CN110208355A - A kind of method of quinones substance and carboxymethyl-lysine interaction efficiency in measurement solution - Google Patents
A kind of method of quinones substance and carboxymethyl-lysine interaction efficiency in measurement solution Download PDFInfo
- Publication number
- CN110208355A CN110208355A CN201910406744.6A CN201910406744A CN110208355A CN 110208355 A CN110208355 A CN 110208355A CN 201910406744 A CN201910406744 A CN 201910406744A CN 110208355 A CN110208355 A CN 110208355A
- Authority
- CN
- China
- Prior art keywords
- solution
- cml
- substance
- interaction efficiency
- quinones
- 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
Links
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)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention discloses a kind of methods of quinones substance and carboxymethyl-lysine (CML) interaction efficiency in measurement solution.The cyclic voltammetry curve that the method passes through measurement CML addition front and back catechol substance solution, the peak point current and voltage characteristic value of record CML addition front and back catechol substance solution respectively, then by calculating the slip of reduction peak current, the interaction efficiency of quinones substance and CML in solution can be obtained.In the method for the invention, phenolic substances aoxidizes to form quinones substance after, can rapidly in system CML interact, reduce the side reaction of quinones substance；Substance is few in the adhesion amount of electrode surface, and detection accuracy is high；Reduce the interference of polyphenol in the prior art and its oxidation product in factors such as working electrode attachment, quinones substance related side effects to quinones substance and CML interaction；Measuring method of the present invention is simple simultaneously, and analysis time is short, has good repeatability and convenience, use cost is lower, using wide.
Description
Technical field
The present invention relates to food safety detections and technical field of analytical chemistry, more particularly, in a kind of measurement solution
The method of quinones substance and carboxymethyl-lysine (CML) interaction efficiency.
Background technique
CML (carboxymethyl-lysine) is to study a kind of most commonly used typical advanced glycosylation end products (AGEs) at present,
It is widely present in varieties of food items.CML can accumulate in the tissue after digesting and assimilating, and it is strong to human body that existing research is proved it
There are potential hazards for health.Therefore research reduces the means of CML content, can effectively reduce its potential hazard to human health.
Catechol substance itself can be oxidized to form corresponding adjacent benzene diquines while playing antioxidation
Substance, adjacent benzene diquinone substance is easy to that Michael addition reaction occurs with the amino on CML as strong electrophilic body, to reach
The purpose of elimination system CML.Currently, the method for measuring interaction efficiency between adjacent benzene diquinone substance and CML is mainly to utilize control
Potential electrolysis coulomb method processed aoxidizes the catechol substance in solution to obtain corresponding adjacent benzene diquinone substance, then utilizes
Residence time radial measures the interaction dynamics between adjacent benzene diquinone substance and CML.Controlled potential eletrolysis coulomb method prepares adjacent benzene two
Quinones substance requires the selected cycle voltammetry behavior of catechol substance on the working electrode (s reversible, and does not have obvious absorption
Property.Corresponding quinones substance (4- methyl neighbour's benzene diquinone) successfully only is prepared using 4- methyl pyrocatechol at present, and utilizes
Residence time radial determines 4- methyl neighbour's benzene diquinone and the interaction situation of CML in detail.
Most of polyphenols containing catechol structure, such as: catechins, rutin, Quercetin etc., easily
It is adsorbed in working electrode surface, and the quinones substance that its oxidation is formed is prone to the side reactions such as polymerization, rearrangement, because without having
Standby a possibility that preparing corresponding quinones substance using bulk electrolysis with coulometry.Therefore, it is impossible to be measured using existing means molten
The case where above-mentioned polyphenols oxidation gained quinones substance and CML interact in liquid.
Therefore, for above-mentioned detection method the shortcomings that, it is necessary to which a kind of wider array of detection method of use scope is provided.
Summary of the invention
It is an object of the invention to be directed to the prior art, detected using controlled potential eletrolysis coulomb-residence time radial combination method
During quinones substance and CML interaction efficiency, the type of catechol substance applicatory is less, application range
Limited deficiency provides a kind of method for measuring quinones substance and CML interaction efficiency in solution.The method of the invention utilizes neighbour
The electro-chemical activity of benzenediol substance adds the reduction peak of catechol substance before and after CML by cyclic voltammetry
Electric current calculates reduction peak current slip, to obtain the interaction efficiency of quinones substance and CML in solution；Side of the present invention
Method is suitable for most of catechol substances, and measuring method is simple, convenient, testing result is accurate, reliable, has stability
And repeatability, it has broad application prospects in terms of the detection and evaluation of the interaction efficiency of quinones substance and CML in food.
Above-mentioned purpose of the invention is achieved by following scheme:
The method of carboxymethyl-lysine (CML) content, includes the following steps: in a kind of measurement solution
S1. catechol substance is dissolved in buffer and obtains solution A；CML is dissolved in buffer and obtains solution B；It will be adjacent
Benzenediol substance and CML are dissolved in buffer and obtain solution C；
S2. using glassy carbon electrode as working electrode, platinum filament is to electrode, and silver/saturation silver chlorate is reference electrode, each electrode
It is connected with electrochemical workstation, constructs three-electrode system, solution A, solution B and solution C is carried out respectively using cyclic voltammetry
Detection, obtains the cyclic voltammetry curve of every part of solution, and record the peak point current and voltage characteristic value of every part of solution respectively；
S3. it according to the step S2 peak point current measured and voltage characteristic value, is calculated, can be measured according to following formula
The interaction efficiency of quinones substance and CML in solution:
Interaction efficiency (reduction peak current slip, %)=(IPC1 (phenol)-IPC1 (phenol+CML))/IPC1 (phenol)；
The wherein IPC1 (phenol)For the reduction peak peak point current of the solution A；The IPC1 (phenol+CML)For going back for the solution C
Parent peak peak point current.
Since the structure of catechol substance has electro-chemical activity, in cyclic voltammetry scan, when voltage forward direction
When scanning, catechol substance aoxidizes to form corresponding quinones substance in electrode surface, in subsequent negative sense scanning process,
Quinones substance is reduced to original phenolic substances in electrode surface, forms a pair of of redox peaks；When in solution system CML with
Quinones substance reaction, causes the consumption of quinones substance, then in negative sense scanning process, the reduction peak point current of solution C is compared with solution A
It is remarkably decreased, by reduction peak current slip in phenolic substances cyclic voltammetry curve before and after measurement addition CML, can calculate
To the interaction efficiency of quinones substance and CML.
When original controlled potential eletrolysis coulomb method is detected, by applying certain voltage, pass through the phenol inside system
(probably needing 40 minutes) after a period of time, all oxidations form quinone, and then quinone is reacted with CML again, measures its interaction efficiency；By
Longer in the time that phenolic substances is oxidized into quinones substance needs, this requires the quinones substances of generation to want highly stable, no
Then when serial side reaction occurs for quinones substance, or attachment hinders subsequent preparation process on the electrode, that is, it will affect detection
As a result accuracy, and work as quinones substance and adhere to for a long time on the electrode, it will cause the irreversible damage of reticulated vitreous carbon electrodes
Evil.And the entire scanning process of cyclic voltammetry that the present invention uses is no more than 3 minutes, phenolic substances once aoxidizes shape on the electrode
At quinones substance, quinones substance can and system coexist CML reaction, occur side reaction a possibility that just reduce, will not
It is attached to electrode surface for a long time, reduces the damage to electrode.
Preferably, the catechol substance is catechol, 4- methyl pyrocatechol, protocatechuic acid, protocatechuic acid
In ethyl ester, caffeic acid, chlorogenic acid, Rosmarinic acid, rutin, (+)-catechin, (-)-epicatechin, luteolin or Quercetin
It is one or more.Detection method of the present invention is applicable to a variety of catechol substances, has a wide range of application.
Preferably, in cyclic voltammetry test process, the scanning potential range of electrochemical workstation is -0.8~1.2V；It sweeps
Retouching rate is 0.01~0.10V/s；Sensitivity is 10-5A/V；Preliminary sweep direction is forward direction；Scanning number of segment is 2；Temperature is 25
±1℃。
Preferably, before the solution A, solution B and solution C are detected, the oxygen in solution need to first be removed.
It is highly preferred that before the solution A, solution B and solution C are detected, be passed through respectively into every part of solution nitrogen with
Remove oxygen.
It is highly preferred that the time that is passed through of the nitrogen is 5~10min.
Preferably, the glassy carbon working electrode diameter is 3mm；The glassy carbon working electrode need to drip before scanning every time
Add and polish on the chamois leather that partial size is 0.05 μm of aluminium oxide suspension, then wash with distilled water.Before testing, to vitreous carbon electricity
The polishing of pole can effectively remove the attachment of electrode surface, guarantee that electrode surface is clean, raising detection standard before testing
True property.
Preferably, the buffer is formulated using phosphate.
Preferably, the pH of the buffer is 5.0~8.0, wherein phosphatic concentration is 0.2M.
Preferably, when the solute in solution A is luteolin or Quercetin, solvent is 0.2M phosphate buffer and second
The mixed liquor of alcohol, volume ratio 4:1.
Preferably, in the solution A and C, the concentration of catechol substance is 0.5mM.
Preferably, in the Solutions Solution B and C, the concentration of CML is 0.5~7.5mM.
Compared with prior art, the invention has the following advantages:
(1) present invention utilizes cyclic voltammetry, can rapidly and system so that phenolic substances aoxidizes after forming quinones substance
In CML interaction, reduce the side reaction of quinones substance；By can be effective to the polishing of glassy carbon electrode before testing every time
The attachment of electrode surface is removed, detection accuracy is improved；Reduce in the prior art polyphenol and its oxidation product in working electrode
Interference of the factors such as attachment, quinones substance related side effect to quinones substance and CML interaction.
(2) method of the invention is simple, and analysis time is short, has good repeatability and convenience, and use cost is lower,
Quinones substance and CML interaction research field with good application prospect, compensate for prior art means and be only capable of measurement 4- first
The weakness of base neighbour's benzene diquinone and CML interaction.
Detailed description of the invention
Fig. 1 is the cyclic voltammogram (pH 7.0, sweep speed 0.01V/s) of catechol and CML interaction.
Fig. 2 is the cyclic voltammogram (pH 7.0, sweep speed 0.01V/s) of 4- methyl pyrocatechol and CML interaction.
Fig. 3 is the cyclic voltammogram (pH 7.0, sweep speed 0.01V/s) of protocatechuic acid and CML interaction.
Fig. 4 is the cyclic voltammogram (pH 7.0, sweep speed 0.05V/s) of protocatechuic acid and CML interaction.
Fig. 5 is the cyclic voltammogram (pH 7.0, sweep speed 0.05V/s) of ethyl protocatechuate and CML interaction.
Fig. 6 is the cyclic voltammogram (pH 7.0, sweep speed 0.01V/s) of caffeic acid and CML interaction.
Fig. 7 is the cyclic voltammogram (pH 7.0, sweep speed 0.01V/s) of chlorogenic acid and CML interaction.
Fig. 8 is the cyclic voltammogram (pH 7.0, sweep speed 0.01V/s) of Rosmarinic acid and CML interaction.
Fig. 9 is the cyclic voltammogram (pH 7.0, sweep speed 0.05V/s) of rutin and CML interaction.
Figure 10 is the cyclic voltammogram (pH 7.0, sweep speed 0.05V/s) of (+)-catechin and CML interaction.
Figure 11 is the cyclic voltammogram (pH 7.0, sweep speed 0.05V/s) of (-)-epicatechin and CML interaction.
Figure 12 is the cyclic voltammogram (pH 7.0, sweep speed 0.05V/s) of luteolin and CML interaction.
Figure 13 is the cyclic voltammogram (pH 7.0, sweep speed 0.05V/s) of Quercetin and CML interaction.
Specific embodiment
The present invention is made combined with specific embodiments below and further being elaborated, the embodiment is served only for explaining this
Invention, is not intended to limit the scope of the present invention.Test method as used in the following examples is normal unless otherwise specified
Rule method；Used material, reagent etc., unless otherwise specified, for the reagent and material commercially obtained.
Embodiment 1
A kind of method of quinones substance and CML interaction efficiency in measurement solution, follows the steps below test:
S1. catechol substance is dissolved in buffer and obtains solution A；CML is dissolved in buffer and obtains solution B；It will be adjacent
Benzenediol substance and CML are dissolved in buffer and obtain solution C；
S2. with glassy carbon electrode (diameter 3mm) for working electrode, platinum filament is to electrode, and silver/saturation silver chlorate is reference
Electrode, each electrode are connected with electrochemical workstation, three-electrode system are constructed, using cyclic voltammetry respectively to solution A, solution B
It is detected with solution C, obtains the cyclic voltammetry curve of every part of solution, and record the peak point current and voltage of every part of solution respectively
Characteristic value；Before testing, every part of solution to be measured is passed through 5~10min high pure nitrogen to remove oxygen；Glassy carbon working electrode is every
It need to polish on the chamois leather that the aluminium oxide suspension that partial size is 0.05 μm is added dropwise before secondary scanning, then wash with distilled water；Electrification
The scanning potential range for learning work station is -0.8~1.2V；Sweep speed is 0.01~0.10V/s；Sensitivity is 10-5A/V；Just
Beginning scanning direction is forward direction；Scanning number of segment is 2；Temperature is 25 ± 1 DEG C；
S3. it according to the step S2 peak point current measured and voltage characteristic value, is calculated, can be measured according to following formula
The interaction efficiency of quinones substance and CML are as follows:
Interaction efficiency=(reduction peak current slip, %)=(IPC1 (phenol)-IPC1 (phenol+CML))/IPC1 (phenol)；
The wherein IPC1 (phenol)For the reduction peak peak point current of the solution A；The IPC1 (phenol+CML)For going back for the solution C
Parent peak peak point current.
1, the influence of the pH value, sweep speed and CML concentration of buffer for testing result is probed into
According to the process of above-mentioned steps S1, using NaH2PO4、Na2HPO4, secure ph is 5.0,7.0,8.0 respectively
Then 0.2M phosphate buffer dissolves a certain amount of catechol or 4- methyl pyrocatechol, configuration obtains solution A, wherein adjacent
The concentration of benzenediol or 4- methyl pyrocatechol is 0.5mM；
Take a certain amount of CML be dissolved in 0.2M phosphate buffer solution prepare obtain solution B, wherein the concentration of CML be 0.5~
7.5mM；
A certain amount of catechol (or 4- methyl pyrocatechol) and CML are dissolved in buffer, magnetic agitation, which mixes, to be prepared
It obtaining solution C, guarantees that the concentration of catechol (or 4- methyl pyrocatechol) in solution C is 0.5mM, the concentration of CML is 0.5~
7.5mM。
According to the detection process in above-mentioned steps S2, different sweep speeds (0.01,0.05 and 0.10V/s) progress is converted
Detection, measures that result is as shown in Table 1 and Table 2, and wherein table 1 is adjacent benzene diquinone and CML (5.0mM) interaction efficiency under different condition
Testing result, table 2 are the testing result of 4- methyl neighbour's benzene diquinone and CML (5.0mM) interaction efficiency under different condition, and table 3 is 4-
The detection knot of methyl neighbour's benzene diquinone and various concentration CML (0.5-7.5mM) the interaction efficiency at 7.0 sweep speed 0.01V/s of pH
Fruit.Wherein reduction current slip shows that more greatly the extent of reaction is bigger, i.e. the efficiency reacted with CML of quinones substance is higher.
The interaction efficiency of adjacent benzene diquinone and CML under 1 different condition of table
The interaction efficiency of 4- methyl neighbour's benzene diquinone and CML under 2 different condition of table
It is found that the method for the invention is preferable in the condition stability inferior of pH 7.0 and 8.0 from Tables 1 and 2, RSD value exists
Between 0.00 to 9.22, stability is preferable；In pH 5.0, due to the lower side of causing of interaction efficiency between quinones substance and CML
Method stability is poor, and RSD value is higher.Therefore it is mutual to be more suitable for quinones substance and CML in the solution system of pH 7.0 and 8.0 for this method
Make the detection of efficiency.
The present invention is judged by reduction peak current slip in phenolic substances cyclic voltammetry curve before and after measurement addition CML
The interaction of CML and quinones substance, slip is bigger, and interaction efficiency is higher.Adjacent benzene diquinone or 4- methyl neighbour's benzene diquinone are in difference
Under pH, same scan rate conditions sequentially with CML interaction efficiency are as follows: 7.0 > pH of pH8.0 > pH 5.0；Control is utilized with existing
Potential electrolysis coulomb method processed prepares 4- methyl neighbour benzene diquinone, then using residence time radial measurement 4- methyl neighbour benzene diquinone substance with
The CML efficiencies that interact under condition of different pH are consistent (Food Chemistry, 2018,244:25-28), i.e. pH 8.0
7.0 > pH of > pH 5.0, so quinones substance and the method for CML interaction efficiency are accurate in a kind of measurement solution of the present invention
Property is higher.
The interaction efficiency of 4- methyl neighbour's benzene diquinone and various concentration CML under 3 pH 7.0 of table, sweep speed 0.01V/s
As shown in Table 3, under pH 7.0, sweep speed 0.01V/s, using this method measurement 4- methyl neighbour's benzene diquinone from it is different
The stability of concentration C ML interaction efficiency is preferable, and RSD value range is 0.35-5.62.With the increase of system CML content, 4- methyl
The interaction efficiency of adjacent benzene diquinone and CML dramatically increase, and meet theory expectation.
2, influence of the different substituents to quinones substance and CML interaction efficiency on phenyl ring is probed into
Test process in test process reference embodiment 1, the difference is that, solution A is respectively catechol, 4- first
Base catechol or protocatechuic acid are dissolved in phosphate buffer (0.2M, pH7.0) preparation and obtain, and the concentration of polyphenols is
0.5mM；Solution C is respectively catechol, 4- methyl pyrocatechol or protocatechuic acid and CML be dissolved in phosphate buffer (0.2M,
PH7.0 it) prepares and obtains, wherein polyphenols concentration is 0.5mM, and the concentration of CML is 5.0mM.In test process, electrochemistry work
Make the operating parameter stood are as follows: scanning potential range, -0.8-1.2V；Sweep speed, 0.01V/s；Sensitivity, 10-5A/V；Initially sweep
Direction is retouched, it is positive；Scanning number of segment, 2.The cyclic voltammetry curve of every part of solution is obtained, and records the peak value electricity of every part of solution respectively
Stream and voltage characteristic value, and calculated according to the formula in embodiment 1.Calculated result is as shown in table 4.
The interaction efficiency of table 4 different quinones substances and CML
As can be known from Table 4, under the same terms, CML and the interaction efficiency that the protocatechuic acid quinone formed is aoxidized by protocatechuic acid
Highest, it is with the adjacent benzene diquinone interaction efficiency that is formed is aoxidized by catechol placed in the middle, it is formed with being aoxidized by 4- methyl pyrocatechol
4- methyl neighbour's benzene diquinone interaction efficiency is minimum.The electronics that there is methyl group on phenyl ring electron effect to increase quinones substance
Cloud density, therefore reduce the activity of its electrophilic reaction；There is carboxylic group on phenyl ring Draw electronic effect to reduce quinones object
The cloud density of matter, therefore enhance the activity of its electrophilic reaction.To sum up, test result of the present invention meets theory expectation, and
Stability with higher (RSD value range is 0.00-9.22).
3, protocatechuic acid, protocatechuic acid carboxyethyl are oxidized to the extent of reaction of corresponding quinones substance and CML
Test process in test process reference embodiment 1, the difference is that, solution A is respectively protocatechuic acid or original
Catechu acetoacetic ester is dissolved in phosphate buffer (0.2M, pH7.0) preparation and obtains, and the concentration of polyphenols is 0.5mM；Solution
C is respectively that protocatechuic acid or ethyl protocatechuate and CML are dissolved in phosphate buffer (0.2M, pH7.0) preparation and obtain, wherein more
Phenolic substances concentration is 0.5mM, and the concentration of CML is 5.0mM.In test process, the operating parameter of electrochemical workstation are as follows: scanning
Potential range, -0.8-1.2V；Sweep speed, 0.05V/s；Sensitivity, 10-5A/V；Preliminary sweep direction, it is positive；Number of segment is scanned,
2.The cyclic voltammetry curve of every part of solution is obtained, and records the peak point current and voltage characteristic value of every part of solution respectively, and according to
Formula in embodiment 1 is calculated.Calculated result is as shown in table 5.
The interaction efficiency of table 5 different catechol quinones substances and CML
As can be known from Table 5, under the same terms, CML and the interaction efficiency that the protocatechuic acid quinone formed is aoxidized by protocatechuic acid
More high-efficient than with the interaction that aoxidizes the ethyl protocatechuate quinone formed by ethyl protocatechuate, the ethyl esterified effect of carboxyl weakens
The Draw electronic effect of carboxyl, thus its electrophilic reaction ability declines, test result of the present invention meets theory expectation, and has higher
Stability (RSD value range be 0.39-6.22).
4, different phenolic acids aoxidize the extent of reaction for the quinones substance and CML to be formed
Test process in test process reference embodiment 1, the difference is that, solution A is respectively caffeic acid, chlorogenic acid
Or Rosmarinic acid is dissolved in phosphate buffer (0.2M, pH7.0) preparation and obtains, the concentration of polyphenols is 0.5mM；Solution
C is respectively caffeic acid, chlorogenic acid or Rosmarinic acid and CML is dissolved in phosphate buffer (0.2M, pH7.0) preparation and obtains, wherein
Polyphenols concentration is 0.5mM, and the concentration of CML is 5.0mM.In test process, the operating parameter of electrochemical workstation are as follows: sweep
Retouch potential range, -0.8-1.2V；Sweep speed, 0.01V/s；Sensitivity, 10-5A/V；Preliminary sweep direction, it is positive；Scanning Section
Number, 2.The cyclic voltammetry curve of every part of solution is obtained, and records the peak point current and voltage characteristic value of every part of solution respectively, and press
It is calculated according to the formula in embodiment 1.Calculated result is as shown in table 6.
The different phenolic acids of table 6 aoxidize the extent of reaction for the quinones substance and CML to be formed
As can be known from Table 6, under the same terms, CML be higher than with the caffeic acid quinone interaction efficiency formed by coffee acid oxidase and
By chlorogenic acid or the quinones substance of Rosmarinic acid oxidation, large-scale substituent group bring is empty on chlorogenic acid quinone and Rosmarinic acid quinone phenyl ring
Between steric effect weaken its interaction efficiency with CML, test result of the present invention meets theory expectation, and stabilization with higher
Property (RSD value range be 2.80-7.27).
5, Flavonoid substances aoxidize the extent of reaction for the quinones substance and CML to be formed
Test process in test process reference embodiment 1, the difference is that, solution A is respectively to take rutin, (+)-youngster
Theine or (-)-epicatechin are dissolved in phosphate buffer (0.2M, pH7.0) preparation and obtain, or take luteolin or Quercetin
It is dissolved in the mixed liquor (volume ratio: 4:1, pH 7.0) of 0.2M phosphate buffer and ethyl alcohol, polyphenols concentration is
0.5mM；Solution C is respectively rutin, (+)-catechin or (-)-epicatechin and CML be dissolved in phosphate buffer (0.2M,
PH7.0 it) prepares and obtains, or be dissolved in the mixed liquor of 0.2M phosphate buffer and ethyl alcohol for luteolin or Quercetin and CML
(volume ratio: 4:1, pH 7.0) preparation obtains, and wherein polyphenols concentration is 0.5mM, and the concentration of CML is 5.0mM.It tested
Cheng Zhong, the operating parameter of electrochemical workstation are as follows: scanning potential range, -0.8-1.2V；Sweep speed, 0.05V/s；Sensitivity,
10-5A/V；Preliminary sweep direction, it is positive；Scanning number of segment, 2.The cyclic voltammetry curve of every part of solution is obtained, and records every part respectively
The peak point current and voltage characteristic value of solution, and calculated according to the formula in embodiment 1.Calculated result is as shown in table 7.
7 Flavonoid substances of table aoxidize the interaction efficiency for the quinones substance and CML to be formed
As can be known from Table 7, under the same terms, CML is with the luteolin quinone interaction efficiency formed is aoxidized by luteolin
Highest in selected flavones, this is lower related with its phenyl ring cloud density, and test result of the present invention meets theory expectation, RSD
Value range is 5.48-42.73, and part Flavonoid substances measuring stability is bad.
To sum up, the present invention is suitable for detecting CML imitates from the reaction that a variety of different phenolic substancess aoxidize the quinones substance to be formed
Rate meets theory expectation, shows that testing result is accurate, while the RSD value of testing result is smaller, shows detection method and detection knot
Fruit has stability.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of shield range can also be made on the basis of above description and thinking for those of ordinary skill in the art
Other various forms of variations or variation, there is no necessity and possibility to exhaust all the enbodiments.It is all of the invention
Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle
Within the scope of.
Claims (10)
1. a kind of method of quinones substance and carboxymethyl-lysine interaction efficiency in measurement solution, which is characterized in that including as follows
Step:
S1. catechol substance is dissolved in buffer and obtains solution A；CML is dissolved in buffer and obtains solution B；By adjacent benzene two
Phenolic substances and CML are dissolved in buffer and obtain solution C；
S2. using glassy carbon electrode as working electrode, platinum filament is to electrode, and silver/saturation silver chlorate is reference electrode, each electrode and electricity
Chem workstation is connected, and constructs three-electrode system, is detected respectively to solution A, solution B and solution C using cyclic voltammetry,
The cyclic voltammetry curve of every part of solution is obtained, and records the peak point current and voltage characteristic value of every part of solution respectively；
S3. it according to the step S2 peak point current measured and voltage characteristic value, is calculated according to following formula, solution can be measured
The interaction efficiency of middle quinones substance and CML:
Interaction efficiency/%=(IPC1 (phenol)-IPC1 (phenol+CML))/IPC1 (phenol)；
The wherein IPC1 (phenol)For the reduction peak peak point current of the solution A；The IPC1 (phenol+CML)For the reduction peak of the solution C
Peak point current.
2. the method that measurement measures quinones substance and CML interaction efficiency in solution according to claim 1, which is characterized in that
The catechol substance is catechol, 4- methyl pyrocatechol, protocatechuic acid, ethyl protocatechuate, caffeic acid, green original
One of acid, Rosmarinic acid, rutin, (+)-catechin, (-)-epicatechin, luteolin or Quercetin are a variety of.
3. measuring the method for quinones substance and CML interaction efficiency in solution according to claim 1, which is characterized in that circulation
In voltammetry test process, the scanning potential range of electrochemical workstation is -0.8~1.2V；Sweep speed be 0.01~
0.10V/s；Sensitivity is 10-5A/V；Preliminary sweep direction is forward direction；Scanning number of segment is 2；Temperature is 25 ± 1 DEG C.
4. measuring the method for quinones substance and CML interaction efficiency in solution according to claim 1, which is characterized in that described
Before solution A, solution B and solution C are detected, the oxygen in solution need to be first removed.
5. measuring the method for quinones substance and CML interaction efficiency in solution according to claim 4, which is characterized in that described
Before buffer solution A, buffer solution B and mixed solution C are detected, it is passed through nitrogen into every part of solution respectively to remove oxygen.
6. measuring the method for quinones substance and CML interaction efficiency in solution according to claim 5, which is characterized in that described
The time that is passed through of nitrogen is 5~10min.
7. measuring the method for quinones substance and CML interaction efficiency in solution according to claim 1, which is characterized in that described
Glassy carbon working electrode diameter is 3mm；Before scanning every time oxygen of the partial size for 0.05 μm need to be added dropwise in the glassy carbon working electrode
Change and polish on the chamois leather of aluminium suspension, then wash with distilled water.
8. measuring the method for quinones substance and CML interaction efficiency in solution according to claim 1, which is characterized in that described
Buffer is formulated using phosphate；The pH of the buffer is 5.0~8.0, wherein phosphatic concentration is 0.2M.
9. measuring the method for quinones substance and CML interaction efficiency in solution according to claim 2, which is characterized in that when molten
When solute in liquid A is luteolin or Quercetin, solvent is the mixed liquor of 0.2M phosphate buffer and ethyl alcohol, and volume ratio is
4:1。
10. measuring the method for quinones substance and CML interaction efficiency in solution according to claim 1, which is characterized in that described
In solution A and C, the concentration of catechol substance is 0.5mM；In the solution B and C, the concentration of CML is 0.5~7.5mM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910406744.6A CN110208355B (en) | 2019-05-16 | 2019-05-16 | Method for measuring interaction efficiency of quinone substances and carboxymethyl lysine in solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910406744.6A CN110208355B (en) | 2019-05-16 | 2019-05-16 | Method for measuring interaction efficiency of quinone substances and carboxymethyl lysine in solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110208355A true CN110208355A (en) | 2019-09-06 |
| CN110208355B CN110208355B (en) | 2022-07-05 |
Family
ID=67787472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910406744.6A Active CN110208355B (en) | 2019-05-16 | 2019-05-16 | Method for measuring interaction efficiency of quinone substances and carboxymethyl lysine in solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110208355B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101349673A (en) * | 2008-09-04 | 2009-01-21 | 南京大学 | Electrochemical method for non-eletricity enriching and measuring trace amount tervalence inorganic arsenic in water system |
| CN102288669A (en) * | 2011-05-04 | 2011-12-21 | 青岛大学 | Electrochemical method based on graphene-modified electrode for simultaneous determination of rutin and quercetin |
| CN102809592A (en) * | 2012-07-13 | 2012-12-05 | 江苏大学 | Electro-polymerization preparation method of electrochemical sensor for quickly detecting EGCG (Epigallocatechin-3-Gallate) |
| CN105918772A (en) * | 2016-05-30 | 2016-09-07 | 华南理工大学 | Class-I carboxymethyl lysine removing agent and application thereof |
-
2019
- 2019-05-16 CN CN201910406744.6A patent/CN110208355B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101349673A (en) * | 2008-09-04 | 2009-01-21 | 南京大学 | Electrochemical method for non-eletricity enriching and measuring trace amount tervalence inorganic arsenic in water system |
| CN102288669A (en) * | 2011-05-04 | 2011-12-21 | 青岛大学 | Electrochemical method based on graphene-modified electrode for simultaneous determination of rutin and quercetin |
| CN102809592A (en) * | 2012-07-13 | 2012-12-05 | 江苏大学 | Electro-polymerization preparation method of electrochemical sensor for quickly detecting EGCG (Epigallocatechin-3-Gallate) |
| CN105918772A (en) * | 2016-05-30 | 2016-09-07 | 华南理工大学 | Class-I carboxymethyl lysine removing agent and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李玉婷: "儿茶素捕获与抑制羧甲基赖氨酸双效机制的研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110208355B (en) | 2022-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | Electrochemical behavior and voltammetric determination of tryptophan based on 4-aminobenzoic acid polymer film modified glassy carbon electrode | |
| CN102288669B (en) | Electrochemical method based on graphene-modified electrode for simultaneous determination of rutin and quercetin | |
| CN103320498B (en) | Detection reagent for aspartate aminotransferase | |
| CN104634853A (en) | Method for detecting concentration of acrylamide in solution | |
| CN105466980B (en) | A kind of plant live body ascorbic acid detection method based on microelectrode biosensor | |
| CN106770601B (en) | The electrochemical method of capsaicine in a kind of detection food | |
| CN106290512A (en) | Modified electrode and its preparation method and application | |
| CN105572199A (en) | Working electrode biological reactant and electrode type test strip | |
| CN106290537A (en) | The method of L-type Tryptophan concentration in detection solution | |
| CN106442667A (en) | Method for detecting blood glucose by virtue of persimmon tannin@graphene@Pt-Pd non-enzymatic sensor | |
| CN104569121B (en) | Method for detecting lead ion concentration in solution | |
| CN106645340B (en) | With method carmine in the monatomic composite material detection food of graphene-supported Pt | |
| CN107102052B (en) | Based on the uric acid electrochemical sensor containing active copper carbon dots and its application | |
| CN110208355A (en) | A kind of method of quinones substance and carboxymethyl-lysine interaction efficiency in measurement solution | |
| CN104655700B (en) | Food preservative electrochemical sensor and preparation method and application | |
| CN110308141A (en) | A kind of Electrochemiluminescince detecting catechol | |
| CN108982618A (en) | Nanogold/graphene modified screen printing electrode, preparation method and application | |
| CN109374706A (en) | A method of trace carbadox is detected with the structure mesoporous carbon CMK-8 Direct Electrochemistry sensor of cube Ia3d | |
| CN109374708A (en) | With the method for hydroxylated multi-walled carbon nanotubes the@cubic mesoporous measurement of carbon composite membrane electrochemical sensor trace olaquindox and carbadox | |
| Karaosmanoglu et al. | Electrochemical analysis of beverage phenolics using an electrode modified with poly (3, 4-ethylenedioxithiophene) | |
| Zhu et al. | 9, 10‐Anthraquinone Modified Glassy Carbon Electrode and Its Application for Hemoglobin Determination | |
| CN103884753B (en) | A kind of preparation method of rhodamine 6G/oxine film modified electrod and application | |
| CN206974948U (en) | A kind of biology sensor for detecting residual tetracycline | |
| CN104931553A (en) | Preparation and detection method of tetracycline aptamer sensor based on screen-printed electrode | |
| CN104931565A (en) | Preparation of screen-printed electrode aptamer sensor for detecting tetracycline residue |
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 |