WO2013004152A1 - Dispositif de détection de substance oxydable et procédé y associé - Google Patents

Dispositif de détection de substance oxydable et procédé y associé Download PDF

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Publication number
WO2013004152A1
WO2013004152A1 PCT/CN2012/077850 CN2012077850W WO2013004152A1 WO 2013004152 A1 WO2013004152 A1 WO 2013004152A1 CN 2012077850 W CN2012077850 W CN 2012077850W WO 2013004152 A1 WO2013004152 A1 WO 2013004152A1
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Prior art keywords
column
inlet
detector
liquid chromatography
performance liquid
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PCT/CN2012/077850
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English (en)
Chinese (zh)
Inventor
王兵
王涛
邢艳平
谭鹏
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北京泰克美科技有限公司
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Publication of WO2013004152A1 publication Critical patent/WO2013004152A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/64—Electrical detectors

Definitions

  • the present invention relates to a detection apparatus and method in the field of high performance liquid chromatography, and more particularly to an apparatus and method for detecting an oxidizable substance. Background technique
  • Antioxidants are substances that prevent the adverse effects of oxygen. They are a class of substances that help capture and neutralize free radicals, thereby eliminating free radical damage.
  • Food antioxidants are food additives that prevent or delay the oxidative deterioration of foods, improve food stability, and extend shelf life. However, food antioxidants are heated, especially at high temperatures, such as after frying, and are easily decomposed or volatilized to lose antioxidant activity. In order to increase the number of repeated use of edible oils, many manufacturers add antioxidants that exceed several times or even dozens of times in the processing of fried foods. Thus, after frying, the residual amount of antioxidants in finished products and used oils It still meets the current national standards for the use of antioxidants, which is a serious hazard to human health. In response to the use of antioxidants, the state has issued various standards for the detection of antioxidants, providing a basis for the detection of antioxidants.
  • Hair dyes are a class of cosmetics containing dyes. According to the degree of firmness after dyeing, it can be divided into temporary, semi-permanent and permanent. Among them, permanent hair dyes are divided into oxidation dyes, vat dyes and natural melanin dyes. Oxidation dyes are among the first synthetic dyes used for hair dyeing, and are currently the most widely used permanent hair dye materials. Oxidized hair dyes have become the most popular hair dyes due to their excellent dyeing effect, wide color tone change and long maintenance time.
  • the principle of the oxidative hair dye is that the aniline substance is oxidized into a dye intermediate under the action of an oxidizing agent, and then a coupling reaction occurs under the action of a coupling agent (benzenediol) to produce a color and dye the hair.
  • the oxidative hair dye is mainly composed of an oxidizing dye and an oxidizing agent.
  • the dye components in the hair dye are mostly aromatic amine compounds, and more than 4 substances in the compound are carcinogenic, so the safety of the hair dye has been extremely popular. Great concern. Allergic reactions caused by hair dyes are also very common, and long-term use may also cause teratogenicity, mutagenicity, carcinogenesis and endocrine effects.
  • the methods for detecting oxidative dyes in hair dyes mainly include gas chromatography, gas chromatography-mass spectrometry and liquid chromatography.
  • the "Hygienic Standards for Cosmetics” promulgated by the Ministry of Health of the People's Republic of China (2007 edition) clearly stipulates 93 kinds of hair dyes that are temporarily allowed to use, and sets limits.
  • the use of some dosage forms in oxidative hair dyes may cause cancer, and the components of the oxidative dyes may also be partially oxidized, and there are also problems similar to antioxidants, so that the actual use amount cannot be accurately determined when it is detected.
  • the problem to be solved by the present invention is to provide a detecting device and method capable of accurately measuring the actual added amount of an oxidizable substance.
  • the basic principle of the present invention is to reduce the oxidation product of the easily oxidizable substance in the substance to be tested into the oxidizable substance, and the reducing device is an electrochemical reactor or a reduction column, thereby avoiding the cause of the substance to be tested. Partial oxidation leads to the problem that the measured content is lower than the actual content, and the harm to human health caused by the measurement error to the excessive monitoring of the limited substance is reduced.
  • the invention provides a detecting device for an oxidizable substance, comprising:
  • a high performance liquid chromatography pump an injector, a reduction device, a high performance liquid chromatography column, and a detector; wherein, the outlet of the high performance liquid chromatography pump is connected to an inlet of the injector, the The sample outlet of the sample is connected to the inlet of the reduction device, and the outlet of the reduction device is connected to the inlet of the high performance liquid chromatography column, and the outlet of the high performance liquid chromatography column Connected to the inlet of the detector;
  • outlet of the high performance liquid chromatography pump is connected to the inlet of the injector, and the outlet of the injector is connected to the inlet of the high performance liquid chromatography column,
  • the outlet of the high performance liquid chromatography column is connected to the inlet of the reduction device, and the outlet of the reduction device is connected to the inlet of the detector;
  • outlet of the high performance liquid chromatography pump is connected to the inlet of the reduction device, and the outlet of the reduction device is connected to the inlet of the injector, and the outlet of the injector a sample port is connected to the inlet of the high performance liquid chromatography column, and the sample port of the high performance liquid chromatography column is injected with the detector Connected to the mouth;
  • the outlet of the high performance liquid chromatography pump is connected to the inlet of the injector, and the outlet of the injector is connected to the inlet of the high performance liquid chromatography column,
  • the outlet of the high performance liquid chromatography column is connected to the inlet of the detector, and the reduction device is disposed in the injector.
  • the reduction device is an electrochemical reactor.
  • the electrochemical reactor is a Coulomb detector.
  • the outlet of the high performance liquid chromatography pump is connected to the inlet of the sampler, the outlet of the sampler is connected to the inlet of the reduction device, and the sample of the reduction device is sampled.
  • a port is connected to the inlet of the enrichment column or the quantification ring through the six-way valve, and the sample port of the enrichment column or the quantification ring passes through the six-way valve and the high-performance liquid chromatography column
  • the sample port is connected, and the outlet of the high performance liquid chromatography column is connected to the inlet of the detector.
  • the precolumn is further included;
  • the sample outlet of the sampler is connected to the inlet of the pre-column, and the outlet of the pre-column is connected to the inlet of the reduction device.
  • the reducing device is a reduction column
  • the outlet of the high performance liquid chromatography pump is connected to the inlet of the sampler, the outlet of the sampler is connected to the inlet of the reduction column, and the sample of the reduction column is sampled.
  • the port is connected to the inlet of the high performance liquid chromatography column, and the outlet of the high performance liquid chromatography column is connected to the inlet of the detector.
  • the detector is a UV detector, an amperometric detector, a differential detector, a fluorescence detector, a secondary array tube detector or a speech detector.
  • the oxidizable substance is preferably oxidized and the main structure does not change after oxidation, and the oxidizable substance is an antioxidant, an oxidative dye or a traditional Chinese medicine polyphenol.
  • the present invention also provides a method of detecting an oxidizable substance using the above-described detecting device.
  • the apparatus for detecting oxidizable substances provided by the present invention comprises a high performance liquid chromatography pump, an injector, a reduction device, a high performance liquid chromatography column (HPLC column) and a detector, and the reduction device Before being connected to the injector, may be connected between the injector and the high performance liquid chromatography column, or may be connected between the high performance liquid chromatography column and the detector, Can be set In the injector.
  • the invention adds a reducing device in the separation detecting device using the high-performance liquid chromatography column, which can reduce the oxidation product of the easily oxidizable substance in the substance to be tested into the oxidizable substance, and then adopts a detector for detection, thereby avoiding The problem that the substance to be tested is lower than the actual content due to partial oxidation can accurately determine the actual addition amount of the oxidizable substance, and reduce the harm to human health caused by the measurement error to the excessive monitoring of the limited substance.
  • the present invention utilizes the reduction device to perform on-line reduction of the oxidation product of the oxidizable substance, thereby avoiding detection error caused by reoxidation of the oxidation product of the easily oxidizable substance during off-line reduction, that is, It is avoided that the oxidation product of the oxidizable substance is first reduced, and then injected to cause the oxidation product of the oxidizable substance to be reoxidized after reduction.
  • the invention reduces the oxidation product of the substance to be tested by adjusting the electrode voltage of the electrochemical reactor such as the Coulomb detector, or by the action of the reduction column, and then uses the detector to detect, thereby greatly reducing the unstable substance due to oxidation.
  • the detection error of the content below the actual content provides a solution for controlling the excessive addition of some limited substances, and also provides a new detection device and detection method for the accurate determination of oxidizable substances.
  • the on-line reduction of the sample is achieved by setting the working electrode voltage of the electrochemical reactor, such as the Coulomb detector, to a negative voltage.
  • the electrochemical reactor is connected before the injector, after the HPLC column, or between the injector and the HPLC column.
  • the electrochemical reactor When the electrochemical reactor is between the injector and the HPLC column, the electrochemical reactor is connected to the inlet of the high performance liquid chromatography column through a six-way valve, and the connection of the system is changed by a six-way valve. , Online reduction detection of easily oxidizable substances.
  • the invention realizes the feasibility of connecting the electrochemical reactor to the front of the column by means of valve switching by connecting a six-way valve in the system, and avoids the occurrence of an excessive system pressure accident and the resulting one. Series of questions.
  • the invention will utilize an electrochemical reactor such as a coulometric detector to achieve separation prior to HPLC column separation.
  • the oxidation product is reduced on-line to achieve accurate determination of easily oxidizable substances; or the oxidation product of oxidizable substances such as antioxidants is reduced on-line by a reduction column and then separated and detected.
  • connection position of the reduction column is after the injector, before the HPLC chromatography column, that is, between the injector and the HPLC color column, the oxidation product of the easily oxidizable substance is directly reduced by the reduction column and then used. Detector detection.
  • the invention fully utilizes the characteristics of the electrochemical reactor such as the Coulomb detector, or the characteristics of the reduction column, and can restore the characteristics of the sample for use in the sample processing, and provides a new detection method for the analysis of the oxidizable substance and method.
  • Figure 1 is a schematic diagram of the flow path of an electrochemical reactor and detector in a series system after HPLC column.
  • Fig. 2 (a) is a schematic diagram of the system flow path before the injection of the electrochemical reactor between the injector and the color column; (b) the electrochemical reactor is connected to the injector and the color column. Schematic diagram of the system flow path after injection.
  • Figure 3 is a schematic diagram of the flow path of the TBHQ system for detecting antioxidants in front of a color column.
  • Figure 4 is a color-peak peak of a TBHQ sample that has been reduced by an electrochemical reactor.
  • Figure 5 is a color-peak peak for direct loading (unreduced) of TBHQ samples.
  • Figure 6 is a plot of electrode voltage -200 mV in an electrochemical reactor with an ampere detector electrode voltage of +600 mV.
  • Figure 7 is an electrode voltage OmV in an electrochemical reactor with an ampere detector electrode voltage of +600 mV.
  • Figure 8 is a graph showing changes in the TBHQ peak (280 nm) before and after heating.
  • Figure 9 is a schematic illustration of the change in degradation products before and after heating.
  • Figure 10 is a schematic diagram showing the change of the TBHQ peak before and after the addition of the reduction column. detailed description
  • the invention provides an apparatus for detecting oxidizable substances, comprising:
  • a high performance liquid chromatography pump an injector, a reduction device, a high performance liquid chromatography column, and a detector; wherein, the outlet of the high performance liquid chromatography pump is connected to an inlet of the injector, the a sample port of the sample device is connected to the inlet of the reducing device, and the sample port of the reducing device is high
  • the inlet of the liquid chromatography column is connected, and the outlet of the high performance liquid chromatography column is connected to the inlet of the detector;
  • outlet of the high performance liquid chromatography pump is connected to the inlet of the injector, and the outlet of the injector is connected to the inlet of the high performance liquid chromatography column,
  • the outlet of the high performance liquid chromatography column is connected to the inlet of the reduction device, and the outlet of the reduction device is connected to the inlet of the detector;
  • outlet of the high performance liquid chromatography pump is connected to the inlet of the reduction device, and the outlet of the reduction device is connected to the inlet of the injector, and the outlet of the injector a sample port is connected to the inlet of the high performance liquid chromatography column, and the sample port of the high performance liquid chromatography column is connected to the inlet of the detector;
  • the outlet of the high performance liquid chromatography pump is connected to the inlet of the injector, and the outlet of the injector is connected to the inlet of the high performance liquid chromatography column,
  • the outlet of the high performance liquid chromatography column is connected to the inlet of the detector, and the reduction device is disposed in the injector.
  • the detecting device of the present invention is suitable for detecting unstable oxidizable substances, and the oxidizable substance is preferably a substance which is easily oxidized and does not change after the oxidation, and more preferably an antioxidant, an oxidative dye or a traditional Chinese medicine polyphenol. Preferred is the antioxidant tert-butyl hydroquinone (TBHQ).
  • TBHQ tert-butyl hydroquinone
  • the high performance liquid chromatography pump is a power device
  • the injector is a sample introduction device, both of which are well known to those skilled in the art
  • the high performance liquid chromatography column (HPLC column) Separation devices well known to those skilled in the art can be selected for different samples to be separated.
  • the reducing device is a device capable of reducing an oxidation product of an easily oxidizable substance in a substance to be tested, and the invention reduces the oxidation product of an easily oxidizable substance in the substance to be tested into the oxidizable substance by a reducing device, thereby avoiding waiting for
  • the problem of measuring the content of the substance due to partial oxidation is lower than the actual content, and reducing the harm to human health caused by the measurement error to the excessive monitoring of the limited substance.
  • the reducing device is preferably a reduction column or an electrochemical reactor, wherein the reduction column can reduce an oxidation product of an oxidizable substance such as an antioxidant to the oxidizable substance through a reducing agent therein, and the present invention
  • the column is not particularly limited, and a reduction column commonly used in the art, such as a powder reduction column; the electrochemical reactor is a special chemical reactor such as a Coulomb detector, and the electrochemical reactor of the present invention
  • the working electrode voltage is set to a negative voltage, and the oxidation product of the easily oxidizable substance in the substance to be tested can be reduced to the oxidizable substance to realize on-line reduction of the sample.
  • the detector may be a detector commonly used in the art, such as a UV detector, an amperometric detector, a differential detector, a fluorescence detector, a secondary array tube detector or a speech detector.
  • the apparatus and method for detecting oxidizable substances provided by the present invention have the following various implementations:
  • the apparatus for detecting oxidizable substances of the present invention comprises a high performance liquid chromatography pump, an injector, an electrochemical reactor or a reduction column, and a high performance liquid color.
  • a column and a detector wherein an outlet of the high performance liquid chromatography pump is connected to an inlet of the injector, and an outlet of the injector and the high performance liquid chromatography column Connected to the sample port, the outlet of the high performance liquid chromatography column is connected to the inlet of the electrochemical reactor or the reduction column, and the outlet of the electrochemical reactor or the reduction column and the detector
  • the inlets are connected.
  • the substance to be tested is introduced into the HPLC column through the sampler, and separated by the mobile phase elution, and the oxidized product and the oxidation product of the oxidizable substance are discharged from the outlet of the HPLC color column at different times.
  • the oxidizable substance and the oxidation product of the oxidizable substance are sequentially flowed into an electrochemical reactor having a negative working voltage, or sequentially flowed into the reduction column, and then detected by a detector, according to which the oxidizable substance is not Receiving an electrochemical reactor having a negative working voltage, or a reduction column, and the oxidation product of the oxidizable substance is subjected to an electrochemical reactor having a negative working voltage, or the reducing column is reduced to the oxidizable substance
  • the basic principle analyzing the test results, and obtaining the content information of the substance to be tested.
  • the chromatographic conditions for separation by HPLC color column are common chromatographic conditions in the field, and can be selected according to different samples to be tested;
  • the negative voltage of the device, or the type of the reduction column, can be adjusted according to different oxidizable substances.
  • the present invention can also separate the substance to be tested into an electrochemical reactor having an operating voltage of OmV, and then perform detection by a detector according to the oxidizable substance and the oxidizable substance.
  • the oxidation products were not affected by the electrochemical reactor with an operating voltage of OmV.
  • the results of the analysis confirmed that in the previous detection methods, the oxidation products of the oxidizable substances were not found or ignored. The result is lower than the actual content.
  • the apparatus for detecting an oxidizable substance of the present invention comprises a high performance liquid chromatography pump, an injector, an electrochemical reactor or a reduction column, a high performance liquid chromatography column and a detector, wherein the high performance liquid chromatography pump outlet Connected to the inlet of the injector, the outlet of the injector is connected to the inlet of the electrochemical reactor or the reduction column, and the outlet of the electrochemical reactor or the reduction column And the high performance liquid chromatography column
  • the inlets of the high performance liquid chromatography column are connected to the inlet of the detector.
  • the oxidizable substance to be tested is subjected to reduction by an electrochemical reactor whose working voltage is a negative voltage, or a reduction column, and then separated by a HPLC color column, and then detected by a detector, and finally analyzed.
  • the detection result obtains information on the content of the easily oxidizable substance to be tested.
  • the detection device preferably further includes a six-way valve and an enrichment column or a quantification ring through which the outlet of the electrochemical reactor passes the enrichment column or quantification
  • the inlets of the loop are connected, and the outlet of the enrichment column or the loop is connected to the inlet of the HPLC column through the six-way valve, and the invention realizes the electrochemical reactor by means of valve switching.
  • the detecting device preferably further comprises a pre-column, which may also be called a guard column, connected to the Between the injector and the electrochemical reactor, the electrochemical reactor is protected to effectively prevent contamination of impurities in the sample.
  • the detection device Before the detection, the detection device is first cleaned, specifically: the mobile phase is sequentially driven by the first high-performance liquid chromatography pump through the pre-column, the electrochemical reactor, and then enters the enrichment column through the six-way valve. Or the loop, and then flow out of the outlet into the waste bottle; the second high-performance liquid chromatography pump drives the mobile phase into the HPLC column through the six-way valve, and then flows out into the waste bottle through the detector to complete the cleaning.
  • the injector injects the substance to be tested, and continues to inject the mobile phase with the first high-performance liquid chromatography pump, and the material to be tested sequentially passes through the pre-column and the electrochemical reactor under the action of the mobile phase, under a negative voltage.
  • the oxidation product of the oxidizable substance in the substance to be tested is reduced to the oxidizable substance, and enters the enrichment column or the quantification ring through the six-way valve; according to the calculation of the pipe volume, the sample to be tested is obtained from the injection.
  • the oxidizable substance in the enrichment column or the quantitative loop is injected into an HPLC color column, and then detected by a detector to obtain a detection result.
  • the apparatus for detecting an oxidizable substance of the present invention comprises a high performance liquid chromatography pump, an injector, an electrochemical reactor or a reduction column, a high performance liquid chromatography column and a detector, wherein the high performance liquid chromatography pump outlet Connected to the inlet of the electrochemical reactor or the reduction column, the outlet of the electrochemical reactor or the reduction column is connected to the inlet of the injector, and the sample inlet of the sampler Connected to the inlet of the high performance liquid chromatography column, the outlet of the high performance liquid chromatography column is connected to the inlet of the detector.
  • the reduction column is subjected to reduction, and then injected into the HPLC column through the injector for separation, and then the detector is used for detection, and finally the detection result is analyzed to obtain the content information of the substance to be tested.
  • the apparatus for detecting an oxidizable substance of the present invention comprises a high performance liquid chromatography pump, an injector, an electrochemical reactor or a reduction column, a high performance liquid chromatography column and a detector, wherein the high performance liquid chromatography pump outlet Connected to the inlet of the injector, the outlet of the injector is connected to the inlet of the high performance liquid chromatography column, and the outlet of the high performance liquid chromatography column is The inlets of the detectors are connected, and the reduction device is disposed in the injector.
  • the present invention allows an electrochemical reactor, such as the core component of a Coulomb detector, to be mounted in the injector to form an integrated detection device that is substantially identical to the detection method in which the electrochemical reactor is placed outside the injector.
  • This embodiment specifically describes an apparatus for detecting an oxidizable substance provided by the present invention, and an experiment for measuring an antioxidant TBHQ and an oxidation product thereof using the apparatus provided by the technical solution of the present invention;
  • the apparatus includes an injector, a high-efficiency liquid Phase chromatography pump, HPLC color column, electrochemical reactor and amperometric detector;
  • FIG. 1 is a schematic diagram of a flow path of the electrochemical reactor and the detector in a series system after the HPLC color column,
  • the electrochemical reactor working electrode voltage can be set according to the specific conditions.
  • the antioxidant t-butyl hydroquinone (TBHQ) and its oxidation product were determined under the following chromatographic conditions.
  • the working voltage of the electrochemical reactor is set to a negative voltage, and the oxidation product of the antioxidant TBHQ is reduced on-line;
  • the amperometric detector acts as a detector to detect the antioxidant TBHQ and its oxidation products.
  • the sample enters the system through the injector. Under the mobile phase elution, the antioxidant TBHQ entering the HPLC column is separated from its oxidation product. After passing through the electrochemical reactor, at the set voltage (-200mV). Its oxidation product is in turn reduced to the antioxidant TBHQ. After the detector, two color peaks appear in the output spectrum, and the two color peaks are determined by mass spectrometry as antioxidant TBHQ. One color peak is the unoxidized TBHQ in the original sample, and the second peak is the peak of the TBHQ obtained after the TBHQ oxidation product is reduced by the electrochemical reactor. Analysis of the two color peaks can provide information about TBHQ and its oxidation products.
  • the electrode voltage in the electrochemical reactor was set to OmV, and the amperage detector electrode voltage was +600 mV.
  • the experiment was repeated under the above-mentioned color language detection conditions.
  • the detected chromatogram is shown in Figure 7. From Figure 7, we can see a sigma peak of TBHQ because the electrode voltage of the electrochemical reactor is set to 0 mV and the oxidation product of TBHQ cannot be reduced. Theoretically, the peak area of the TBHQ peak in Figure 7 is the same as the peak area of the first TBHQ color peak in Figure 6.
  • This embodiment specifically describes an apparatus for detecting oxidizable substances provided by the present invention, which comprises a high performance liquid chromatography pump, an injector, an electrochemical reactor, a precolumn, an enrichment column or a quantitative loop, and an HPLC.
  • a high performance liquid chromatography pump an injector, an electrochemical reactor, a precolumn, an enrichment column or a quantitative loop, and an HPLC.
  • Column six-way valve and detector;
  • the electrochemical reactor is coupled between the injector and an HPLC column;
  • the six-way valve is connected between the electrochemical reactor and the HPLC column;
  • the precolumn is connected between the injector and the electrochemical reactor for protecting the electrochemical reactor;
  • the detector includes a ultraviolet detector, an amperometric detector, a differential detector, a fluorescence detector, and two Level array tube detector, qualifier detector, etc.
  • An electrochemical reactor is connected between the injector and the HPLC column to detect oxidizable unstable materials and their oxidation products.
  • Fig. 2 (a) is a schematic diagram of the system flow path before the injection of the electrochemical reactor between the injector and the color column
  • Figure 2 (b) is when the electrochemical reactor is connected between the injector and the color column Schematic diagram of the system flow path after injection.
  • the analysis system flow path is shown in Figure 2 (a).
  • the mobile phase passes through the pre-column, electrochemical reactor, and then enters the enrichment column or loop through the switching valve, and then flows out from the outlet of the enrichment column or loop into the waste bottle;
  • 2 # ⁇ drives the mobile phase through the switching valve, into the HPLC column, and then flows out into the waste bottle through the detector.
  • the sampler injects the sample into the system, and continues to inject the mobile phase with the 1# pump. Under the mobile phase, the sample passes through the pre-column and the electrochemical reactor, and the oxidation product is reduced to the substance to be tested at the set voltage.
  • the switching valve enters the enrichment column or loop. After a certain period of time, the switching valve is switched. At this time, the system flow path is as shown in Fig. 2 (b), and the mobile phase injected by the 1# pump flushes the pre-column and the electrochemical reactor for protection, and flows directly to the waste through the switching valve.
  • the mobile phase injected by the 2# pump is injected into the HPLC column by the conversion valve through the switching valve, and then separated by the detector and then flowed into the waste bottle.
  • the guard column between the injector and the electrochemical reactor can effectively prevent contamination of the electrochemical reactor by impurities in the sample.
  • Figure 4 is the peak of the TBHQ sample after electrochemical reactor reduction (reduction voltage -200mV)
  • Figure 5 is the chromatic peak of the TBHQ sample directly loaded (unreduced)
  • Figure 4 is significantly larger than the reduction peak area of Figure 4 The peak area of the sample that was not reduced. It is shown that the electrochemical reactor is closer to the true value than when the electrochemical reactor is not applied.
  • the detecting device comprises a high performance liquid chromatography pump, an injector, a reduction column, an HPLC column, and a detector;
  • the reduction column is coupled between the injector and the HPLC column;
  • the detector includes a UV detector, an amperometric detector, a differential detector, a fluorescence detector, a secondary array tube detector, a speech detector, and the like.
  • a reduction column was placed in front of the HPLC column to detect the oxidant TBHQ.
  • the detection system flow path is shown in Figure 3.
  • Figure 3 shows the flow path of the antioxidant TBHQ system before the column is added to the reduction column.
  • the sample enters the analytical system through the sampler.
  • the sample containing TBHQ and its oxidation product passes through the reduction column, the oxidation product is reduced to TBHQ.
  • the test substance in the system is a single antioxidant TBHQ, and the HPLC column is passed.
  • the antioxidant TBHQ is separated from other substances.
  • the peak of the TBHQ of the substance to be tested can be seen in the spectrum of the detector output, and the chrominance peak is analyzed to obtain the relevant information of TBHQ.

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Abstract

L'invention concerne un dispositif de détection de substance oxydable, qui comprend une pompe HPLC, un injecteur, une colonne chromatographique HPLC, un détecteur et un réacteur électrochimique ; ou comprend une pompe HPLC, un injecteur, une colonne chromatographique HPLC, un détecteur et une colonne de réduction. Le réacteur électrochimique ou la colonne de réduction peut être positionné après le dispositif de séparation, ou entre l'injecteur et le dispositif de séparation ou avant l'injecteur. Le produit d'oxydation de la substance à analyser peut être réduit par ajustement de la tension d'électrode du réacteur électrochimique, puis détecté par le détecteur, ou peut être réduit par la colonne de réduction puis détecté par le détecteur. De cette façon, une erreur de détection par laquelle le contenu détecté est inférieur au contenu réel, laquelle est produite par l'oxydation de la substance oxydable, peut être diminuée de façon significative. L'invention fournit une solution de régulation d'addition en excès de certaines substances limitées et fournit un nouveau dispositif de détection et un procédé pour celui-ci pour mesurer de façon précise une substance oxydable.
PCT/CN2012/077850 2011-07-04 2012-06-29 Dispositif de détection de substance oxydable et procédé y associé WO2013004152A1 (fr)

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CN201110184118.0A CN102288694B (zh) 2011-07-04 2011-07-04 一种易氧化物质的检测装置及方法
CN201110184118.0 2011-07-04

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CN102288694B (zh) * 2011-07-04 2015-04-01 北京泰克美高新技术有限公司 一种易氧化物质的检测装置及方法
CN105699504B (zh) * 2016-01-15 2018-01-02 青岛检验检疫技术发展中心 在线氧化还原易氧化物质的实时检测装置
CN106018596B (zh) * 2016-05-17 2018-09-14 华南理工大学 一种在线微波辅助手性衍生-液质联用分析系统及方法
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