CN102236004A - Liquid chromatogram potential type detector and detection method thereof - Google Patents
Liquid chromatogram potential type detector and detection method thereof Download PDFInfo
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Abstract
The invention discloses a liquid chromatogram potential type detector and a detection method thereof. In the detector, a detector base is used as a frame for supporting all assemblies, a detection pool is a cavity in the detector base, a working electrode is arranged at the upper part of the detector base and filled with internal liquid which is separated from a sample solution in the detection pool by a polymer sensitive film, one end of an internal reference electrode is arranged in the internal liquid, one ends of an external reference electrode and an assistant electrode are arranged in the detection pool, and the other ends of the internal reference electrode, the external reference electrode and the assistant electrode are respectively connected with an electrochemical workstation. The detection method comprises the following steps of: preparing the working electrode; putting the working electrode, the external reference electrode and the assistant electrode in the detection pool and connecting the working electrode, the external reference electrode and the assistant electrode in the detection pool with the electromechanical workstation; and recording the change of potential difference among the working electrode and the reference electrodes with time to obtain a chromatogram. By the adoption of the detector and the detection method thereof, the limitation that electrical neutral compounds cannot be detected by using the traditional liquid chromatogram potential detection technology is broken through; and the invention provides a practical detection method which has the advantages of good repeatability, wide application range, easiness in operation, low cost and the like.
Description
Technical field
The present invention relates to a kind of analytical instrument of liquid chromatography, specifically a kind of liquid chromatography electric potential type detecting device and detection method thereof.
Background technology
Liquid chromatography has been widely used in analytical chemistry and biochemical field as a kind of important separate analytical technique.Detecting device is one of core component of liquid chromatograph, plays important effect in liquid chromatographic system, and according to the needs of analytic sample, the sensitivity and the selectivity of development of new detecting device and raising detecting device are analytical work person's research directions always.At present, liquid chromatography detecting device commonly used has ultraviolet-visible detector, fluorescence detector, differential refraction detector and electrochemical detector etc., and novel detection technique such as mass spectrum, flame ionization detector also is applied in the liquid-phase chromatographic analysis gradually in addition.In these technology, electrochemical detector has advantage significantly at aspects such as selectivity, detectability, responding range, prices, especially can measure those does not have uv absorption or can not fluorescigenic material, has obtained to use widely in the mensuration of the metabolin in various inorganic and organic cation-anion, biological tissue and body fluid, food additives, environmental contaminants, biochemical product, agricultural chemicals, medicine etc.
Electrochemical detector commonly used at present mainly is ampere and electric conductivity detector, and electric current is the basis with alive pass between polarized electrode and contrast electrode to measure for the former, and the latter is a foundation with the resistance variations of measuring liquid then.But there are some defectives in ampere detector, and for example electrode surface is contaminated easily, and does not still have effective cleaning measure at present, and electrochemical window is narrower, and reappearance is relatively poor etc., has limited its widespread use in liquid chromatographic detection.The sensitivity of electric conductivity detector is subjected to the strong influence of background ions, needs the inhibition system to eliminate the interference of strong electrolyte background ions in the moving phase usually, is subjected to the influence of ambient temperature bigger in addition.
Electric potential detector is to adopt a kind of electrochemical detector of ion-selective electrode as means of testing, and it measures ion activity in the solution according to the size of film potential.That electric potential detector has is highly sensitive, selectivity good, device is simple and be easy to advantages such as microminiaturization.Yet for a long time, its application as liquid chromatogram detector is actually rare, because ion-selective electrode only produces response to specific ion, liquid chromatogram detector requires that a lot of materials are all had response.Through the retrieval of prior art being found Mark E.Meyerhoff seminar adopts potassium ion-selective electrode as detecting device, the inorganic zwitterion after chromatographic resolution at first by an ion exchange column to displace K
+, the K that displaces by mensuration then
+Determine to treat measured ion concentration (M.Trojanowicz, M.E.Meyerhoff, Anal.Chim.Acta, 1989,222,95-107).Find by retrieval in addition, Luc J.Nagels seminar with anion-selective membrane as the polymkeric substance sensitive membrane, adopt the liquid chromatography electric potential detector to measure carboxylic acid, phosphate and nucleotide (S.Picioreanu, I.Poels, J.Frank, etc., Anal.Chem.2000,72,2029-2034).Conventional detection only limits to measure a class ionic compound, and versatility is relatively poor, and sensitivity is subjected to having a strong impact on of background ions.Up to now, still do not have liquid phase chromatogram electric potential type detecting device and measure electric neutrality molecular studies report.
Summary of the invention
There are deficiencies such as versatility difference at liquid chromatography electric potential type detecting device of the prior art, the invention provides a kind of versatility good, highly sensitive liquid chromatography electric potential type detecting device and detection method thereof.
For achieving the above object, the technical solution adopted in the present invention is:
A kind of liquid chromatography electric potential type of the present invention detecting device comprises detector base body, working electrode, detection cell, outer contrast electrode, auxiliary electrode, chromatographic column interface pipeline and waste liquid outlet pipeline, wherein:
Detector base body is for supporting the pedestal of each assembly; Detection cell is for being located at a cavity in the detector base body; Working electrode is positioned at detector base body top, and its lower end has an aperture to communicate with detection cell, fills internal-filling liquid in the working electrode, by the polymkeric substance sensitive membrane that the bottom is attached on the aperture internal-filling liquid and sample solution in the detection cell is separated; Internal reference electrode one end is arranged in the internal-filling liquid, and the other end links to each other with electrochemical workstation; Outer contrast electrode, an end is located in the detection cell, and the other end links to each other with electrochemical workstation; Auxiliary electrode, an end is located in the detection cell, and the other end links to each other with electrochemical workstation; Chromatographic column interface pipeline, the passage of joint detection pond and liquid-phase chromatographic column; The waste liquid outlet pipeline, the passage of eliminating detection cell waste liquid.
Described internal-filling liquid is an oxidizing agent solution, and oxidizing agent solution is permanganate solution, dichromate solution, superoxide salt solusion, perchlorate solution or hypochlorite solutions.
Described polymkeric substance sensitive membrane is: polymeric matrix material, plastifier, ion exchanger and organic salt, be that 20-40: 40-80: 1-15: 0-10 mixes by ratio of weight and the number of copies, then be added in the tetrahydrofuran solution, stirring makes it to become homogeneous solution, at room temperature place 12-24h after being mixed, treat promptly to obtain resilient polymkeric substance sensitive membrane after tetrahydrofuran volatilizes fully.
Described polymeric matrix material is Polyvinylchloride, poly-butylacrylic acid ester, butyl polyacrylate, polyetherimide, rubber or sol-gel film; Plastifier is neighbour-nitrobenzene octyl ether, two-2-ethylhexyl ester in the last of the ten Heavenly stems, dibutyl sebacate or di-n-octyl sebacate; Ion exchanger is three-dodecyl methyl ammonium chloride or three-myristyl ammonio methacrylate; Organic salt is four (dodecyl)-four (4-chlorphenyl) ammonium borates.
Described polymkeric substance sensitive membrane thickness is 100-300 μ m.
The material of described detector base body is organic glass, quartz glass, high temp glass or stupalith.
Working electrode and auxiliary electrode form the loop applying extrinsic current, and sense of current is to make oxygenant in the internal-filling liquid be discharged into the outside surface of polymkeric substance sensitive membrane; The size of current that is applied is 0.1-10 μ A.
The detection method of a kind of liquid chromatography electric potential type of the present invention detecting device may further comprise the steps:
Preparation comprises the working electrode of internal reference electrode, internal-filling liquid and polymkeric substance sensitive membrane;
Working electrode, outer contrast electrode and auxiliary electrode all are placed in the detection cell, and the other end is connected with electrochemical workstation;
Potential difference (PD) between writing task electrode and the contrast electrode promptly obtains chromatogram over time.
Advantage of the present invention and beneficial effect are:
1. the present invention has broken through the limitation that traditional liquid chromatography current potential detection technique can't be measured the electric neutrality compound, and a kind of detection method of practicality is provided, and has advantages such as favorable reproducibility, the scope of application be wide, simple to operate, cheap.
2. the present invention has suitable application prospects as a kind of novel liquid chromatogram detector, utilizes redox reaction, and is applied widely by measuring the multiple reductive agent of a kind of oxygenant indirect determination, has versatility, has remarkable economical and social benefit.
3. the present invention has utilized the oxygenant ion to stride the outside surface that film is discharged into the polymkeric substance sensitive membrane from the internal-filling liquid of ion-selective electrode, and burst size is controlled, and a kind of method that reagent is measured reductive agent of not having is provided.Utilize impressed current to quicken the renewal of polymkeric substance sensitive membrane outside surface oxygenant simultaneously.
Description of drawings
Fig. 1 is a liquid chromatography electric potential type detector arrangement synoptic diagram of the present invention;
Fig. 2 is the chromatogram of variable concentrations catecholamine among the embodiment 1;
Fig. 3 is the linear relationship chart of variable concentrations catecholamine among the embodiment 1;
Fig. 4 A is not for applying the chromatogram under the current condition among the embodiment 1;
Fig. 4 B is for applying the chromatogram under the extrinsic current condition among the embodiment 1.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
As shown in Figure 1, liquid chromatography electric potential type detecting device of the present invention comprises detector base body 6, working electrode 3, detection cell 5, outer contrast electrode 7, auxiliary electrode 8, chromatographic column interface pipeline 9 and waste liquid outlet pipeline 10, wherein: detector base body 6, for supporting the pedestal of each assembly; Working electrode 3 is positioned at detector base body 6 tops, and its lower end has an aperture to communicate with detection cell 5, fills internal-filling liquid 2 in the working electrode, by the polymkeric substance sensitive membrane 4 that the bottom is attached on the aperture sample solution in internal-filling liquid 2 and the detection cell 5 is separated; Internal reference electrode 1 one ends are arranged in the internal-filling liquid 2, and the other end links to each other with electrochemical workstation, are used to indicate the related potential of the concentration of measured matter; Detection cell 5 is for being located at a cavity (detection cell 5 volumes are less than or equal to 20 μ L, and in the present embodiment, detection cell 5 volumes are 5 μ L) in the detector base body 6; Outer contrast electrode 7 one ends are located in the detection cell 5, the other end with, be used to provide the measurement potential reference; Auxiliary electrode 8 one ends are located in the detection cell 5, and the other end links to each other with electrochemical workstation, are used to make itself and working electrode 3 to form the loop, to apply extrinsic current; The passage of the chromatographic column of chromatographic column interface pipeline 9 joint detection ponds 5 and liquid chromatograph; Waste liquid outlet pipeline 10 by measuring in the chromatographic column interface pipeline 9 importing detection cells 5, is discharged by waste liquid outlet pipeline 10 from the terminal eluent that flows out of liquid-phase chromatographic column then for getting rid of the passage of detection cell 5 waste liquids.
Oxidizing agent solution in 4 pairs of internal-filling liquids 2 of polymkeric substance sensitive membrane has selective response.It is the polymkeric substance sensitive membrane of 100-300 μ m that this polymkeric substance sensitive membrane 4 adopts thickness; Internal-filling liquid 2 is an oxidizing agent solution, and oxidizing agent solution is permanganate solution, dichromate solution, superoxide salt solusion, perchlorate solution or hypochlorite solutions; Internal reference electrode 1 and outer contrast electrode 7 are the Ag/AgCl silk; Auxiliary electrode 8 is the Pt silk; Chromatographic column interface pipeline 9 is polyetheretherketone, teflon or ETFE with the piping material of waste liquid outlet pipeline 10, and the pipeline internal diameter is 0.127-0.508mm; Chromatographic column interface pipeline 9 is placed with waste liquid outlet pipeline 10 best angles at 45; The material of detector base body 6 can be organic glass, quartz glass, high temp glass or stupalith.
Polymkeric substance sensitive membrane 4 adopts polymeric matrix material, plastifier, ion exchanger and organic salt, be that 20-40: 40-80: 1-15: 0-10 mixes by ratio of weight and the number of copies, then be added in the tetrahydrofuran solution, stirring makes it to become homogeneous solution, at room temperature place 12-24h after being mixed, promptly obtain resilient polymkeric substance sensitive membrane, thickness can be 100-300 μ m.
Described polymeric matrix material is Polyvinylchloride, poly-butylacrylic acid ester, butyl polyacrylate, polyetherimide, rubber or sol-gel film; Plastifier is neighbour-nitrobenzene octyl ether, two-2-ethylhexyl ester in the last of the ten Heavenly stems, dibutyl sebacate or di-n-octyl sebacate; Ion exchanger is three-dodecyl methyl ammonium chloride or three-myristyl ammonio methacrylate; Organic salt is four (dodecyl)-four (4-chlorphenyl) ammonium borates.
The principle of work of apparatus of the present invention is:
Oxygenant in the mensuration process in working electrode 3 internal-filling liquids 2 can be constantly from film in opposite directions sample solution ooze out, when the reducing substances after liquid chromatography is separated passes through detection cell 5, oxygenant generation oxidation-reduction reaction with polymkeric substance sensitive membrane 4 outside surfaces causes the change of oxygenant activity.Polymkeric substance sensitive membrane 4 can produce the selectivity potential response to its surperficial oxygenant, and its potential value is by the activity decision of the oxygenant on polymkeric substance sensitive membrane 4 surfaces.Potential difference (PD) between writing task electrode and the contrast electrode promptly obtains chromatogram over time.In whole mensuration process, apply an extrinsic current to drive the oxygenant ion flow from the transhipment of internal-filling liquid outside film, in time replenish the used up oxygenant in electrode film surface, film is restored.Atomic absorption spectrography (AAS) shows further that also oxygenant can constantly ooze out from internal-filling liquid.
The detection method of liquid chromatography electric potential type detecting device of the present invention may further comprise the steps:
Preparation comprises the working electrode 3 of internal reference electrode 1, internal-filling liquid 2 and polymkeric substance sensitive membrane 4;
Working electrode 3, outer contrast electrode 7 all are placed in the detection cell with auxiliary electrode 8, and the other end is connected with electrochemical workstation;
Potential difference (PD) between writing task electrode and the contrast electrode promptly obtains chromatogram over time.
The preparation of working electrode 3 may further comprise the steps:
Preparation polymkeric substance sensitive membrane 4: with polymeric matrix material, plastifier, ion exchanger and organic salt, be that 20-40: 40-80: 1-15: 0-10 mixes by ratio of weight and the number of copies, be added to then in the tetrahydrofuran solution that (mass volume ratio of above-mentioned solid matter and tetrahydrofuran is 40-150mg: 2mL), stir and make it to become homogeneous solution;
Above-mentioned homogeneous solution is at room temperature placed 12-24h, obtain resilient polymkeric substance sensitive membrane;
Polymkeric substance sensitive membrane with card punch cut-off footpath 0.2-1.0cm attaches on the aperture of working electrode 3 bottoms;
Internal reference electrode 1 is inserted formation working electrode in the working electrode that is full of internal-filling liquid 2 (oxygenant).
Present embodiment is an example to measure dopamine, adrenaline and norepinephrine simultaneously.Its determination step is as follows:
A. being prepared as of working electrode: get mass content 15% 3-dodecyl methyl ammonium chloride, mass content 25% Polyvinylchloride, mass content 60% neighbour-nitrobenzene octyl ether 240mg altogether, be added in the 3mL tetrahydrofuran solution, in flat small beaker (diameter 3.6cm), place 12h under the room temperature, treat promptly to obtain resilient polymkeric substance sensitive membrane after tetrahydrofuran volatilizes fully, thickness is 130 μ m.With the polymkeric substance sensitive membrane of above-mentioned polymkeric substance sensitive membrane, then attach on the aperture of working electrode lower end by tetrahydrofuran with card punch cut-off footpath 0.6cm.Internal-filling liquid is the 0.1M liquor potassic permanganate, contains 0.02M NaCl solution.Use the moving phase balance up to obtaining a stable baseline before the sample introduction.
B. test sample is: dopamine, adrenaline and norepinephrine, be mixed with 0.01M mixing storing solution with moving phase, and the sample solution of variable concentrations storing solution dilution thus obtains, and preservation, standby is placed in the dark place.
C. chromatographic condition: Agilent TC-C18 (2) chromatographic column (4.6 * 250mm, 5 μ m), moving phase is the 20mM sodium citrate solution, contains 1.0 * 10
-3M NaCl solution, flow velocity are 0.8mL/min, and 30 ℃ of column temperatures, sample size are 50 μ L.
D. described detector base body is an organic glass.
E. be under the condition of 0.5 μ A at impressed current, with electric potential type detecting device of the present invention and above-mentioned chromatographic condition test sample, the record chromatogram as shown in Figure 2.
F. as shown in Figure 3, dopamine, adrenaline and norepinephrine are all 6 * 10
-6-2 * 10
-5In the M scope, peak height and concentration present good linear relationship, and related coefficient is respectively 0.997,0.998 and 0.996.Three's lowest detectable limit can reach 1 * 10
-6M.
G. in order to illustrate that impressed current is to improving the effect of sensitivity, at first measure according to above-mentioned chromatographic condition sample introduction under the situation of zero current, the record chromatogram is shown in Fig. 4 A, under identical chromatographic condition, measure same sample then, apply the electric current of 0.5 μ A simultaneously, the record chromatogram is shown in Fig. 4 B.The result shows that under the condition of impressed current, 3 kinds of catecholamines have all reached baseline separation, and chromatographic peak profile is more sharp-pointed.
Be with the difference of embodiment 1: internal-filling liquid 2 oxygenants are potassium bichromate solution, and present embodiment is an example to measure dopamine, adrenaline and norepinephrine simultaneously, and its determination step is as follows:
A. being prepared as of working electrode: get mass content 15% 3-dodecyl methyl ammonium chloride, mass content 25% Polyvinylchloride, mass content 60% neighbour-nitrobenzene octyl ether 240mg altogether, be added in the 3mL tetrahydrofuran solution, in flat small beaker (diameter 3.6cm), place 12h under the room temperature, treat promptly to obtain resilient polymkeric substance sensitive membrane after tetrahydrofuran volatilizes fully, thickness is 130 μ m.With the polymkeric substance sensitive membrane of above-mentioned polymkeric substance sensitive membrane, then attach on the aperture of working electrode lower end by tetrahydrofuran with card punch cut-off footpath 0.6cm.Internal-filling liquid is the 0.1M potassium bichromate solution, contains 0.02M NaCl solution.Use the moving phase balance up to obtaining a stable baseline before the sample introduction.
B. test sample is: dopamine, adrenaline and norepinephrine, be mixed with 0.01M mixing storing solution with moving phase, and the sample solution of variable concentrations storing solution dilution thus obtains.Preservation, standby is placed in the dark place.
C. chromatographic condition: Agilent TC-C18 (2) chromatographic column (4.6 * 250mm, 5 μ m), moving phase is the 20mM sodium citrate solution, contains 1.0 * 10
-3M NaCl solution, flow velocity are 0.8mL/min, and 30 ℃ of column temperatures, sample size are 50 μ L.
D. described detector base body is an organic glass.
E. be under the condition of 1.0 μ A at impressed current, with electric potential type detecting device of the present invention and above-mentioned chromatographic condition test sample.
Embodiment 3
Be with the difference of embodiment 1: present embodiment is an example to measure uric acid, xanthine and hypoxanthine simultaneously.Its determination step is as follows:
A. being prepared as of working electrode: get mass content 10% 3-dodecyl methyl ammonium chloride, mass content 25% Polyvinylchloride, mass content 65% neighbour-nitrobenzene octyl ether 240mg altogether, be added in the 3mL tetrahydrofuran solution, in flat small beaker (diameter 3.6cm), place 12h under the room temperature, treat promptly to obtain resilient polymkeric substance sensitive membrane after tetrahydrofuran volatilizes fully, thickness is 130 μ m.With the polymkeric substance sensitive membrane of above-mentioned polymkeric substance sensitive membrane, then attach on the aperture of working electrode lower end by tetrahydrofuran with card punch cut-off footpath 0.6cm.Internal-filling liquid is the 0.08M liquor potassic permanganate, contains 0.02M NaCl solution.Use the moving phase balance up to obtaining a stable baseline before the sample introduction.
B. test sample is: uric acid, xanthine and hypoxanthine, be mixed with 0.01M mixing storing solution with moving phase, and the sample solution of variable concentrations storing solution dilution thus obtains.Preservation, standby is placed in the dark place.
C. chromatographic condition: Agilent TC-C18 (2) chromatographic column (4.6 * 250mm, 5 μ m), moving phase is HAc-NaAc buffer solution (pH4.0), contains 1.0 * 10
-3M NaCl solution, flow velocity are 1.0mL/min, and 30 ℃ of column temperatures, sample size are 50 μ L.
D. described detector base body is an organic glass.
E. be under the condition of 0.5 μ A at impressed current, with electric potential type detecting device of the present invention and above-mentioned chromatographic condition test sample.
Be with the difference of embodiment 1: present embodiment is an example to measure clenobuterol hydrochloride and bromine ethamine simultaneously.Its determination step is as follows:
A. being prepared as of working electrode: get mass content 15% 3-dodecyl methyl ammonium chloride, mass content 25% Polyvinylchloride, mass content 60% neighbour-nitrobenzene octyl ether 160mg altogether, be added in the 3mL tetrahydrofuran solution, in flat small beaker (diameter 3.0cm), place 12h under the room temperature, treat promptly to obtain resilient polymkeric substance sensitive membrane after tetrahydrofuran volatilizes fully, thickness is 100 μ m.With the polymkeric substance sensitive membrane of above-mentioned polymkeric substance sensitive membrane, then attach on the aperture of working electrode lower end by tetrahydrofuran with card punch cut-off footpath 0.6cm.Internal-filling liquid is the 0.1M liquor potassic permanganate, contains 0.02M NaCl solution.Use the moving phase balance up to obtaining a stable baseline before the sample introduction.
B. test sample is: clenobuterol hydrochloride (uncle's 2-[(fourth amino) methyl]-4-amino-3,5-dichlorbenzyl alcohol hydrochloride) and bromine ethamine, being mixed with 0.01M mixing storing solution with moving phase, the sample solution of variable concentrations storing solution dilution thus obtains.Preservation, standby is placed in the dark place.
C. chromatographic condition: Agilent XDB-C18 chromatographic column (4.6 * 150mm, 5 μ m), moving phase is methyl alcohol: 2.8mM trifluoracetic acid buffer solution (pH2.55)=10: 90, contain 1.0 * 10
-3MNaCl solution, flow velocity are 1.0mL/min, and 30 ℃ of column temperatures, sample size are 50 μ L.
D. described detector base body is an organic glass.
E. be under the condition of 0.2 μ A at impressed current, with electric potential type detecting device of the present invention and above-mentioned chromatographic condition test sample.
Be with the difference of embodiment 1: present embodiment is an example with the content of measuring Vc in the Vc Lonicera and Forsythia sheet.Its determination step is as follows:
A. being prepared as of working electrode: get mass content 10% 3-dodecyl methyl ammonium chloride, mass content 25% Polyvinylchloride, mass content 55% neighbour-nitrobenzene octyl ether, mass content 10% 4 (dodecyl)-four (4-chlorphenyl) ammonium borate is 240mg altogether, be added in the 3mL tetrahydrofuran solution, place 12h under the room temperature in flat small beaker (diameter 3.6cm), treat promptly to obtain resilient polymkeric substance sensitive membrane after tetrahydrofuran volatilizes fully, thickness is 130 μ m.With the polymkeric substance sensitive membrane of above-mentioned polymkeric substance sensitive membrane, then attach on the aperture of working electrode lower end by tetrahydrofuran with card punch cut-off footpath 0.6cm.Internal-filling liquid is the 0.1M liquor potassic permanganate, contains 0.02M NaCl solution.Use the moving phase balance up to obtaining a stable baseline before the sample introduction.
B. test sample is: vitamin C, be mixed with the 0.01M storing solution with moving phase, and the sample solution of variable concentrations storing solution dilution thus obtains.Preservation, standby is placed in the dark place.
C. chromatographic condition: Agilent XDB-C18 chromatographic column (4.6 * 150mm, 5 μ m), moving phase is the 0.1M potassium dihydrogen phosphate, contains 1.0 * 10
-3M NaCl solution, flow velocity are 1.0mL/min, and 30 ℃ of column temperatures, sample size are 50 μ L.
D. described detector base body is an organic glass.
E. be under the condition of 1.0 μ A at impressed current, with electric potential type detecting device of the present invention and above-mentioned chromatographic condition test sample.
Claims (10)
1. liquid chromatography electric potential type detecting device, it is characterized in that: comprise detector base body (6), working electrode (3), detection cell (5), outer contrast electrode (7), auxiliary electrode (8), chromatographic column interface pipeline (9) and waste liquid outlet pipeline (10), wherein:
Detector base body (6) is for supporting the pedestal of each assembly;
Detection cell (5) is for being located at a cavity in the detector base body (6);
Working electrode (3), be positioned at detector base body (6) top, its lower end has an aperture to communicate with detection cell (5), fills internal-filling liquid (2) in the working electrode, and polymkeric substance sensitive membrane (4) sample solution that internal-filling liquid (2) and detection cell (5) is interior that is attached on the aperture by the bottom separates; Internal reference electrode (1) one end of working electrode (3) is arranged in the internal-filling liquid (2), and the other end links to each other with electrochemical workstation;
Outer contrast electrode (7), an end are located in the detection cell (5), and the other end links to each other with electrochemical workstation;
Auxiliary electrode (8), an end are located in the detection cell (5), and the other end links to each other with electrochemical workstation;
Chromatographic column interface pipeline (9), the passage of joint detection pond (5) and liquid-phase chromatographic column;
Waste liquid outlet pipeline (10), the passage of eliminating detection cell (5) waste liquid.
2. according to the described liquid chromatography electric potential type of claim 1 detecting device, it is characterized in that: described internal-filling liquid (2) is an oxidizing agent solution, and oxidizing agent solution is permanganate solution, dichromate solution, superoxide salt solusion, perchlorate solution or hypochlorite solutions.
3. according to the described liquid chromatography electric potential type of claim 1 detecting device, it is characterized in that: described polymkeric substance sensitive membrane (4) is:
Polymeric matrix material, plastifier, ion exchanger and organic salt, be that 20-40: 40-80: 1-15: 0-10 mixes by ratio of weight and the number of copies, then be added in the tetrahydrofuran solution, stirring makes it to become homogeneous solution, at room temperature place 12-24h after being mixed, treat promptly to obtain resilient polymkeric substance sensitive membrane after tetrahydrofuran volatilizes fully.
4. according to the described liquid chromatography electric potential type of claim 3 detecting device, it is characterized in that: described polymeric matrix material is Polyvinylchloride, poly-butylacrylic acid ester, butyl polyacrylate, polyetherimide, rubber or sol-gel film; Plastifier is neighbour-nitrobenzene octyl ether, two-2-ethylhexyl ester in the last of the ten Heavenly stems, dibutyl sebacate or di-n-octyl sebacate; Ion exchanger is three-dodecyl methyl ammonium chloride or three-myristyl ammonio methacrylate; Organic salt is four (dodecyl)-four (4-chlorphenyl) ammonium borates.
5. according to the described liquid chromatography electric potential type of claim 4 detecting device, it is characterized in that: described polymkeric substance sensitive membrane (4) thickness is 100-300 μ m.
6. according to the described liquid chromatography electric potential type of claim 1 detecting device, it is characterized in that: the material of described detector base body (6) is organic glass, quartz glass, high temp glass or stupalith.
7. according to the described liquid chromatography electric potential type of claim 1 detecting device, it is characterized in that: working electrode (3) and auxiliary electrode (8) form the loop applying extrinsic current, and sense of current is to make oxygenant in the internal-filling liquid (2) be discharged into the outside surface of polymkeric substance sensitive membrane (4).
8. according to the described electric potential type detecting device that is used for liquid chromatography of claim 7, it is characterized in that: the size of current that is applied is 0.1-10 μ A.
9. the detection method of a liquid chromatography electric potential type detecting device is characterized in that may further comprise the steps:
Preparation comprises the working electrode (3) of internal reference electrode (1), internal-filling liquid (2) and polymkeric substance sensitive membrane (4);
Working electrode (3), outer contrast electrode (7) all are placed in the detection cell with auxiliary electrode (8), and the other end is connected with electrochemical workstation;
Potential difference (PD) between writing task electrode and the contrast electrode promptly obtains chromatogram over time.
10. according to the detection method of the described liquid chromatography electric potential type of claim 9 detecting device, it is characterized in that: the preparation of described working electrode (3) may further comprise the steps:
Preparation polymkeric substance sensitive membrane (4): with polymeric matrix material, plastifier, ion exchanger and organic salt, be that 20-40: 40-80: 1-15: 0-10 mixes by ratio of weight and the number of copies, then be added in the tetrahydrofuran solution, stir and make it to become homogeneous solution;
Above-mentioned homogeneous solution is at room temperature placed 12-24h, treat to obtain the polymkeric substance sensitive membrane after tetrahydrofuran volatilizes fully;
With tetrahydrofuran solution it is attached on the aperture of working electrode (3) bottom;
To promptly form working electrode in internal reference electrode (1) the insertion internal-filling liquid (2).
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| US4566949A (en) * | 1983-10-19 | 1986-01-28 | Hewlett-Packard Company | Method of operating a self cleaning electrochemical detector |
| JP2001066283A (en) * | 1999-08-26 | 2001-03-16 | Dkk Toa Corp | Electrochemical detector and liquid chromatography |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105301069A (en) * | 2015-09-30 | 2016-02-03 | 王竞 | Liquid analysis method and device adopting ion-selective-electrode method |
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