CN108535350A - The detection method and detection device of acetone aldehyde in honey - Google Patents

The detection method and detection device of acetone aldehyde in honey Download PDF

Info

Publication number
CN108535350A
CN108535350A CN201810423587.5A CN201810423587A CN108535350A CN 108535350 A CN108535350 A CN 108535350A CN 201810423587 A CN201810423587 A CN 201810423587A CN 108535350 A CN108535350 A CN 108535350A
Authority
CN
China
Prior art keywords
electrode
honey
carbon
carbon nanotube
glass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810423587.5A
Other languages
Chinese (zh)
Other versions
CN108535350B (en
Inventor
吴小波
张文娟
文阳平
曾志将
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangxi Agricultural University
Original Assignee
Jiangxi Agricultural University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangxi Agricultural University filed Critical Jiangxi Agricultural University
Priority to CN201810423587.5A priority Critical patent/CN108535350B/en
Publication of CN108535350A publication Critical patent/CN108535350A/en
Application granted granted Critical
Publication of CN108535350B publication Critical patent/CN108535350B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • G01N27/416Systems
    • G01N27/48Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses the detection methods and detection device of acetone aldehyde in a kind of honey comprising following steps:S1, detecting electrode of purchasing;S2, the detecting electrode is modified using carbon nanotube;S3, using being detected to honey by the detecting electrode that the carbon nanotube is modified, obtain the pyroracemic aldehyde content data in honey.The present invention provides a kind of methods and detection device detecting acetone aldehyde in honey using electrochemical method, it mainly analyzes that quick, at low cost, easy to operate, high sensitivity, stability is good, good selective using by glass-carbon electrode that carboxy-functionalized multi-walled carbon nanotube is modified to be detected to the acetone aldehyde in honey, having.

Description

The detection method and detection device of acetone aldehyde in honey
Technical field
The present invention relates to bee raising fields, and in particular to the detection method of acetone aldehyde and detection dress in a kind of honey It sets.
Background technology
There is one kind on the market and originate from Zelanian Manuka honey, with very strong antibacterial activity, active material One of be exactly pyroracemic aldehyde.It is further explored since the applicable value of pyroracemic aldehyde obtains, the measurement of acetone aldehyde has been carried out greatly Quantifier elimination, common technique are to use such as high performance liquid chromatography, ion pair chromatography chromatographic technique and mass spectrography, capillary Electrophoresis tube method of testing etc. is detected.However these methods are due to its specific standardization program, complicated sample pretreatment process And it is long to cause detection process to take, in addition, since above-mentioned technology must arrange in pairs or groups expensive instrument, such as all kinds of chromatographs, Mass spectrograph etc. is used, therefore its testing cost is excessively high, is not suitable for promoting.
Invention content
For the above-mentioned prior art the problem of, the present invention provides in a kind of detection honey using electrochemical method The method and detection device of acetone aldehyde, mainly using the glass modified by carboxy-functionalized multi-walled carbon nanotube Carbon electrode is detected the acetone aldehyde in honey, have analyze quick, at low cost, easy to operate, high sensitivity, Stability is good, good selective.
The technical solution adopted by the present invention to solve the technical problems is as follows:
On the one hand, a kind of detection method of acetone aldehyde in honey is provided, which is characterized in that include the following steps:
S1, detecting electrode of purchasing;
S2, the detecting electrode is modified using carbon nanotube;
S3, using being detected to honey by the detecting electrode that the carbon nanotube is modified, obtain in honey Pyroracemic aldehyde content data.
Preferably, step S1 includes:
S11, the bare electrode surface of the detecting electrode is polishing to smooth, is then rinsed well with deionized water;
And S12, use in ultrasonic wave that deionized-distilled water, absolute ethyl alcohol, deionized-distilled water is in step S11 successively The bare electrode of acquisition is handled, and each processing procedure used time is 4-10 minutes, is then dried at room temperature.
Preferably, in step S1, the detecting electrode includes glass-carbon electrode, uses carbon nanotube to the glass in step S2 Carbon electrode is modified.
Preferably, the step S2 includes:
S21,0.15-0.45mg mL are made-1Cmc soln and 0.8-1.2mg mL-1Carboxymethyl it is fine Tie up element-carbon nano tube suspension;
S22, the chitosan solution for preparing 0.15-0.25%, and by the carboxymethyl cellulose-carbon nano tube suspension With chitosan solution by volume 10:1 is mixed, to obtain mixed liquor;
And S23, the mixed liquor of 3-8 μ L dropped on the glass-carbon electrode and dried, carbon nanotube is thus completed to institute State the modification of glass-carbon electrode.
Preferably, the step S3 includes:
S31, honey sample is diluted using 0.1mol/L phosphate buffers, is used in combination NaOH solution will be after dilution Honey sample pH value of solution is adjusted to 9-11;
S32, using the detecting electrode modified by the carbon nanotube, lied prostrate according to square wave voltammetry and/or cycle Peace method is that 9-11 honey sample solution is detected to after dilution, pH, obtains the pyroracemic aldehyde content data in honey.
Preferably, the honey sample pH value of solution after dilution is adjusted to 10 with NaOH solution in step S31.
On the other hand, a kind of detection device of acetone aldehyde in honey is also provided comprising repaiied by carbon nanotube The detecting electrode of decorations.
Preferably, the step of detecting electrode is modified by carbon nanotube include:
S100,0.15-0.45mg mL are made-1Cmc soln and 0.8-1.2mg mL-1Carboxymethyl Cellulose-carbon nano tube suspension;
S101, the chitosan solution for preparing 0.15-0.25%, and by the carboxymethyl cellulose-carbon nano tube suspension With chitosan solution by volume 10:1 is mixed, to obtain mixed liquor;
And S102, the mixed liquor of 3-8 μ L dropped on the glass-carbon electrode and dried, carbon nanotube is thus completed to institute State the modification of glass-carbon electrode.
Preferably, the detecting electrode includes glass-carbon electrode.
The present invention constructs a kind of novel simple based on Chitosan-carboxymethyl cellulose-multi-walled carbon nanotube electrode Electrochemical sensing platform, and the assay of honey pyroracemic aldehyde is used it for, with high sensitivity, detection limit is low, repeatability And stability is good, it is reactionless to chaff interferent the advantages that.
Description of the drawings
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for For those of ordinary skill in the art, without creative efforts, other are can also be obtained according to these attached drawings Attached drawing.
Fig. 1 is the step flow chart of honey pyroracemic aldehyde detection method of content in embodiment one;
Fig. 2 be the application in chitosan-methylcellulose-multi-walled carbon nanotube, methylcellulose-multi-walled carbon nanotube with And the scanning electron microscope (SEM) photograph of chitosan;
Fig. 3 be the application in chitosan-methylcellulose-multi-walled carbon nanotube, methylcellulose-multi-walled carbon nanotube with And the infrared spectrogram of chitosan;
Fig. 4 is to use bare electrode, methylcellulose-multi-walled carbon nanotube/glass-carbon electrode and chitosan-first in the application respectively The square wave voltammogram of base cellulose-multi wall carbon carbon nanotube/glass-carbon electrode detection pyroracemic aldehyde;
Fig. 5 A are in the application in the phosphate buffer solution (PBS) of different pH value, with chitosan-methylcellulose- The square wave voltammogram of multi wall carbon carbon nanotube/glass-carbon electrode detection pyroracemic aldehyde;
Fig. 5 B are pH value in the application to the influence curve figure of Ipa in the electro-oxidizing-catalyzing of pyroracemic aldehyde;
Fig. 5 C are pH value in the application to the influence curve figure of Epa in the electro-oxidizing-catalyzing of pyroracemic aldehyde;
Fig. 6 A are pyroracemic aldehyde chitosan-methylcellulose-multi wall carbon carbon nanotube/glass carbon of various concentration in the application The square wave voltammogram of electrode detection;
Fig. 6 B are the linear relationship chart between peak point current and acetone aldehyde concentration in the application;
Fig. 7 A are chitosan-methylcellulose-multi wall carbon carbon nanotube/glass-carbon electrode in the application in 0.1mol/L PBS In reproducibility;
Fig. 7 B are chitosan-methylcellulose-multi wall carbon carbon nanotube/glass-carbon electrode in the application in 0.1mol/L PBS In repeatability.
Specific implementation mode
In order to make the purpose of the present invention, technical solution and advantage be more clearly understood, below in conjunction with drawings and examples, The present invention will be described in further detail.It should be understood that specific embodiment described herein is only used for explaining this hair It is bright, it is not intended to limit the present invention.
Embodiment one:
As shown in Figure 1, the detection method of acetone aldehyde includes the following steps in the honey of the present invention:
S1, detecting electrode of purchasing, in the present embodiment, the detecting electrode is three-electrode system comprising:As work electricity The glass-carbon electrode (GCE) of pole, as the saturation KCl calomel electrodes (SCE) of reference electrode and as the platinum filament of auxiliary electrode (Pt);Specifically, the step S1 includes:
S11, by the bare electrode surface of the glass-carbon electrode on chamois leather with 0.05 μm of Al2O3Grounds travel be polishing to it is smooth, Then it is rinsed well with deionized water;
S12, successively with deionized-distilled water, absolute ethyl alcohol, deionized-distilled water to the bare electrode that is obtained in step S11 into Row ultrasonic cleaning is handled, and each processing procedure used time is 4-10 minutes (preferably 5 minutes), is then dried at room temperature;
S2, using carbon nanotube (CNTs) (preferably multi-walled carbon nanotube (fMWCNTs)) in the detecting electrode Glass-carbon electrode is modified;The glass-carbon electrode is modified using carbon nanotube in step S2, detailed process includes:
S21, carboxymethyl cellulose is dissolved completely in the obtained 0.3mg mL of distilled water-1Cmc soln, with And 1mg multi-walled carbon nanotubes are dispersed in cmc soln described in 1.0mL, prepare 1mg mL-1Carboxymethyl Cellulose-multi-walled carbon nanotube (CMC-fMWCNT) suspension is used in combination ultrasonic agitation uniform;
S22,0.1g chitosans are dispersed in 2% acetic acid (HAc) solution and prepare 0.2% chitosan (CS) solution, and will Carboxymethyl cellulose-the carbon nano tube suspension and chitosan solution by volume 10:1 is mixed, to be mixed Liquid;
S23, the mixed liquor prepared in 5 μ L steps S22 is dropped on the glass-carbon electrode and is dried, thus completed carbon and receive Modification of the mitron to the glass-carbon electrode obtains chitosan-methylcellulose-multi wall carbon carbon nanotube/glass-carbon electrode (CS- CMC-fMWCNTs/GCE);
S24, the phosphate-buffered that the chitosan-methylcellulose-carbon nano tube/glass-carbon electrode is placed on to 0.1mol/L Stirring 55-65s (preferably 60s) in molten (PBS) (pH10.0);The pyroracemic aldehyde solution of predetermined concentration is added to by liquid-transfering gun In container containing 5mL 0.1mol/L PBS, and acetone aldehyde is detected according to square wave voltammetry (SWVs), with complete The electrochemical gaging of the pairs of chitosan-methylcellulose-carbon nano tube/glass-carbon electrode;
And S3, using being detected to honey by the detecting electrode that the carbon nanotube is modified, obtain honey In pyroracemic aldehyde content data;Specifically, the step S3 includes:
S31, honey sample is diluted using 0.1mol/L phosphate buffers, is used in combination NaOH solution will be after dilution Honey sample pH value of solution is adjusted to 10;In the present embodiment, three kinds of different honey samples are obtained from Agricultural University Of Jiangxi's apiary: Lime tree honey, Chinese scholartree honey and jujube tree honey, wherein lime tree honey sample is diluted 10 times respectively with 0.1mol/L PBS, Chinese scholartree honey sample is diluted 100 times, jujube tree honey sample is diluted 1000 times, is used in combination NaOH solution by all samples solution tune It is 10 to save to pH;
S32, using the glass-carbon electrode modified by the carbon nanotube, lied prostrate according to square wave voltammetry and/or cycle Peace method is detected honey sample (honey sample that the pH after dilution the is 10) solution obtained in step S31, obtains honey In pyroracemic aldehyde content data.
Embodiment two:
The present embodiment the difference is that only with embodiment one, and in step S21,0.15mg mL are made-1Carboxymethyl it is fine The plain solution of dimension and 0.8mg mL-1Carboxymethyl cellulose-multi-walled carbon nanotube (CMC-fMWCNT) suspension;Step S22 In, prepare 0.15% chitosan (CS) solution;In step S23, the mixed liquor prepared in 3 μ L steps S22 is dropped in into the glass On carbon electrode and dry;In step S31, the honey sample pH value of solution after dilution is adjusted to 9 with NaOH solution.
Embodiment three:
The present embodiment the difference is that only with embodiment one, and in step S21,0.45mg mL are made-1Carboxymethyl it is fine The plain solution of dimension and 1.2mg mL-1Carboxymethyl cellulose-multi-walled carbon nanotube (CMC-fMWCNT) suspension;Step S22 In, prepare 0.25% chitosan (CS) solution;In step S23, the mixed liquor prepared in 8 μ L steps S22 is dropped in into the glass On carbon electrode and dry;In step S31, the honey sample pH value of solution after dilution is adjusted to 11 with NaOH solution.
Carbon nanotube (CNTs) is as common one of carbon nanomaterial, with good electricity, chemistry, machinery and knot Structure performance fabulous can modify electrode.Since it has many excellent performances, such as high conductivity, big activity Surface area is easy the surface changed, catalytic activity, excellent chemical stability and good biocompatibility, nowadays wide It is general to be used in electrochemical sensor.
Carboxymethyl cellulose (CMC) is a kind of important cellulose derivative with good aqueous solubility, since it has two Parent's property, environment friendly, biocompatibility is non-toxic, good film forming and hydrophily, therefore as the poly- electricity of polysaccharide anion Solution matter is widely used in many fields.CMC can improve electro-catalysis ability adhesive capacity and the sensitivity of composite material, these So that CMC has prodigious advantage in electrochemical sensor application aspect.In addition, carboxymethyl cellulose functionalized carbon nano-tube exists The mixing of with good stability and dissolubility in water, CMC and CNTs can improve the dispersibility of CNTs.It is excellent in the present embodiment Select CMC dispersing Nano carbon tubes.
Chitosan (CS) is the deacetylated derivative of chitin, high molecular weight material, the second abundant natural biological polymerization Object is typically found in ocean crustacean shell and fungal cell wall, and water-soluble solution, chitosan can be used for different applications Such as make hydrogel, film, fiber or sponge.(cellulose, starch, galactomannan are poly- better than other compound of polysaccharide for chitosan Sugar etc.) the advantages of to be its chemical constitution allow in the positions C-2 to carry out specific modification in simple cases, so as to introduce spy Determine group to be used for designed for the selected polymer applied.
Chitosan-methylcellulose-multi-walled carbon nanotube (CS-CMC-fMWCNTs), methylcellulose-are shown in Fig. 2 Scanning electron microscope (SEM) figure of multi-walled carbon nanotube (CMC-fMWCNTs) and chitosan (CS), C figures are shown original in Fig. 2 CS structures, it can be seen that the circular configuration that many chitosan nanos are constituted.Original fMWCNTs is loose filament, curved Bent tied up in knots, and original CMC is smooth, close and uniform structure, so after CMC is added in fMWCNTs, As shown in the B figures in Fig. 2, CMC is adhered to the surfaces fMWCNTs well;CS adherency or embedded is shown in A figures in Fig. 2 To after in fMWCNTs, CS-CMC-fMWCNTs nanotube reticular structures are formed together with CMC simultaneously.
Chitosan-methylcellulose-multi-walled carbon nanotube (CS-CMC-fMWCNTs), methylcellulose-are shown in Fig. 3 The infrared spectrogram of multi-walled carbon nanotube (CMC-fMWCNTs) and chitosan (CS).From the spectrogram of CS, (i.e. the c of Fig. 3 is bent Line) in it can be seen that, in 3440cm-1Left and right is that-OH stretching vibration absworption peaks and the stretching vibration absworption peak of-NH are Chong Die and broadening Multi-absorption peak, in chitosan molecule there is in a large amount of chain, interchain hydrogen bond, because hydrogen bond length and it is strong and weak differ, make Its flexible peak appears in a wider frequency range, causes peak wider.In 2870cm-1Place is the stretching vibration absworption peak of C-H, 1420cm-1Place is=CH2Bending and-CH3Absorption peak is deformed, CS is in 1590-1660cm-1The middle strong absworption peak at place is curved in the faces NH Qu Zhendong, 663cm-1The weak peak at place is wagging vibration absorption peak.In the spectrogram (i.e. the b curves of Fig. 3) of CMC-fMWCNTs In, due to O-H stretching vibrations, in 3454cm-1There is broad peak in left and right.And 1441cm-1It is flexible that C=O in carboxylic group occurs in place Vibration, 1644cm-1It is nearby the C-O stretching vibrations in carboxylic group.CS-CMC-fMWCNTs composite materials spectrogram (i.e. The c curves of Fig. 3) in, CS characteristic absorption peak intensities obviously die down, this shows in the presence of CMC, exists between CS and fMWCNTs Strong interaction.
In addition, the application has also been relevant comparative to Different electrodes for the oxidation response of pyroracemic aldehyde, concrete outcome is such as Shown in Fig. 4, which show in the 0.1mol/LPBS of pH10, use bare electrode (Bare/GCE), methylcellulose-more respectively Wall carbon nano tube/glass-carbon electrode (CS-CMC-fMWCNTs/GCE) and chitosan-methylcellulose-multi wall carbon carbon nanotube/glass Carbon electrode (CS-CMC-fMWCNTs/GCE) detectable concentration is the square wave voltammogram of the pyroracemic aldehyde of 0.32 μm of ol.
Only display is there are one small pyroracemic aldehyde oxidation peak in bare electrode figure, and CMC-fMWCNTs/GCE electrodes with it is naked Electrode is compared, and the oxidation response current of pyroracemic aldehyde has slight increase, this is because the fMWCNTs with high conduction performance promotes The transfer of electronics.However, for CS-CMC-fMWCNTs/GCE, it is observed that the oxidation of pyroracemic aldehyde at about -0.86V Electric current has significant enhancing, makes after mainly being modified on GCE due to CS-CMC-fMWCNTs nanocomposites The relative surface area for obtaining electrode increases, and peak current is caused to be remarkably reinforced, meanwhile, there is no reduction peak in reverse scanning, shows The oxidation of pyroracemic aldehyde is irreversible procedure at the CS-CMC-fMWCNTs/GCE, and result clearly illustrates CS-CMC- as a result, FMWCNTs nanocomposites have good catalytic performance to the electrochemical oxidation of pyroracemic aldehyde.
Further, to CS-CMC-fMWCNTs, pyroracemic aldehyde is electrochemical at various ph values with SWVs research pH value by the application The influence that scholarship and moral conduct is.Fig. 5 A show the volt-ampere response that 160 μM of pyroracemic aldehydes are detected within the scope of the pH of 7-12.Fig. 5 B show sun Relationship of the pole peak point current (Ipa) between pH value.The result shows that with the increase of pH value, the peak value of pyroracemic aldehyde is 10 in pH When reach maximum value, drastically decline with the increase of pH value later.Therefore, it is selected the honey sample after dilution in the application PH value of solution is adjusted to 10 as optimal pH conditions.In addition, Fig. 5 C show relationship of the spike potential (Epa) between pH value, from In as can be seen that with solution ph increase, Epa may infer that there are proton participations linearly to negative potential linear movement The electrochemical process of pyroracemic aldehyde.Relationship between Epa and pH is according to Nernst equations:
Wherein m is the proton number for participating in electrochemical process, it is from Epa slopes to being obtained in pH value;It can be with from Fig. 5 C Find out, the slope of dEpa/dpH is -0.034, so the ratio of m/n is about 1, it means that the quantity of electronics and proton is identical , therefore, the electrode reaction of methyl-glyoxal is related to diproton and bielectron process at CS-CMC-fMWCNTs.
Also SWVs technique studies is used to be detected with CS-CMC-fMWCNTs/GCE nano-complex modified electrodes in the application The pyroracemic aldehyde of various concentration.Fig. 6 A show peak change feelings when detecting various concentration pyroracemic aldehyde with CS-CMC-fMWCNTs/GCE Condition, the acetone aldehyde concentration from a to j is respectively 4.8,8,16,48,80,160,320,480,640 and 800 μM, wherein can see Go out, peak current value increases with the increase of acetone aldehyde concentration, and then peak value display electric current and acetone aldehyde concentration is good in Fig. 6 B Good linear relationship.In addition, when CS-CMC-fMWCNTs/GCE detects various concentration pyroracemic aldehyde, detection limit (LOD) and quantitative limit (LOQ) it is the slope of calibration curve to calculate separately as 3s/m and 10s/m, wherein m, and s is that sample is not added under the same conditions The standard deviation of duplicate measurements when analyte, according to correlation formula, it is respectively 0.21 μM and 0.7 μ that can calculate LOD and LOQ M, it can be seen that, the satisfactory range of linearity can get to detect pyroracemic aldehyde using CS-CMC-fMWCNTs/GCE in the application It is limited with detection, testing cost is low, high sensitivity, and the quantitative electrochemical that can be used for pyroracemic aldehyde measures.
The application further studies the reproducibility, repeatability and stability of CS-CMC-fMWCNTs/GCE.Reproducibility its It is to be modified by different to six roots of sensation glass-carbon electrodes under same steps (i.e. step S2), obtains corresponding CS-CMC- Then fMWCNTs/GCE observes what it respectively realized the response condition of the pyroracemic aldehyde of 48 μm of ol/L.Specifically, such as Fig. 7 A Shown, it is 3.18% to standard deviation (RSD) to be calculated in figure;In addition, using identical CS-CMC-fMWCNTs/GCE 25 retests are carried out to 48 μm of ol/L pyroracemic aldehydes, measure the stability of modified electrode, be calculated to standard deviation (RSD) be about 2.77%, it is above-mentioned statistics indicate that, CS-CMC-fMWCNTs/GCE is with good stability to the measurement of pyroracemic aldehyde And repeatability.
Due to there are many substances (amino acid, carbohydrate, inorganic ions, organic acid etc.) in actual honey sample, It can generate certain interference to pyroracemic aldehyde detection micro in actual sample, therefore the application is investigated above-mentioned interfering substance Influence to Electrochemical Detection trace acetone aldehyde.Specifically, the application uses several chaff interferents of SWVs technique studies to pyroracemic aldehyde The influence of detection.Under the optimal conditions of the studies above (such as pH=10), it is separately added into 48 μm of ol/L pyroracemic aldehyde samples Fructose, sodium citrate, tryptophan, sodium acetate are as chaff interferent, with CS-CMC-fMWCNTs/GCE to the acetone containing chaff interferent Aldehyde sample is detected.As shown in table 1, the peak current of pyroracemic aldehyde responds no significant changes, signal intensity substantially all 5% with Under, it is indicated above CS-CMC-fMWCNTs/GCE and the measurement of pyroracemic aldehyde is had good selectivity.
The influence of disturbance object pair 48 μM/L pyroracemic aldehyde peak point currents is added in table 1
Table 2 shows in step S3 the detected value of three kinds of different honey sample pyroracemic aldehydes and adds into above-mentioned three kinds of honey The actual measured amount for adding the pyroracemic aldehydes (16 μm of ol/L, 160 μm of ol/L) of doses pyroracemic aldehyde afterwards, it can be seen that showing all bees The rate of recovery of sweet sample is in the range of 89.9-108.5%, and RSD values are all within 5%, hence it is demonstrated that the detection of the application Method is sufficient to the pyroracemic aldehyde quantitative analysis in practical honey sample.
The detection of acetone aldehyde and the rate of recovery in 2 honey of table
Example IV:
The present embodiment additionally provides a kind of detection device that can realize above-mentioned detection method comprising is carried out by carbon nanotube The detecting electrode of modification, the detecting electrode include glass-carbon electrode, and the step that the detecting electrode is modified by carbon nanotube Suddenly include:
S100,0.15-0.45mg mL are made-1Cmc soln and 0.8-1.2mg mL-1Carboxymethyl Cellulose-carbon nano tube suspension;
S101, the chitosan solution for preparing 0.15-0.25%, and by the carboxymethyl cellulose-carbon nano tube suspension With chitosan solution by volume 10:1 is mixed, to obtain mixed liquor;
And S102, the mixed liquor of 3-8 μ L dropped on the glass-carbon electrode and dried, carbon nanotube is thus completed to institute State the modification of glass-carbon electrode.
It should be noted that the technical characteristic in above-described embodiment one to three can carry out arbitrary combination, and combines and obtain skill Art scheme all belongs to the scope of protection of the present invention.
In conclusion the present invention construct a kind of honey pyroracemic aldehyde detection method based on CS-CMC-fMWCNTs/GCE and Device, with detection sensitivity height, detection limit is low, and repeatability and stability are good, it is reactionless to chaff interferent the advantages that, can be Pyroracemic aldehyde is successfully detected in 0.5 to 80 μM of the range of linearity, and low detection is limited to 0.21 μM.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.

Claims (9)

1. the detection method of acetone aldehyde in a kind of honey, which is characterized in that include the following steps:
S1, detecting electrode of purchasing;
S2, the detecting electrode is modified using carbon nanotube;
S3, using being detected to honey by the detecting electrode that the carbon nanotube is modified, obtain the acetone in honey Aldehyde data.
2. detection method according to claim 1, which is characterized in that step S1 includes:
S11, the bare electrode surface of the detecting electrode is polishing to smooth, is then rinsed well with deionized water;
And S12, in ultrasonic wave successively with deionized-distilled water, absolute ethyl alcohol, deionized-distilled water to being obtained in step S11 Bare electrode handled, each processing procedure used time is 4-10 minutes, is then dried at room temperature.
3. detection method according to claim 1, which is characterized in that in step S1, the detecting electrode includes glass carbon electricity Pole is modified the glass-carbon electrode using carbon nanotube in step S2.
4. detection method according to claim 3, which is characterized in that the step S2 includes:
S21,0.15-0.45mg mL are made-1Cmc soln and 0.8-1.2mg mL-1Carboxymethyl cellulose Element-carbon nano tube suspension;
S22, the chitosan solution for preparing 0.15-0.25%, and by the carboxymethyl cellulose-carbon nano tube suspension and shell Glycan solution by volume 10:1 is mixed, to obtain mixed liquor;
And S23, the mixed liquor of 3-8 μ L dropped on the glass-carbon electrode and dried, carbon nanotube is thus completed to the glass The modification of carbon electrode.
5. detection method according to claim 1, which is characterized in that the step S3 includes:
S31, honey sample is diluted using 0.1mol/L phosphate buffers, is used in combination NaOH solution by the honey after dilution Sample solution pH is adjusted to 9-11;
S32, using the detecting electrode modified by the carbon nanotube, according to square wave voltammetry and/or cyclic voltammetry It is that 9-11 honey sample solution is detected to after dilution, pH, obtains the pyroracemic aldehyde content data in honey.
6. detection method according to claim 5, which is characterized in that with NaOH solution by the bee after dilution in step S31 Sweet sample solution pH is adjusted to 10.
7. the detection device of acetone aldehyde in a kind of honey, which is characterized in that include the detection modified by carbon nanotube Electrode.
8. detection device as claimed in claim 7, which is characterized in that the step that the detecting electrode is modified by carbon nanotube Suddenly include:
S100,0.15-0.45mg mL are made-1Cmc soln and 0.8-1.2mg mL-1Carboxymethyl cellulose Element-carbon nano tube suspension;
S101, the chitosan solution for preparing 0.15-0.25%, and by the carboxymethyl cellulose-carbon nano tube suspension and shell Glycan solution by volume 10:1 is mixed, to obtain mixed liquor;
And S102, the mixed liquor of 3-8 μ L dropped on the glass-carbon electrode and dried, carbon nanotube is thus completed to the glass The modification of carbon electrode.
9. detection device as claimed in claim 7, which is characterized in that the detecting electrode includes glass-carbon electrode.
CN201810423587.5A 2018-05-06 2018-05-06 Method and device for detecting content of methylglyoxal in honey Active CN108535350B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810423587.5A CN108535350B (en) 2018-05-06 2018-05-06 Method and device for detecting content of methylglyoxal in honey

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810423587.5A CN108535350B (en) 2018-05-06 2018-05-06 Method and device for detecting content of methylglyoxal in honey

Publications (2)

Publication Number Publication Date
CN108535350A true CN108535350A (en) 2018-09-14
CN108535350B CN108535350B (en) 2019-12-31

Family

ID=63476386

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810423587.5A Active CN108535350B (en) 2018-05-06 2018-05-06 Method and device for detecting content of methylglyoxal in honey

Country Status (1)

Country Link
CN (1) CN108535350B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101101273A (en) * 2007-06-29 2008-01-09 浙江大学 Carbon nano tube modified blood sugar biosensor
CN101354374A (en) * 2008-07-07 2009-01-28 浙江大学 Chitosan-carbon nano-tube-dye-enzyme multi-layer film prepared by self-assembling for layer upon layer
JP2012225762A (en) * 2011-04-19 2012-11-15 Toyo Univ Method of detecting glycosylated protein and biosensor chip for detecting glycosylated protein
CN103439390A (en) * 2013-08-27 2013-12-11 西北工业大学 Electrochemical method for detecting melamine in dairy products or food
CN105758915A (en) * 2016-03-02 2016-07-13 常州大学 Preparation of carboxymethyl cellulose-chitosan composite material and identification of tryptophan enantiomer by modified electrode of composite material through electrochemical process

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101101273A (en) * 2007-06-29 2008-01-09 浙江大学 Carbon nano tube modified blood sugar biosensor
CN101354374A (en) * 2008-07-07 2009-01-28 浙江大学 Chitosan-carbon nano-tube-dye-enzyme multi-layer film prepared by self-assembling for layer upon layer
JP2012225762A (en) * 2011-04-19 2012-11-15 Toyo Univ Method of detecting glycosylated protein and biosensor chip for detecting glycosylated protein
CN103439390A (en) * 2013-08-27 2013-12-11 西北工业大学 Electrochemical method for detecting melamine in dairy products or food
CN105758915A (en) * 2016-03-02 2016-07-13 常州大学 Preparation of carboxymethyl cellulose-chitosan composite material and identification of tryptophan enantiomer by modified electrode of composite material through electrochemical process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ELECTROCHEMICAL DETERMINATION OF METHYLGLYOXAL AS A BIOMARKER IN: "Electrochemical determination of methylglyoxal as a biomarker in human plasma", 《BIOSENSORS AND BIOELECTRONICS》 *

Also Published As

Publication number Publication date
CN108535350B (en) 2019-12-31

Similar Documents

Publication Publication Date Title
CN103926294B (en) Preparation and application of CS/IL-GR modified bovine serum albumin molecular imprinting electrode
Kilele et al. A novel electrochemical sensor for selective determination of theophylline in pharmaceutical formulations
Sadeghi et al. Voltammetric sensor based on carbon paste electrode modified with molecular imprinted polymer for determination of sulfadiazine in milk and human serum
Hu et al. Determination of dimetridazole using carbon paste electrode modified with aluminum doped surface molecularly imprinted siloxane
Ma et al. Novel electrochemical sensing platform based on a molecularly imprinted polymer-decorated 3D-multi-walled carbon nanotube intercalated graphene aerogel for selective and sensitive detection of dopamine
Gu et al. β‐Cyclodextrin‐Functionalized Gold Nanoparticles/Poly (L‐cysteine) Modified Glassy Carbon Electrode for Sensitive Determination of Metronidazole
Zhang et al. Electrochemical layer-by-layer modified imprinted sensor based on multi-walled carbon nanotubes and sol–gel materials for sensitive determination of thymidine
Yu et al. A facile strategy for ratiometric electrochemical sensing of quercetin in electrolyte solution directly using bare glassy carbon electrode
Wang et al. Boronic acid based imprinted electrochemical sensor for rutin recognition and detection
Khorablou et al. Flexible and highly sensitive methadone sensor based on gold nanoparticles/polythiophene modified carbon cloth platform
Rahemi et al. Electrochemical Determination of the Herbicide Bentazone Using a Carbon Nanotube β‐Cyclodextrin Modified Electrode
Sun et al. Amperometric immunosensor for carbofuran detection based on gold nanoparticles and PB-MWCNTs-CTS composite film
Ziyatdinova et al. Surfactant/carbon nanofibers-modified electrode for the determination of vanillin
CN107179348B (en) A kind of double-template trace electrochemical sensor and its preparation method and application
Dhanjai et al. Modified stainless steel microneedle electrode for polyphenolics detection
Mirabi-Semnakolaii et al. Sensitive determination of herbicide trifluralin on the surface of copper nanowire electrochemical sensor
Peng et al. A simple and sensitive method for the voltammetric analysis of theobromine in food samples using nanobiocomposite sensor
Fatah et al. Application of molecularly imprinted electrochemical sensor for trace analysis of Metribuzin herbicide in food samples
CN109085225A (en) A kind of preparation method of the protein electrochemistry trace sensor of step sedimentation modification carbon electrode
Sharma et al. Cellulose fabricated pencil graphite sensor for the quantification of hazardous herbicide atrazine
CN105866211B (en) A kind of preparation method and application of ampicillin molecular engram sensor
CN101576530B (en) Method for measuring dopamine by utilizing graphite nano-sheet/Nafion composite film to modify electrode
CN111175358A (en) Preparation method of cyfluthrin molecular imprinting electrochemiluminescence sensor and method for detecting cyfluthrin
Huang et al. Redox hydrogel based immunosensing platform for the label-free detection of a cancer biomarker
CN107102043B (en) A kind of preparation method of multi-walled carbon nanotube/poly- L-Histidine modified glassy carbon electrode and its application in measurement hydroquinone

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant