preferably, molten using OH free radical of the square wave voltammetry to various concentration in the step 3 and step 4 Liquid and solution to be detected are detected.
The present invention is include at least the following beneficial effects: (1) carboxylated g-C prepared by the present invention3N4Nanoparticle has larger Specific surface area, preferable electric conductivity and water dispersible;(2) aptamer sensor that the present invention constructs is to hydroxyl radical free radical Detection, construction method is quick, and high sensitivity, selectivity are good, is not necessarily to preprocessing process, and hydroxyl radical free radical can be effectively detected Concentration;(3) present invention establishes the linear equation of detection hydroxyl radical free radical, and the range of linearity is wide, and detection limit is low;(4) anti-interference In terms of ability, electrochemical sensor of the present invention has good anti-interference to other active oxygen radicals.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this The research and practice of invention and be understood by the person skilled in the art.
Detailed description of the invention
Fig. 1 is g-C in the prior art3N4The transmission electron microscope picture of material;
Fig. 2 is carboxylated g-C of the present invention3N4The transmission electron microscope picture of nanoparticle;
Fig. 3 is carboxylated g-C of the present invention3N4The infrared spectrogram of nanoparticle;
Fig. 4 is carboxylated g-C of the present invention3N4The Zeta potential figure of nanoparticle;
Fig. 5 is the present invention (a) chitosan/GCE, (b) bulk-g-C in one embodiment3N4/chitosan/ GCE,(c)carboxylated-g-C3N4/chitosan/GCE and(d)ssDNA/carboxylated-g-C3N4/ The cyclic voltammogram of chitosan/GCE;
Fig. 6 is the present invention (a) chitosan/GCE, (b) bulk-g-C in one embodiment3N4/chitosan/ GCE,(c)carboxylated-g-C3N4/chitosan/GCE and(d)ssDNA/carboxylated-g-C3N4/ The impedance diagram of chitosan/GCE;
Fig. 7 is present invention O in one embodiment2 ·-,1O2, H2O2To ssDNA/carboxylated-g-C3N4/ The interference histogram of chitosan/GCE sensor;
Fig. 8 is present invention ssDNA/carboxylated-g-C in one embodiment3N4/ chitosan/GCE is not through With concentration·OH processing, in conjunction with the square wave voltammogram scanned after methylene blue;
Fig. 9 is the Fe of various concentration in one embodiment of the invention2+Linear relationship chart between response current.
Specific embodiment
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art referring to specification text Word can be implemented accordingly.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein are not precluded one or more The presence or addition of a other elements or combinations thereof.
The present invention provides a kind of method that free radical is quickly detected based on electrochemical sensor, comprising the following steps:
1. preparing carboxylated g-C3N4Nanoparticle
It takes 8.00g melamine to mix with 2.50g NaCl and 3.12g KCl to be fully ground in the agate mortar to uniform Afterwards, powder is placed in Muffle furnace and is calcined 4 hours for 670 DEG C, heating rate is 10 DEG C/min.After being cooled to room temperature, it can obtain bright orange The salt frit of color.Obtained salt frit is further processed: salt frit being ground into uniform powder first, then uses dilute hydrochloric acid The salt in product is removed, product is re-dispersed into ultrapure water and is centrifuged again, removes big nitridation carbon particle by centrifugation.It collects Supernatant is dialysed with the bag filter that molecular weight is 500 in ultrapure water to remove remaining Na+, K+, Cl-.Finally, after dialysing Solution freeze-drying, carboxylated azotized carbon nano particle can be obtained.
2. constructing electrochemical sensor
2-1. glass-carbon electrode pre-treatment
Glass-carbon electrode (GCE) is successively polished to mirror surface with 0.3 and 0.05 μm of alumina powder, then uses dehydrated alcohol It is successively 30 seconds ultrasonic with ultrapure water, and dried up at room temperature with pure nitrogen gas.
2-2. carboxylated g-C3N4The preparation of NPs/CS electrode
It takes the azotized carbon nano particle solution of 5 μ L, 3mg/mL to drip on electrode, at room temperature after natural drying, 5 μ L is added dropwise, On 1% chitosan (CS) solution to electrode, naturally dry, makes carboxylated g-C at room temperature3N4NPs is fixed on electrode surface.
2-3.ssDNA/g-C3N4The preparation of NPs/CS electrode
First carboxylated-g-C is handled with EDC/NHS (1:1) solution3N4NPs/CS electrode, activated carboxyl.Then, 5 μ L, 4 μM of ssDNA is by the amino of its end in conjunction with the azotized carbon nano particle of carboxylated.After 40min, ultrapure water is used Fall unbonded ssDNA, electrode can obtain ssDNA/carboxylated-g-C after natural drying at room temperature3N4NPs/CS electrode.
3. establishing detection·The standard curve of OH free radical
The configuration of 3-1. standard solution
The present invention is generated using Fenton's reaction·OH free radical: Fe2++H2O2→Fe3++(OH)-+ OH. ferrous sulfate and mistake The molar concentration rate of hydrogen oxide is 1:6, pH 3.5.Various concentration is configured with the ferrous sulfate of brand-new and the hydrogen peroxide of brand-new OH free-atom aqueous solution.
3-2. Specification Curve of Increasing
Present invention signaling molecule detected is methylene blue, and the reduction by being integrated to methylene blue on ssDNA can obtain To electrochemical signals.Due to·OH free radical has damage ssDNA chain, leads to the fracture of ssDNA, therefore, with various concentration· OH free radical removes processing ssDNA, different degrees of damage can be caused to ssDNA, so that ssDNA is integrated to the amount of methylene blue not Together, to generate different current-responsives.Peak point current i is recorded, according to the concentration relationship of current value and OH free radical, is established Linearity curve.
3-3. is extracted in meat·OH free radical prepares liquid to be detected in aforementioned manners, utilizes ssDNA/ of the present invention carboxylated-g-C3N4NPs/CS electrode detects it.
4. before being detected, ssDNA/carboxylated-g-C of the present invention3N4NPs/CS electrode also needs to carry out
4-1. chemical property detection: firstly, synthesis carboxylated azotized carbon nano particle by transmission electron microscope (TEM, HITACHI, Japan), Fourier Transform Infrared Spectroscopy (FTIR, VARIAN Cary 5000, the U.S.), ZETA current potential (ZP, Nano ZS90, Malvern instrument company, Britain), x-ray photoelectron spectroscopy (XPS, Thermo ESCALAB250Xi, the U.S.) technology pair It is characterized, it was demonstrated that material successfully synthesizes.Then, cyclic voltammetric (CV) and electrochemical impedance spectrometry (EIS) research material are utilized Chemical property.Using square wave voltammetry (SWV) research sensor to the electrochemical response of detection object, and to various concentration 's·OH free radical is detected.All electrochemical measurements of the present invention CHI760E electrochemical workstation (Shanghai, occasion China) into Row, three-electrode system: saturated calomel electrode is as reference electrode, and platinum electrode is used as to electrode, and glass-carbon electrode is as work electricity Pole.
As can be seen that two-dimension plane structure is presented in block-like carbonitride from Fig. 1 and Fig. 2, partial size is other in the micron-scale, with block The carbonitride of shape is compared, carboxylated g-C of the present invention3N4Nanoparticle is uniformly dispersed, and partial size is about 20nm, and electron microscope proves Carboxylated g-C3N4Nanoparticle successfully synthesizes.
As can be seen that 1706cm from Fig. 3 and Fig. 4-1The peak at place is the characteristic absorption peak of C=O, 1393cm-1And 1580cm-1The peak at place is the characteristic absorption peak of-COO, 3000cm-1To 3500cm-1The broad peak at place is the characteristic absorption peak of-OH He-NH.g- C3N4The Zeta potential value of material is -0.056mV, close to zero, and carboxylated g-C3N4The Zeta potential of nanoparticle be- 24mV shows elecrtonegativity.The above characterization illustrates carboxylated g-C3N4Nanoparticle successfully synthesizes.
As shown in Figure 5 and Figure 6, cyclic voltammetry of the present invention is in the 1mM [Fe (CN) containing 0.1M KCl6 ]3-/4-It is carried out in (1:1), sweeping speed is 100mV/s, and current potential is from -0.4V to 0.7V.Electrochemical impedance test is containing 0.1M KCl 5mM [Fe (CN)6]3-/4-It is carried out in (1:1).The electrochemical impedance figure of cyclic voltammogram and Fig. 6 from Fig. 5 can be seen that phase Than in g-C3N4Material, carboxylated g-C prepared by the present invention3N4Nanoparticle has preferable conductive capability and electrochemical response Ability since ssDNA electric conductivity is poor, causes impedance obviously to become larger, electric current becomes smaller, explanation after modifying upper ssDNA SsDNA is successfully modified on electrode.
The anti-interference detection of 4-2.
Anti-interference further is carried out to the electrochemical sensor of carboxylated g-C3N4 nanoparticle of the present invention preparation Analysis, in addition to·OH free radical, O2 ·-1O2, H2O2It also is all active oxygen radical common in meat, therefore, present invention selection These three free radicals are studied for interference experiment.Selecting the concentration of these three free radicals is·Ten times of OH number of free radical carry out Square wave voltammetric scan, record current changing value.Fig. 7 is to O respectively2 ·-,1O2, H2O2The Interference Detection of progress, each sample detection 3 times.Wherein △ I=I0- I, I0Represent ssDNA not by·The current value obtained when OH processing in conjunction with methylene blue, I represent warp·OH The current value for combining methylene blue to obtain after processing.As shown in fig. 7, the experimental results showed that, these three free radicals are compared to hydroxyl Free radical, electric current do not have significant change, and inventor has found under study for action, and OH free radical has Gao Te to ssDNA chain break It is anisotropic.Therefore, the electrochemical sensor of carboxylated g-C3N4 nanoparticle preparation of the present invention has preferable anti-interference energy Power.
Embodiment 1
Fig. 8 shows ssDNA/carboxylated-g-C3N4/ chitosan/GCE electrode is through 12 kinds of concentration·OH solution Processing, in conjunction with the square wave voltammogram scanned after methylene blue.Wherein the concentration of OH solution is respectively: (a) untreated, (b) 0.002mM, (c) 0.01mM, (d) 0.05mM, (e) 0.1mM, (f) 0.3mM, (g) 0.5mM, (h) 1mM, (i) 2mM, (j) 4mM, (k)8mM and(l)10mM.Top-down 12 curves are corresponding in Fig. 8·OH solution concentration is successively dropped to from (a) concentration (l) concentration.Wherein, Fe is for example used in the embodiment of the present invention 12+Concentration represents·The concentration of OH can be seen that from Fig. 8 and Fig. 9 With Fe2+The increase of concentration,·OH concentration increases, more to the fracture of ssDNA, reduces in conjunction with the amount of methylene blue, current-responsive It reduces, △ I becomes larger.It can see Fe2+There is good linear relationship between current variation value, linear equation is △ I (μ A) =0.9512log [Fe2+]+2.3941(R2=0.9973), the range of linearity is 2 × 10-6-1.0×10-2M, detection are limited to 8 × 10-7M (S/N=3).Based on the linear equation, in shrimp·OH number of free radical is detected, and the results are shown in Table 1.
Embodiment 2
The step of using such as embodiment 1, in chicken·OH number of free radical is detected, and the results are shown in Table 1.
Embodiment 3
The step of using such as embodiment 1, in sausage·OH number of free radical is detected, and the results are shown in Table 1.
1 electrochemical sensor detected value of table (μm ol/g)
Institute's value is that parallel five measurements of each sample obtain, and take its average value.
Comparative example
Using analysis instrument respectively in shrimp, chicken and sausage·OH number of free radical is detected, and the results are shown in Table 2.
2 analysis instrument reference value of table (μm ol/g)
Institute's value is that parallel five measurements of each sample obtain, and take its average value.
From Tables 1 and 2: the present invention is measured using electrochemical sensor prepared by carboxylated g-C3N4 nanoparticle Data are matched with the data result measured in analysis instrument.Therefore the electrochemical aptamer sensor, which has, potentially actually answers With value.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited In specific details and legend shown and described herein.

Claims (6)

1. quickly detecting the method for free radical based on electrochemical sensor, which comprises the following steps:
Step 1 prepares carboxylated g-C3N4Nanoparticle pulverizes melamine and NaCl and KCl last calcining 4h, system Obtain salt frit;The salt frit is by grinding, desalting, and after being centrifuged and dialysing, solution obtained is lyophilized spare;
Step 2 constructs electrochemical sensor, carboxylated g-C prepared by the step 13N4Nanoparticle and chitosan are fixed Carboxylated g-C is made on glass-carbon electrode3N4NPs/CS electrode later modifies ssDNA in carboxylated g-C3N4NPs/CS electricity On extremely, ssDNA/carboxylated-g-C is made3N4NPs/CS electrode;
Step 3 establishes detection·The standard curve of OH free radical, prepares various concentration·OH free-atom aqueous solution, wherein will ssDNA/carboxylated-g-C3N4NPs/CS electrode is working electrode, uses methylene blue as signaling molecule;
Step 4 is extracted in meat·OH free radical, utilizes ssDNA/carboxylated-g-C3N4NPs/CS electrode is to it It is detected.
2. the method for free radical is quickly detected based on electrochemical sensor as described in claim 1, which is characterized in that the step The specific steps of electrochemical sensor are constructed in rapid two are as follows:
1) glass-carbon electrode pre-treatment;Glass-carbon electrode is successively polished to mirror surface with the alumina powder of 0.3 μm and 0.05 μm, then With dehydrated alcohol and ultrapure water successively ultrasound 30s, and dried up at room temperature with pure nitrogen gas;
2) carboxylated g-C is prepared3N4NPs/CS electrode;Take the carboxylated g-C of 3mg/mL3N45 μ L of nano-particle solution drips to electrode On, at room temperature after natural drying, it is added dropwise on 1% chitosan solution to electrode of 5 μ L, naturally dry, makes carboxylated g- at room temperature C3N4NPs is fixed on electrode surface;
3) ssDNA/g-C is prepared3N4NPs/CS electrode;First carboxylated-g-C is handled with EDC/NHS solution3N4NPs/CS Electrode, activated carboxyl, then, by carboxylated-g-C3N4NPs/CS electrode is handled with 4 μM of 5 μ L of ssDNA solution After 40min, unbonded ssDNA is fallen with ultrapure water, electrode can obtain ssDNA/ after natural drying at room temperature carboxylated-g-C3N4NPs/CS electrode.
3. the method for free radical is quickly detected based on electrochemical sensor as described in claim 1, which is characterized in that the step The preparation method of standard solution described in rapid three are as follows: generated using Fenton's reaction·OH free radical, wherein ferrous sulfate and peroxidating The molar concentration rate of hydrogen is 1:6, pH 3.5;Various concentration is configured with the ferrous sulfate of brand-new and the hydrogen peroxide of brand-new OH free-atom aqueous solution.
4. the method for free radical is quickly detected based on electrochemical sensor as described in claim 1, which is characterized in that the step Carboxylated g-C described in rapid one3N4The preparation step of nanoparticle specifically: it is mixed to weigh melamine, NaCl and KCl in proportion After closing grinding uniformly, powder is placed in 670 DEG C of calcining 4h in Muffle furnace, heating rate is 10 DEG C/min;It, can after being cooled to room temperature Obtain the salt frit of glassy yellow;Salt frit is ground into uniform powder later, then removes the salt in product with dilute hydrochloric acid, from Product is re-dispersed into ultrapure water and is centrifuged again by the heart, removes big nitridation carbon particle;Supernatant is collected, is with molecular weight 500 bag filter is dialysed in ultrapure water to remove remaining Na+, K+, Cl-;Finally, the solution after dialysis is lyophilized, carboxylic can be obtained Base g-C3N4Nanoparticle.
5. the method for free radical is quickly detected based on electrochemical sensor as claimed in claim 4, which is characterized in that melamine The ratio of amine, NaCl and KCl is 4:1:1.2-1.3.
6. the method for free radical is quickly detected based on electrochemical sensor as described in claim 1, which is characterized in that the step Rapid three and step 4 in, using square wave voltammetry to various concentration·OH free-atom aqueous solution and solution to be detected are detected.
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CN112697826A (en) * 2020-12-07 2021-04-23 武汉科技大学 CaO-Al2O3Method for measuring free radicals of oxide-containing melt
CN112697826B (en) * 2020-12-07 2023-04-14 武汉科技大学 CaO-Al 2 O 3 Method for measuring free radicals of oxide-containing melt
CN113003668A (en) * 2021-02-02 2021-06-22 同济大学 Method for synchronously removing PPCPs (pentatricopeptide repeats) by inactivating urine by using singlet oxygen generated in situ by three-dimensional electrochemical reactor
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CN113109288B (en) * 2021-03-11 2021-12-17 首都师范大学 Method for rapidly detecting free radicals by utilizing terahertz spectrum
CN115180600A (en) * 2022-08-03 2022-10-14 重庆工商大学 Method for preparing nanosheet with large area-diameter ratio
CN115201309A (en) * 2022-08-13 2022-10-18 昆明理工大学 Preparation method and application of hydroxyl radical electrochemical sensor
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