CN112903795B - Electrochemical detection method for content of 5-hydroxymethylfurfural - Google Patents
Electrochemical detection method for content of 5-hydroxymethylfurfural Download PDFInfo
- Publication number
- CN112903795B CN112903795B CN202110446874.XA CN202110446874A CN112903795B CN 112903795 B CN112903795 B CN 112903795B CN 202110446874 A CN202110446874 A CN 202110446874A CN 112903795 B CN112903795 B CN 112903795B
- Authority
- CN
- China
- Prior art keywords
- electrode
- hydroxymethylfurfural
- content
- solution
- detected
- 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.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems 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)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
The invention relates to the technical field of food safety detection, in particular to an electrochemical detection method for 5-hydroxymethylfurfural content. The invention provides an electrochemical detection method of 5-hydroxymethylfurfural content, which comprises the following steps: placing a working electrode, a reference electrode and a counter electrode three-electrode system in a solution to be detected; obtaining the characteristic peak current value of the liquid to be detected by adopting a differential pulse voltammetry; obtaining the content of 5-hydroxymethylfurfural in the liquid to be detected through the characteristic peak current value according to a standard working curve; the working electrode is selected from glassy carbon electrodes modified with black phosphorus alkene. The electrochemical detection method for 5-hydroxymethylfurfural content provided by the invention has the advantages of simple electrode manufacturing, convenient operation, short analysis time and low cost, can accurately and efficiently detect the 5-hydroxymethylfurfural content in various samples to be detected, and has the characteristics of good stability, high sensitivity, high specificity and the like, and the lowest detection limit can reach 0.055 mu g/ml.
Description
Technical Field
The invention relates to the technical field of food safety detection, in particular to an electrochemical detection method for 5-hydroxymethylfurfural content.
Background
5-hydroxymethyl furfural (5-hydroxymethyl furfurfurral), also known as 5-hydroxymethyl-2-furfural, is a furfural compound which can be produced in the process of food thermal processing and has more active chemical properties. The 5-hydroxymethylfurfural has certain functions of enhancing aroma and mixing color, and is widely applied to foods such as coffee, honey, dairy products, fruit juice and the like. Research shows that a small amount of 5-hydroxymethylfurfural has a beneficial effect of resisting oxidation on a human body, but high concentration of 5-hydroxymethylfurfural can cause damage to skin, eyes, mucous membranes, respiratory tracts and the like, and has neurotoxicity, genetic toxicity, potential carcinogenicity, mutagenicity and the like. Therefore, it is necessary to pay attention to the content of 5-hydroxymethylfurfural in food.
At present, the detection method of 5-hydroxymethylfurfural mainly comprises a high performance liquid chromatography, a gas chromatography-mass spectrometry combined method and the like. These methods have problems of high price, long time consumption, high requirement on operators and the like.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for electrochemical detection of 5-hydroxymethylfurfural content, which is used for solving the problems in the prior art.
In order to achieve the above objects and other related objects, the present invention provides a method for electrochemically detecting the content of 5-hydroxymethylfurfural, including:
placing a working electrode, a reference electrode and a counter electrode three-electrode system in a solution to be detected;
obtaining the characteristic peak current value of the liquid to be detected by adopting a differential pulse voltammetry;
obtaining the content of 5-hydroxymethylfurfural in the liquid to be detected through the characteristic peak current value according to a standard working curve;
the working electrode is selected from glassy carbon electrodes modified with black phosphorus alkene.
In some embodiments of the invention, the reference electrode is selected from a metal-metal refractory salt electrode, preferably a saturated calomel electrode or a silver/silver chloride electrode.
In some embodiments of the invention, the counter electrode is selected from inert electrode electrodes, preferably from tungsten electrodes, platinum electrodes or gold electrodes.
In some embodiments of the present invention, the method for preparing a glassy carbon electrode modified with black phosphorus alkene comprises: and uniformly distributing the black phosphorus alkene dispersion liquid on the surface of the glassy carbon electrode subjected to the activation treatment, and drying.
In some embodiments of the invention, the coating amount of the black phosphorus on the surface of the glassy carbon electrode modified with the black phosphorus is 14-71 mu g/cm2。
In some embodiments of the present invention, the electrode activating solution used in the activation treatment is selected from an aqueous solution of sulfuric acid.
In some embodiments of the invention, the liquid to be tested is selected from one or more combinations of food products, preferably coffee-based beverages and prepared milk.
In some embodiments of the invention, the method of establishing the standard operating curve comprises:
placing a working electrode, a reference electrode and a counter electrode three-electrode system in a 5-hydroxymethylfurfural solution with preset gradient concentration;
obtaining characteristic peak parameters of a preset gradient concentration 5-hydroxymethylfurfural solution by adopting a differential pulse voltammetry method;
and providing a standard working curve according to the characteristic peak parameters corresponding to the 5-hydroxymethylfurfural solution with each preset gradient concentration.
In some embodiments of the present invention, the solvent of the 5-hydroxymethylfurfural solution with a preset gradient concentration is a phosphate buffer, and the pH of the phosphate buffer is 4-9.
In some embodiments of the present invention, the characteristic peak parameter is a characteristic reduction peak current value, preferably, the characteristic reduction peak current value is a peak current value of a characteristic reduction peak;
and/or in the differential pulse voltammetry, the lower scanning limit of a potential window is-1.6 to-2.0V, and the upper scanning limit is-0.2 to 0.2V;
and/or, the standard operating curve is linear.
Drawings
Fig. 1 shows a schematic diagram of DPV of a black phosphene-modified electrode in 5-hydroxymethylfurfural solutions (pH 8) with different concentrations in example 1 of the present invention.
FIG. 2 is a graph showing a standard working curve of the relationship between the characteristic reduction peak current value and the concentration of 5-hydroxymethylfurfural in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments, and other advantages and effects of the present invention will be apparent to those skilled in the art from the disclosure of the present specification.
The inventor of the invention provides an electrochemical detection method of 5-hydroxymethylfurfural content through a large amount of practical researches, and the electrochemical detection method has the characteristics of low cost, easy operation, high sensitivity, good specificity and the like, can be used for quickly and quantitatively detecting the 5-hydroxymethylfurfural content in various samples to be detected, and has good industrial prospect.
The invention provides an electrochemical detection method of 5-hydroxymethylfurfural content, which comprises the following steps:
1) putting a working electrode, a reference electrode and a counter electrode into a solution to be detected;
2) obtaining characteristic peak parameters of the liquid to be detected by adopting a Differential Pulse Voltammetry (DPV);
3) obtaining the content of 5-hydroxymethylfurfural in the liquid to be detected through characteristic peak parameters according to a standard working curve;
the working electrode is selected from glassy carbon electrodes modified with black phosphorus alkene.
The electrochemical detection method for the content of the 5-hydroxymethylfurfural provided by the invention can comprise the following steps: and placing the working electrode, the reference electrode and the counter electrode in the solution to be detected. The working electrode, the reference electrode and the counter electrode can generally form a three-electrode system, the system generally comprises two loops, one loop can comprise the working electrode and the reference electrode and can be used for testing the electrochemical reaction process of the working electrode, and the other loop can comprise the working electrode and the counter electrode and can play a role in transmitting electrons to form a loop. The working electrode in the three-electrode system can be a glassy carbon electrode modified with Black phosphorus (Black phosphorus), and the glassy carbon electrode modified with Black phosphorus has more obvious advantages in the aspects of sensitivity, specificity and the like when being used for measuring the content of 5-hydroxymethylfurfural in a complex mixture.
Among the above electrochemical detection methods, suitable methods for providing a glassy carbon electrode modified with black phosphene (working electrode) should be known to those skilled in the art. For example, the preparation method of the glassy carbon electrode modified with black phosphorus alkene can comprise the following steps: and uniformly distributing the black phosphorus alkene dispersion liquid on the surface of the glassy carbon electrode subjected to the activation treatment, and drying. The black phosphene used may have a sheet diameter of 0.1 to 5 μm, 0.1 to 0.3 μm, 0.3 to 0.5 μm, 0.5 to 1 μm, 1 to 2 μm, 2 to 3 μm, or 3 to 5 μm. During the coating process, the black phosphene is generally uniformly dispersed in an appropriate amount of solvent (e.g., water, etc.) at an appropriate concentration. For example, the content of the black phosphorus in the black phosphorus dispersion liquid can be 0.2-0.5 mg/mL, 0.2-0.3 mg/mL, 0.3-0.4 mg/mL, or 0.4-0.5 mg/mL. The prepared glassy carbon electrode modified with black phosphorus alkene has the advantages that the black phosphorus alkene attached to the surface of the glassy carbon electrode is generally uniformly distributed and has proper black phosphorus alkene coatingIn general, the coating can be applied once or more (e.g., 1-10 times, 1-2 times, 2-4 times, 4-6 times, or 6-10 times, etc.) on the surface of the electrode to form a suitable uniformly distributed coating. For example, the coating amount of the black phosphorus alkene on the surface of the glassy carbon electrode modified with the black phosphorus alkene can be 14-71 mu g/cm2、14～17μg/cm2、17～20μg/cm2、20～25μg/cm2、25～30μg/cm2、30～35μg/cm2、35～40μg/cm2、40～45μg/cm2、45～50μg/cm2、50～55μg/cm2、55～60μg/cm2、60～65μg/cm2Or 65 to 71 μ g/cm2。
In the above electrochemical detection method, one skilled in the art can select a suitable electrode type for the reference electrode included in the three-electrode system. For example, the reference electrode may be selected from metal-metal refractory salt electrodes and the like, and more specifically may be selected from (saturated) calomel electrodes, silver/silver chloride electrodes and the like.
In the above electrochemical detection method, one skilled in the art can select an appropriate electrode type to be used for the counter electrode included in the three-electrode system. For example, the counter electrode may be selected from inert electrodes and the like, and more specifically may be selected from tungsten electrodes, platinum electrodes, gold electrodes and the like.
In the above electrochemical detection method, the three-electrode system used is usually a three-electrode system subjected to an activation treatment. For example, a glassy carbon electrode modified with black phosphene may be generally prepared from a glassy carbon electrode subjected to an activation treatment. Suitable methods for activation treatment of the three-electrode system will be known to those skilled in the art. For example, a glassy carbon electrode (of unmodified black phosphene) may be placed in a suitable electrode activation solution, washed with water, and dried after the electrode output is stabilized (e.g., scanned using cyclic voltammetry). For example, the electrode activation solution used in the activation treatment may be an aqueous solution of sulfuric acid.
In the electrochemical detection method, the three-electrode system before being subjected to the activation treatment can be further subjected to polishing treatment so as to ensure the accuracy of measurement. For example, the surface of a glassy carbon electrode (not subjected to activation treatment) can be polished to a mirror surface, and the three-electrode system can be placed in a suitable electrochemical probe solution to observe whether a suitable peak potential difference exists between an oxidation peak and a reduction peak.
In the electrochemical detection method, the liquid to be detected is basically or mostly liquid, so that the three-electrode system can be placed in the liquid to be detected to realize the detection of the content of the target substance. The test solution can be formed in a suitable manner for samples to be tested in different states, and these methods should be known to those skilled in the art. For example, the sample to be tested can be appropriately dissolved, diluted, or the like with a diluent (e.g., phosphate buffer or the like). For another example, the sample to be tested may be selected from one or more combinations of foods and the like, preferably may be selected from one or more combinations of coffee beverages, prepared milk and the like, the coffee beverages may generally meet the standards of GB-T30767-.
In the above electrochemical detection method, the whole detection process can be performed under the protection of gas. Suitable methods of providing gas shielding should be known to those skilled in the art. For example, the gas shielding conditions may be provided by an inert gas (e.g., nitrogen, noble gases, helium, neon, argon, krypton, etc.). For another example, an inert gas may be continuously introduced into the liquid to be measured to displace a gas that may be contained in the liquid to be measured and may affect the measurement result.
The electrochemical detection method for the content of the 5-hydroxymethylfurfural provided by the invention can also comprise the following steps: and obtaining characteristic peak parameters of the liquid to be detected by adopting a differential pulse voltammetry. After the three-electrode system is placed in the liquid to be detected, characteristic peak parameters (for example, a characteristic reduction peak current value, more specifically, a peak current value of a characteristic reduction peak) corresponding to 5-hydroxymethylfurfural in the liquid to be detected can be measured by a differential pulse voltammetry, and the position of the characteristic peak corresponding to 5-hydroxymethylfurfural in a scanning map of the differential pulse voltammetry can be located between-1.3V and-1.4V. Generally speaking, differential pulsed voltammetry is used to obtain the results relative to other analytical methodsA better peak pattern is obtained to facilitate the discrimination of characteristic reduction peaks. The parameters of the differential pulse voltammetry can be appropriately adjusted by those skilled in the art to obtain a suitable detection profile and further obtain characteristic reduction peak parameters. For example, in the differential pulse voltammetry measurement, the lower scanning limit of the potential window may be-1.6 to-2.0V, -1.6 to-1.7V, -1.7 to-1.8V, -1.8 to-1.9V, or-1.9 to-2.0V, and the upper scanning limit may be-0.2 to 0.2V, -0.2 to-0.1V, -0.1 to 0V, 0 to 0.1V, or 0.1 to 0.2V. In one embodiment of the present invention, the scanning range can be-0.2 to-1.8V, the amplitude can be 0.04 to 0.06V, the pulse width can be 0.04 to 0.06sec, the sampling width can be 0.016 to 0.018sec, the pulse period can be 0.4 to 0.6sec, and the sensitivity can be 1.0 × 10-4～1.0×10-6。
The electrochemical detection method for the content of the 5-hydroxymethylfurfural provided by the invention can also comprise the following steps: and obtaining the content of the 5-hydroxymethylfurfural in the liquid to be detected through the characteristic peak parameters according to the standard working curve. And after the characteristic peak parameter corresponding to the liquid to be detected is obtained, calculating to obtain the content of the 5-hydroxymethylfurfural in the liquid to be detected according to the corresponding relation between the characteristic peak parameter and the content of the 5-hydroxymethylfurfural by using a pre-calibrated standard working curve.
In the electrochemical detection method, the method for calculating the standard working curve may include:
placing a working electrode, a reference electrode and a counter electrode three-electrode system in a 5-hydroxymethylfurfural solution with preset gradient concentration;
obtaining characteristic peak parameters of a preset gradient concentration 5-hydroxymethylfurfural solution by adopting a differential pulse voltammetry method;
and providing a standard working curve according to the characteristic peak parameters corresponding to the 5-hydroxymethylfurfural solution with each preset gradient concentration. The principle of the method for establishing the standard working curve is basically the same as that of the electrochemical detection method for the content of the 5-hydroxymethylfurfural provided above, except that the detection target is replaced by a preset gradient concentration of 5-hydroxymethylfurfural solution. Since the content of 5-hydroxymethylfurfural in the 5-hydroxymethylfurfural solution with the preset gradient concentration is known, a standard working curve between the characteristic peak parameter and the content of 5-hydroxymethylfurfural can be established.
Among the above electrochemical detection methods, suitable methods for providing a 5-hydroxymethylfurfural solution with a preset gradient concentration should be known to those skilled in the art. For example, the solvent of the 5-hydroxymethylfurfural solution with the preset gradient concentration can be phosphate buffer solution, and the pH of the phosphate buffer solution can be 4-9, 4-5, 5-6, 6-6.5, 6.5-7, 7-7.5, 7.5-8, or 8-9. For another example, in the 5-hydroxymethylfurfural solution with a preset gradient concentration, the concentration range of the 5-hydroxymethylfurfural may be 0.1 to 1000 μ g/mL.
The electrochemical detection method for 5-hydroxymethylfurfural content provided by the invention has the advantages of simple electrode manufacturing, convenient operation, short analysis time and low cost, can accurately and efficiently detect the 5-hydroxymethylfurfural content in various samples to be detected, has the characteristics of good stability, high sensitivity, high specificity and the like, has the lowest detection limit of 0.055 mu g/ml, can be suitable for various requirements of on-line monitoring, and has good industrialization prospect.
The present application is further illustrated by the following examples, which are not intended to limit the scope of the present application.
Example 1
Establishing a standard working curve of 5-hydroxymethylfurfural:
step 1: polishing and activating the glassy carbon electrode:
step 1.1: sequentially polishing the surface of a glassy carbon electrode (model: CHI104 with a diameter of 3mm, purchased from Shanghai Chenghua apparatus Co., Ltd.) to a mirror surface by using alumina powder with a diameter of 1 μm, 0.3 μm and 0.05 μm, and washing the surface of the electrode with deionized water before replacing the alumina powder with different particle diameters for polishing; then ultrasonic cleaning is carried out for 5min by using deionized water, absolute ethyl alcohol and deionized water in sequence, and alumina powder and other pollutants adsorbed on the surface of the electrode are thoroughly removed; and then blown dry with nitrogen.
Step 1.2: saturated calomel electrode (model: CHI150, available from Shanghai Chenhua apparatus, Inc.), platinum electrode (model: CHI115, available from Shanghai Chenhua apparatus, Limited public place)Department) and the polished and dried glassy carbon electrode three-electrode system are placed in 5ml of 5mmol/L [ Fe (CN) ] containing 0.1mol/LKCl6]3-/4-Scanning a cyclic voltammogram in the electrochemical probe solution, and observing whether the peak potential difference between an oxidation peak and a reduction peak meets the standard (Delta E is more than or equal to 59 mV)pLess than or equal to 100mV), if not, repeating the polishing process until the polishing is qualified, namely the electrode is polished.
Step 1.3: placing a saturated calomel electrode, a platinum electrode and a qualified polished glassy carbon electrode three-electrode system in 5ml of sulfuric acid solution containing 0.1mol/L, and scanning to be stable (20 circles) by adopting a cyclic voltammetry method; and taking out, washing the surface of the electrode with deionized water, and blow-drying with nitrogen gas to finish the activation of the electrode.
Step 2: preparing a black phosphorus alkene modified electrode:
0.2mg/mL of black phosphorus alkene dispersion liquid (the diameter of a sheet is 100 nanometers to 5 micrometers, the solvent is water, the supplier is Jiangsu Xiancheng nano material science and technology Co., Ltd.) is subjected to ultrasonic dispersion for 5 minutes, 8 mu l of the black phosphorus alkene dispersion liquid which is uniformly subjected to ultrasonic dispersion is absorbed by a liquid transfer gun and is dripped on the surface of a glassy carbon electrode (the corresponding coating amount is about 23 mu g/cm)2) And naturally drying the electrode to form a uniform black phosphorus alkene film on the surface of the electrode.
And step 3: establishing a standard curve of the relation between the current value of the characteristic peak of the 5-hydroxymethylfurfural and the concentration:
step 3.1: preparing a phosphoric acid buffer solution with the pH value of 8 by adopting sodium dihydrogen phosphate and disodium hydrogen phosphate with the concentration of 0.2 mol/L;
step 3.2: taking a phosphate buffer solution with the pH value of 8 as a solvent, preparing a 5-hydroxymethylfurfural standard solution with the concentration of 100 mu g/mL, and diluting the 5-hydroxymethylfurfural standard solution with the phosphate buffer solution with the pH value of 8 into 5-hydroxymethylfurfural standard solutions with the concentrations of 10 mu g/mL, 5 mu g/mL, 1 mu g/mL, 0.5 mu g/mL and 0.1 mu g/mL respectively; and introducing nitrogen into the 5-hydroxymethylfurfural standard solution to prevent the interference of active gas in the solution, particularly the interference of oxygen.
Step 3.3: placing the glassy carbon working electrode, saturated calomel electrode and platinum electrode three-electrode system modified with black phosphorus alkene into 5ml of 5-hydroxymethylfurfural standard solution, standing for 1 minute, and then adopting differencePulse Voltammetry (DPV) measurement, scanning range of-0.2V to-1.8V, amplitude of 0.05V, pulse width of 0.05sec, sampling width of 0.0167sec, pulse period of 0.5sec, and sensitivity of 1 × 10-5Measuring the reduction peak current value of the 5-hydroxymethylfurfural in the standard solution, wherein the DPV characteristic peak is positioned in the range of-1.3 to-1.4V, and the DPV graphs of the 5-hydroxymethylfurfural standard solutions with different concentrations are shown in figure 1; establishing a standard working curve for detecting 5-hydroxymethylfurfural by taking the concentration as a horizontal coordinate and the peak current value as a vertical coordinate, and obtaining a fitting curve I as shown in figure 2p＝0.473CHMF+0.0206, where I is the reduction peak current value in units of μ A, CHMFIs the concentration of 5-HMF, in units of μ g/mL; the electrode has good linear relation (R) to 5-hydroxymethylfurfural20.998), calculated to a limit of detection of 0.055 μ g/mL.
Further evaluation of the reproducibility of electrochemical detection of 5-hydroxymethylfurfural: the same black phosphorus alkene modified glassy carbon electrode is used for carrying out parallel determination on 100 mu g/mL 5-hydroxymethylfurfural solution for 30 times, and the test conditions are as follows: pH8, DPV parameter settings: the scanning range is-0.2V to-1.8V, the amplitude is 0.05V, the pulse width is 0.05sec, the sampling width is 0.0167sec, the pulse period is 0.5sec, and the sensitivity is 1 multiplied by 10-5And measuring the relative standard deviation RSD of the peak current value to be 0.32%, which shows that the glassy carbon electrode modified by the black phosphorus alkene has good repeatability.
Quantitative and rapid detection of the content of 5-hydroxymethylfurfural in the prepared milk:
three different commercially available branded recombined milks A, B, C were purchased as samples to be tested. 5mL of the prepared milk sample to be tested was aspirated by a pipette gun, diluted with 5mL of a phosphate buffer solution having pH8, and mixed well. And (3) sucking 5mL of diluent into an electrolytic cup, connecting the diluent into a three-electrode system (same as the step 3.3 part in the embodiment), measuring by adopting a Differential Pulse Voltammetry (DPV), substituting the obtained characteristic peak current value into the standard working curve established in the embodiment, respectively measuring three times aiming at A, B, C samples to be measured, taking the average value of the peak currents, and calculating to obtain the content of the 5-hydroxymethylfurfural in the modulated milk to be measured, wherein the result is shown in Table 1. As can be seen from the data in table 1, the detection results obtained by the detection method provided herein are very close to those of HPLC.
TABLE 1 DPV and HPLC detection of 5-hydroxymethylfurfural content in conditioned milk
Example 2
Establishing a standard working curve of 5-hydroxymethylfurfural:
method for establishing standard working curve of 5-hydroxymethylfurfural referring to example 1, only the reference electrode was replaced with a silver/silver chloride electrode, and the obtained standard working curve was Ip＝0.452CHMF+0.0034，R20.995, detection limit 0.057 μ g/ml.
Further evaluation of the reproducibility of electrochemical detection of 5-hydroxymethylfurfural: the same black phosphorus alkene modified glassy carbon electrode is used for carrying out parallel determination on a 100 mu g/mL 5-hydroxymethyl furfural solution for 30 times under the optimal condition, and the test conditions are as follows: pH8, DPV parameter settings: the scanning range is-0.2V to-1.8V, the amplitude is 0.05V, the pulse width is 0.05sec, the sampling width is 0.0167sec, the pulse period is 0.5sec, and the sensitivity is 1 multiplied by 10-5And measuring the relative standard deviation RSD of the peak current value to be 0.43%, which shows that the glassy carbon electrode modified by the black phosphorus alkene has good repeatability.
Quantitative and rapid detection of 5-hydroxymethylfurfural content in coffee beverage samples:
different brands of coffee beverage A, B, C were purchased commercially as samples to be tested. A 5mL sample of the coffee beverage to be tested was aspirated by a pipette gun, diluted with 5mL of a phosphate buffer solution having pH8, and mixed well. And (3) sucking 5mL of diluent into an electrolytic cup, connecting the electrolytic cup into a three-electrode system (provided in the embodiment), measuring according to the Differential Pulse Voltammetry (DPV) adopted in the step 3.3 to obtain a characteristic reduction peak current value, repeatedly detecting for 3 times to obtain an average value of the reduction peak current, and calculating a standard deviation.
The obtained characteristic reduction peak-to-peak current value was substituted into the standard working curve (I) established in this examplep＝0.452CHMF+0.0034，R20.995, detection limit 0.057 μ g/ml), calculating to obtain coffee beverageThe content of 5-hydroxymethylfurfural in the feed is shown in Table 2, and is compared with the detection result of HPLC. As can be seen from the data in table 2, the detection results obtained by the detection method provided herein are very close to those of HPLC.
TABLE 2 DPV and HPLC detection of 5-hydroxymethylfurfural content in coffee beverages
Example 3
To assess the specificity of this electrode for the electrochemical response of 5-hydroxymethylfurfural, 8 substances that could potentially interfere with the electrochemical response of 5-hydroxymethylfurfural in the brewed milk and coffee beverages were selected, glucose, galactose, lysine, casein, vitamin B1, vitamin B5, K+And Na+A specificity test is performed. The electrolyte containing only 10 μ g/mL 5-hydroxymethylfurfural (phosphate buffer, pH 8) and the electrolyte containing both 10 μ g/mL 5-hydroxymethylfurfural and a certain interfering substance (total 9 samples) were detected using DPV, respectively, and the detection method was referred to the detection conditions in step 3.3 of example 1.
Comparing the characteristic peak shape and the peak current value in the detection result of each sample, it can be found that when 5-hydroxymethylfurfural and an interferent exist simultaneously, no oxidation reduction peak of any interferent appears in the scanning range, no obvious influence is generated on the reduction peak potential of the 5-hydroxymethylfurfural, the interferent only slightly influences the reduction peak current value of the 5-hydroxymethylfurfural, and the percentage change of the peak current value caused by the addition of glucose is minimum and is only 2.75%; na (Na)+、K+The changes brought by galactose and vitamin B1 are all about 5 percent; vitamin B5 caused a 7.68% change in current; the changes caused by lysine and casein were relatively large, slightly over 10%. The results prove that the electrode has specificity for detecting 5-hydroxymethylfurfural in the scanning range, and potential interferents do not undergo redox reaction and thus interfere with detection.
In conclusion, the present invention effectively overcomes various disadvantages of the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (12)
1. An electrochemical detection method for 5-hydroxymethylfurfural content comprises the following steps:
1) putting a working electrode, a reference electrode and a counter electrode into a solution to be detected;
2) obtaining characteristic peak parameters of the liquid to be detected by adopting a differential pulse voltammetry method;
3) obtaining the content of 5-hydroxymethylfurfural in the liquid to be detected through characteristic peak parameters according to a standard working curve;
the working electrode is selected from glassy carbon electrodes modified with black phosphorus alkene; the preparation method of the glassy carbon electrode modified with the black phosphorus alkene comprises the following steps: uniformly distributing the black phosphorus alkene dispersion liquid on the surface of the glassy carbon electrode subjected to activation treatment, and drying; the coating amount of the black phosphorus alkene on the surface of the glassy carbon electrode modified with the black phosphorus alkene is 14-71 mu g/cm2；
The whole detection process is carried out under the condition of gas protection; and continuously introducing gas into the liquid to be detected, wherein the gas is inert gas.
2. The method of claim 1, wherein the reference electrode is selected from metal-metal insoluble salt electrodes.
3. The method for electrochemically detecting the content of 5-hydroxymethylfurfural according to claim 2, wherein the reference electrode is selected from a saturated calomel electrode or a silver/silver chloride electrode.
4. The method of claim 1, wherein the counter electrode is selected from inert electrodes.
5. The method of claim 4, wherein the counter electrode is selected from a tungsten electrode, a platinum electrode, and a gold electrode.
6. The method for electrochemically detecting the content of 5-hydroxymethylfurfural according to claim 1, wherein in the activation treatment, an electrode activation solution used is selected from an aqueous sulfuric acid solution.
7. The electrochemical detection method for 5-hydroxymethylfurfural content according to claim 1, wherein the solution to be detected is selected from one or more combinations of foods.
8. The electrochemical detection method for 5-hydroxymethylfurfural content according to claim 7, wherein the liquid to be detected is selected from one or more of coffee-based beverages and prepared milk.
9. The method for electrochemical detection of 5-hydroxymethylfurfural content according to claim 1, wherein the method for establishing the standard working curve comprises:
placing a working electrode, a reference electrode and a counter electrode three-electrode system in a 5-hydroxymethylfurfural solution with preset gradient concentration;
obtaining characteristic peak parameters of a preset gradient concentration 5-hydroxymethylfurfural solution by adopting a differential pulse voltammetry method;
and providing a standard working curve according to the characteristic peak parameters corresponding to the 5-hydroxymethylfurfural solution with each preset gradient concentration.
10. The electrochemical detection method of 5-hydroxymethylfurfural content according to claim 9, wherein a solvent of a preset gradient concentration 5-hydroxymethylfurfural solution is a phosphate buffer solution, and the pH of the phosphate buffer solution is 4-9.
11. The electrochemical detection method for 5-hydroxymethylfurfural content according to any one of claims 1 to 10, wherein the characteristic peak parameter is a characteristic reduction peak current value;
and/or in the differential pulse voltammetry, the lower scanning limit of a potential window is-1.6 to-2.0V, and the upper scanning limit is-0.2 to 0.2V;
and/or, the standard operating curve is linear.
12. The method for electrochemically detecting a content of 5-hydroxymethylfurfural according to claim 11, wherein the characteristic reduction peak current value is a peak current value of a characteristic reduction peak.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110446874.XA CN112903795B (en) | 2021-04-25 | 2021-04-25 | Electrochemical detection method for content of 5-hydroxymethylfurfural |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110446874.XA CN112903795B (en) | 2021-04-25 | 2021-04-25 | Electrochemical detection method for content of 5-hydroxymethylfurfural |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112903795A CN112903795A (en) | 2021-06-04 |
| CN112903795B true CN112903795B (en) | 2022-07-05 |
Family
ID=76109108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110446874.XA Active CN112903795B (en) | 2021-04-25 | 2021-04-25 | Electrochemical detection method for content of 5-hydroxymethylfurfural |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112903795B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107389764A (en) * | 2017-07-31 | 2017-11-24 | 海南师范大学 | A kind of preparation of black phosphorus alkene modified electrode and the method for detecting rutin |
| CN110208399A (en) * | 2019-05-21 | 2019-09-06 | 新疆农业科学院农产品贮藏加工研究所 | A kind of method of 5 hydroxymethyl furfural content in measurement jujube |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9885119B2 (en) * | 2015-02-12 | 2018-02-06 | Wisconsin Alumni Research Foundation | Electrochemical and photoelectrochemical reduction of furfurals |
| CN106348263A (en) * | 2016-09-28 | 2017-01-25 | 成都新柯力化工科技有限公司 | Multilayer stable black phosphorene and preparation method |
| CN109052347A (en) * | 2018-08-22 | 2018-12-21 | 昆明理工大学 | A kind of method that electric field cooperates with up-stripping black phosphorus preparation nanometer black phosphorus with microwave field |
| CN110205645A (en) * | 2019-04-23 | 2019-09-06 | 电子科技大学 | 5 hydroxymethyl furfural electroxidation is the all-hydrolytic device and reaction method of anode reaction |
| CN111472020B (en) * | 2019-06-04 | 2021-05-04 | 中山大学 | Method for preparing 2,5-furandicarboxylic acid by electrocatalytic oxidation of 5-hydroxymethylfurfural with hydrotalcite-based layered catalyst |
-
2021
- 2021-04-25 CN CN202110446874.XA patent/CN112903795B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107389764A (en) * | 2017-07-31 | 2017-11-24 | 海南师范大学 | A kind of preparation of black phosphorus alkene modified electrode and the method for detecting rutin |
| CN110208399A (en) * | 2019-05-21 | 2019-09-06 | 新疆农业科学院农产品贮藏加工研究所 | A kind of method of 5 hydroxymethyl furfural content in measurement jujube |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112903795A (en) | 2021-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Brunetti et al. | Determination of caffeine at a Nafion‐covered glassy carbon electrode | |
| Mao et al. | Electrochemical nitric oxide sensors based on electropolymerized film of M (salen) with central ions of Fe, Co, Cu, and Mn | |
| Lin et al. | A novel method for simultaneous analysis of three β 2-agonists in foods with the use of a gold-nanoparticle modified glassy carbon electrode and chemometrics | |
| CN112051312B (en) | Electrochemical sensing detection method for paraquat in food and modified electrode thereof | |
| CN108181371B (en) | Electrochemical sensing analysis method for simply and rapidly detecting ochratoxin A in food | |
| Wei et al. | Molecularly imprinted electrochemical sensor for the determination of ampicillin based on a gold nanoparticle and multiwalled carbon nanotube‐coated pt electrode | |
| Brahman et al. | Highly sensitive stripping voltammetric determination of a biomolecule, pyruvic acid in solubilized system and biological fluids | |
| CN111307890B (en) | Manganese oxide/graphene modified electrode and method for detecting salicylic acid in plant tissue based on manganese oxide/graphene modified electrode | |
| CN112903795B (en) | Electrochemical detection method for content of 5-hydroxymethylfurfural | |
| EP3735904A1 (en) | Detecting nicotine in sweat | |
| CN109374706A (en) | A method of trace carbadox is detected with the structure mesoporous carbon CMK-8 Direct Electrochemistry sensor of cube Ia3d | |
| CN113030217A (en) | Enzyme biosensor for detecting inosinic acid, preparation method and application thereof | |
| Norouzi et al. | Ultrasensitive flow-injection electrochemical method using fast fourier transform square-wave voltammetry for detection of vitamin B1 | |
| Zhou et al. | Study on the electrochemical properties of maltol at a carbon paste electrode and its analytical application | |
| Beltagi et al. | Quantification of terbutaline in pharmaceutical formulation and human serum by adsorptive stripping voltammetry at a glassy carbon electrode | |
| CN112903796A (en) | Electrochemical detection method for furfural content | |
| CN114324515B (en) | Electrochemical sensor for detecting glyphosate based on copper porphyrin metal organic framework modified carbon paper electrode | |
| CN110039043A (en) | Three-dimensional copper@carbon core shell nanoparticles, preparation method and the application as enzyme-free glucose electrochemical sensor | |
| CN109781813A (en) | A method of directly quickly detecting nitrite | |
| CN110988069B (en) | Working electrode and preparation method thereof, sensor based on working electrode and detection method | |
| Goyal et al. | Voltammetric Determination of 2′‐Deoxyadenosine and Adenine in Urine of Patients with Hepatocellular Carcinoma Using Fullerene‐C60‐modified Glassy Carbon Electrode | |
| CN109521071B (en) | Electrochemical sensing detection method for benzimidazole pesticide thiabendazole | |
| CN110849949A (en) | Electrochemical detection method for acid scarlet in water | |
| CN106872543B (en) | Method and application based on polyelectrolyte compound film electrode detection nitrite ion | |
| Yang et al. | Sensitive voltammetric determination of neohesperidin dihydrochalcone based on SWNTs modified glassy carbon electrode |
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 |