KR101686852B1 - Disposable sensor for heavy metal ions by modification with terthiophene derivatives and graphene oxide and detecting method using the same - Google Patents
Disposable sensor for heavy metal ions by modification with terthiophene derivatives and graphene oxide and detecting method using the same Download PDFInfo
- Publication number
- KR101686852B1 KR101686852B1 KR1020150114606A KR20150114606A KR101686852B1 KR 101686852 B1 KR101686852 B1 KR 101686852B1 KR 1020150114606 A KR1020150114606 A KR 1020150114606A KR 20150114606 A KR20150114606 A KR 20150114606A KR 101686852 B1 KR101686852 B1 KR 101686852B1
- Authority
- KR
- South Korea
- Prior art keywords
- electrode
- heavy metal
- heavy metals
- sensor
- metal ions
- Prior art date
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
-
- C01B31/0438—
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1813—Water specific cations in water, e.g. heavy metals
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/20—Metals
Abstract
The present invention relates to a sensor for detecting disposable heavy metals, a method of manufacturing the same, and a new heavy metal detection method using the same. The sensor for detecting heavy metals includes a coating layer containing a terthiophene derivative monomer and an oxidized graphene, It is very useful technique to analyze heavy metal ions in real time in the field because it can measure various heavy metal ions without interruption to very low concentration within a very short time of 0.5 second or less.
Description
TECHNICAL FIELD The present invention relates to a high-sensitive disposable heavy metal sensor for detecting heavy metals and a simultaneous instantaneous type heavy metal detection method using the same.
Recently, heavy metal ions, one of the environmental pollutants, are known to be a factor in the biotoxicity and disease induction. In particular, the heavy metal ion in the aqueous solution causes cytotoxicity. When combined with the amyloid fiber in the brain, it is highly related to neurodegenerative diseases such as Alzheimer's disease and Parkinson's disease. Therefore, it is very important to detect the selected heavy metal ions to a low concentration.
Korean Patent Publication No. 2008-0101648 discloses a miniaturization sensor using a stripping voltage-current method for detecting zinc, cadmium and lead ions using electrodes coated with bismuth particles. This method has a disadvantage in that it takes a long time such as a total analysis time of at least 2 minutes since a certain electrodeposition time is required before measuring the concentration of heavy metal ions. Further, there is a limit in lowering the detection limit value, and there is a problem in that there is no selectivity for the detection target ions.
In addition, AAS (atomic absorption spectroscopy) is a typical technique for detecting a trace amount of heavy metals. However, these methods are not only difficult to operate, but also have a disadvantage in that the volume of measuring instruments is so large that they must be sampled in the field and brought to the laboratory for measurement. Therefore, there is a need for a sensor for heavy metal detection that can detect ultra-minute amounts of toxic substances or heavy metals immediately on site, monitor real-time water quality, and is easy to operate and inexpensive.
Therefore, it is required to develop a disposable high-sensitivity heavy metal detection sensor capable of selectively detecting the heavy metal ions to be detected to a low concentration and a method capable of detecting the heavy metal ions at a short time.
It is an object of the present invention to provide a sensor for detecting disposable heavy metals capable of simultaneously detecting various heavy metal ions and a method for simultaneous detection of instant heavy metals.
In order to achieve the above object, the present invention provides an electrode comprising: an electrode; A coating layer comprising a terthiophene derivative monomer formed on the electrode and an oxidized graphene; And a Nafion coating layer formed on the coating layer.
Also, a step of coating a mixed solution containing a terthiophene derivative monomer and an oxidized graphene on the electrode (first step); And a step of coating the coated electrode with a Nafion solution (second step).
The present invention also provides a method for preparing a sample, comprising: adjusting the pH of a sample solution to 5 to 6; And depositing the sample solution on the sensor for detecting heavy metals.
The sensor for detecting heavy metals according to the present invention can detect heavy metal ions at the same time without analyzing other active species, or can analyze heavy metal ions in real time in the field. Therefore, heavy metal ions present in trace amounts in industrial water or groundwater Can be detected immediately and can be very usefully used as a disposable heavy metal ion quantity detection sensor.
1 is a conceptual diagram of a sensor for detecting heavy metals according to an embodiment of the present invention.
2 is a graph showing the results of the reaction of (A) 3,4-diamine-5: 2,5: 2 -tetiophene (DATT), (B) 3- (pyrimidyl- 2,2: 5,2-tertiophene (PATT), (C) 3- (5- [2,2: D) 3- (4- [2,2: 5,2-tertiophenyl] -3-phenyl) -2-acrylic acid (TTPAA) , 2: 3,2-terthiophenyl] -5-acrylic acid (TTTAA).
3 shows the results of a square wave voltammetry analysis of a 0.1 M acetate buffer (a) and a base solution (b) containing 1.0 x 10 -5 M heavy metal ions (HMI) for the modified electrode.
Figure 4 examines the pH effect (A) and the deposition time effect (B) of a solution containing a standard heavy metal ion (HMI) for an atomic absorption spectrometer of 1.0 x 10 -6 M.
5 is 1.0 x 10 -7 M under optimal conditions (A) and the standard heavy metal ions (HMI) for atomic absorption spectrometry obtained by square wave voltammetry with electrodes modified with DATT and oxidized graphene in the 2.5 x 10 -5 M category. And a calibration curve (B).
FIG. 6 is a graph showing changes in signal intensity (A) and atomic absorption spectrophotometry (DATT) and oxide graphene modified electrode (DATT) at the range of 1.0 x 10 -8 M to 5.0 x 10 -5 (B) for the detection of a standard heavy metal ion (HMI) for the analyzer.
The inventors of the present invention have developed a method capable of detecting heavy metals more rapidly and with high sensitivity in the field, and formed a coat layer containing a terthiophene derivative monomer and a graphene oxide on an electrode, It is possible to analyze heavy metals. Thus, the present invention has been completed.
Hereinafter, the present invention will be described in more detail with reference to FIG. 1 through an embodiment.
The present invention provides an electrode comprising: an electrode; A coating layer comprising a terthiophene derivative monomer formed on the electrode and an oxidized graphene; And a Nafion coating layer formed on the coating layer.
At this time, the electrode can be a screen printed carbon electrode, but it is not particularly limited as long as it is an electrode capable of acting as a sensor based on electrochemistry. For example, The potential difference measuring sensor can be classified into two types. Specifically, one of the two types of potential difference measuring sensors is a non-active indicating electrode according to the concentration distribution of the target substance in the sample, And the other is an internal filling solution containing an analyte of known activity and a sample which selectively permeates the analyte by a selective penetration method. Or film that can be adsorbed to the film. An ion selective electrode (ISE) for measuring a potential difference, and the like, but not limited thereto.
In one specific example, the coating layer formed on the electrode can be formed by mixing, for example, di (propylene glycol) methyl ether and tri (propylene glycol) methyl ether in a volume ratio A mixture solution containing terthiophene derivative monomer and oxidized graphene was prepared by dissolving 1.0 to 2.0 mg of terthiophene derivative monomer and 0.02 to 0.1 mg of oxidized graphene in 5 mL of a 1: 1 mixed solvent , The mixed solution may be coated on the screen print carbon electrode to form a terthiophene derivative monomer and an oxidized graphene coating layer on the screen print carbon electrode, A Nafion solution can be coated on the carbon electrode to form a Nafion coating layer.
The thiothiophene derivative monomer may be at least one selected from the group consisting of 3,4-diamine-5: 2,5: 2-thiothiophene (DATT), 3- (pyrimidyl- (TTFAA), 3- (4- [2,2: 5,2-pentafluoro-2- ] -3-phenyl) -2-acrylic acid (TTPAA) and 3- (5-thiophenyl) -2- [2,2: 3,2-tertiophenyl] -5-acrylic acid (TTTAA).
In one specific example, heavy metals can be analyzed using the terthiophene derivative monomer-oxidized graphene / Nafion modified electrode, specifically Cd (II), Pb (II), Hg And at least one selected from the group consisting of iron (II).
The present invention relates to a method for manufacturing a thin film transistor, comprising the steps of: (1) coating a mixed solution containing a terthiophene derivative and an oxidized graphene on an electrode; And a step of coating the coated electrode with a Nafion solution (second step).
In one specific example, 2.5 mL of propylene glycol methyl ether and 2.5 mL of triethylene glycol methyl ether were added to the electrode in a 1: 1 is mixed with a solution of a mixture of a tetryophene derivative monomer and an oxidized graphene.
In the second step, the Nafion solution is coated on the electrode coated with the terthiophene derivative monomer and the oxidized graphene, and coated.
The present invention also provides a method for preparing a sample, comprising: adjusting the pH of a sample solution to 5 to 6; And depositing the sample solution on the sensor for detecting heavy metals.
In one specific example, the simultaneous heavy metal detection method of the present invention comprises: adjusting the pH of the sample solution to 5.4; And depositing the sample solution in the sensor for detecting heavy metals for 300 seconds.
In another specific example, the simultaneous detection method of heavy metals may be at least one selected from the group consisting of Cd (II), Pb (II), Hg (II) and Cu (II) SWV) can be used for simultaneous detection.
Conventional methods for detection of heavy metals and the like include spectrophotometry and inductively coupled plasma mass spectroscopy. However, the above-mentioned methods have a drawback that the equipment itself is quite expensive and the preprocessing time is considerably long, so that there is a problem in continuous use.
Accordingly, the voltage-current method has been proposed as an analytical method capable of solving the above problems, and the inventors of the present application have found that the simultaneous detection method of heavy metals reduces the time when the square-wave voltage and current method having high speed and high sensitivity is used It is confirmed that various heavy metals can be detected.
In another specific example, the simultaneous detection method of heavy metals may be a method of simultaneously detecting at least one selected from the group consisting of Cd (II), Pb (II), Hg (II) and Cu (II) using chronoculometry It can be analyzed quickly in the field.
Therefore, the inventors of the present application have confirmed through experiments that various heavy metal ions can be measured to very low concentrations within a very short time of less than 0.5 second, and that the heavy metals can be analyzed in real time in the field.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by these examples.
≪ Example 1 > Production of a sensor for heavy metal detection
1. Tertiophene derivative monomer synthesis
DATT was synthesized according to a known method ( Chem. Mater . 1996, 8 , 570). PATT was also synthesized according to a known method ( Electrochim. Acta 2013, 104 , 322). Also, TTFAA, TTTAA, and TTPAA are also known methods ( Synth. Met. 2002, 126 , 105). The molecular structure of all used terthiophene derivative monomers is shown in Fig.
2. Manufacture of sensor for heavy metal detection
In order to modify the surface of the screen printed carbon electrode (SPCE), 2.5 mL of dipropylene glycol methyl ether (di (propylene glycol) methyl ether), 1.4 mg of the thiothiophene derivative monomer and 0.07 mg of the oxidized graphene, And 2.5 mL of propylene glycol methyl ether) to prepare a modified solution (volume ratio of 1: 1). 5% Nafion ™ perfluorinated ion exchange resin and dipropylene glycol methyl ether and tri (propylene glycol) methyl ether were purchased from Sigma-Aldrich (USA) Respectively. Standard heavy metal ion (HMI) solutions for atomic absorption spectrometry were purchased from NIST (USA). Other chemicals were purified and used in the American Chemical Society (ACS) reagent grade. Distilled water (18 M Ω / cm) was obtained using a Millipore system.
First, the screen printed carbon electrode (SPCE) was modified by coating 0.3 μL of the previously prepared reforming solution (1.0 × 10 -3 M) and dried in a 40 ° C. oven. The electrode coated with the reforming solution containing the thiothiophene derivative monomer and the oxidized graphene was covered with a 0.01% Nafion ( TM) solution, dried in a CaCl 2 atmosphere at room temperature for 24 hours, coated with Nafion, An electrode modified with graphene oxide was prepared. A conceptual diagram of manufacturing the sensor is shown in Fig.
≪ Example 2 >
1. Square wave voltage and current (SWV) analysis
Square wave voltammetry (SWV) analysis was performed using potentiostat / galvanostat model 273A. At this time, a 3-electrode system using the modified screen printed carbon electrode (SPCE) (diameter: 2.0 mm), Ag / AgCl and carbon as working electrode, reference electrode and auxiliary electrode was used.
The square wave voltammetry (SWV) analysis was performed by scanning a potential from -1.3V to + 0.3V compared to Ag / AgCl, with a pulse amplitude of 25.0 mV, a potential step of 2.0 mV, and a frequency of 10.0 Hz.
2. Time zone charge method (CC) analysis
Time-of-day charge (CC) analysis was performed using BAS CV-50W. In addition, a 3-electrode system using carbon as a working electrode, a reference electrode, and an auxiliary electrode, respectively, was used as in the cine wave current method (SWV) analysis method.
The above time-zone charge analysis shows that from cadmium to -0.9 V, from -0.9 V to -0.5 V for lead and -0.5 to -0.1 V for copper compared to Ag / AgCl, The potential was measured stepwise from -0.1V to + 0.3V. At this time, the step time was 0.5 seconds.
3. Sample preparation
A standard heavy metal ion (HMI) for atomic absorption spectrometry of 1.0 x 10 -2 M containing Cd (II), Pb (II), Cu (II) and Hg The modified electrode was transferred to a conduit containing only the supporting electrolyte solution, followed by voltage and current analysis, and the analysis at a low concentration was carried out in the same preliminary concentration solution containing the electrolyte .
4. Identification of Optimization Condition of Detection Parameters
In order to optimize the sensing environment of the sensor, the current changes according to the pH of the sample solution were observed. As the pH of the solution increased from 2.5 to 5.4 as shown in FIG. 4- (a) The peak current was reduced. Therefore, considering the detection sensitivity and detection ability, the pH of the sample solution was selected as 5.4.
The deposition time was varied from 0 to 450 seconds to find the optimum conditions. After deposition at -1.3 V, stripping was performed to + 0.3 V and the current was measured. As shown in FIG. 4- (b), other ions except for copper increased to 300 seconds, but did not increase significantly after 300 seconds. Therefore, the optimum deposition time was selected as 300 seconds.
5. Disturbance effect
The interference effects of Ni (II), Zn (II), and Mn (II) were investigated during the detection of Cd (II), Pb (II), Cu (II) and Hg (II) First, the electrode was immersed in a solution containing other metal ions for 300 seconds. Oxidative signals of Cd (II), Pb (II), Cu (II) and Hg (II) decreased by about 1.2% to 8.3% due to the presence of other heavy metal ions, .
The results of square wave voltage and current (SWV) analysis for standard heavy metal ion (HMI) analysis for atomic absorption spectrometry are shown in FIG. That is, a positive bipolar stripping peak at -1.07 V, -0.73 V, -0.32 V, and +0.01 V against 0.1 M acetate buffer containing standard heavy metal ions (HMI) for atomic absorption spectrometry at 1.0 x 10 -5 M .
Therefore, it was confirmed that standard modified heavy metal ions (HMI) for atomic absorption spectrometry can be analyzed simultaneously without interfering with other ions by using modified electrode.
6. Calibration Curve of Heavy Metal Ions
As shown in FIG. 5, using a Nafion / DATT-oxidized graphene reforming electrode (NDME) as a square wave voltage-current method under the optimum experimental conditions selected above, a standard heavy metal ion (HMI) The detection calibration curve was obtained. The dynamic range of this electrode is 1.0 x 10 -7 to 2.5 x 10 -5 M and the detection limits are 1.9 x 10 -8 M for Pb (II), 7.2 x 10 -8 M for Hd (II) II) was 0.7 x 10 -8 M, and Cu (II) was 0.4 x 10 -8 M.
The detection standard curve of the standard heavy metal ion (HMI) for atomic absorption spectrometry was obtained using the Nafion / DATT-oxidized graphene reforming electrode (NDME) by the time-zone charge method under the same experimental conditions and is shown in FIG. The dynamic range of this electrode is 1.0 x 10 -7 M to 1.0 x 10 -4 M, the detection limits are 2.8 x 10 -8 M for Pb (II), 1.8 x 10 -8 M for Cd (II) (II) was 2.5 x 10 -8 M, and Cu (II) was 0.4 x 10 -8 M.
Also, for the electrode modified with PATT, TTFAA, TTPAA or TTTAA, the calibration curve was obtained by the same method, and the detection limit was calculated. The results are shown in Table 1 below.
From Table 1, it can be seen that all of the five monomers can be detected at low concentrations. In addition, the detection limit of 5 monomers was similar for cadmium and lead, and the detection limit for copper and mercury was better than the remaining 4 for DATT. Therefore, DATT modified electrode among the five terthiophene derivative monomers showed the highest sensitivity.
Therefore, the analysis method using the time-zone charge method (CC) developed by the present invention has similar detection sensitivity as compared with the conventional stripping current-voltage analysis method and can detect within a shorter time, that is, within 0.5 second, It is a very useful technique to analyze.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It is to be understood that various modifications and changes may be made without departing from the scope of the appended claims.
Claims (9)
And coating the coated electrode with a Nafion solution (second step).
And simultaneously depositing the sample solution on the sensor for detecting heavy metals according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140105148 | 2014-08-13 | ||
| KR20140105148 | 2014-08-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20160021055A KR20160021055A (en) | 2016-02-24 |
| KR101686852B1 true KR101686852B1 (en) | 2016-12-19 |
Family
ID=55449773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150114606A KR101686852B1 (en) | 2014-08-13 | 2015-08-13 | Disposable sensor for heavy metal ions by modification with terthiophene derivatives and graphene oxide and detecting method using the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101686852B1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101717044B1 (en) | 2015-10-15 | 2017-03-17 | 부산대학교 산학협력단 | 6 6 Preparing method of sensor for detecting Chromium and detecting method of Chromium using the same |
| JP7045723B2 (en) * | 2017-03-06 | 2022-04-01 | 学校法人東京女子医科大学 | LYPD1 inhibitor and method for producing biological tissue using it |
| CN106932449A (en) * | 2017-03-08 | 2017-07-07 | 扬州大学 | The preparation method of electrochemical sensor and its application in plumbum ion concentration is detected |
| CN108318554A (en) * | 2017-12-07 | 2018-07-24 | 中国石油化工股份有限公司 | A kind of Electrochemical Detection graphene printing paper electrode and preparation method thereof |
| KR102068610B1 (en) * | 2018-02-28 | 2020-01-21 | 부산대학교 산학협력단 | Preparation method for detecting arsenic ion and detection method of arsenic ion using the same |
| KR102294708B1 (en) * | 2019-09-25 | 2021-08-27 | 부산대학교 산학협력단 | AC potential based strip sensor for detecting heavy metal ions, manufacturing method thereof and simultaneous detection method of heavy metal ions using the same |
| CN111573657A (en) * | 2020-05-21 | 2020-08-25 | 北京交通大学 | Preparation method and application of graphene hydrogel |
| KR102628130B1 (en) * | 2021-05-07 | 2024-01-23 | 부산대학교 산학협력단 | 3D-printing complex for heavy metal ion detection, heavy metal ion detection sensor including the same and heavy metal ion detection method using the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101212012B1 (en) * | 2010-08-17 | 2012-12-13 | 중앙대학교 산학협력단 | Patterning method of graphene using microfluidic systems |
| KR101457272B1 (en) * | 2012-12-18 | 2014-11-07 | 인천대학교 산학협력단 | Biosensor detecting mercury ion using graphene oxide and sensing method thereof |
-
2015
- 2015-08-13 KR KR1020150114606A patent/KR101686852B1/en active IP Right Grant
Non-Patent Citations (2)
| Title |
|---|
| Hui-bog Noh et al. Electrochimica Acta. 2014, 139, pp315-322 |
| Hyoung Soon Han et al. Sensors and Actuators B: Chemical. 2014, Vol. 194, pp. 460-469. |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20160021055A (en) | 2016-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101686852B1 (en) | Disposable sensor for heavy metal ions by modification with terthiophene derivatives and graphene oxide and detecting method using the same | |
| Lin et al. | Glassy carbon electrodes modified with gold nanoparticles for the simultaneous determination of three food antioxidants | |
| Tajik et al. | A sensitive chlorpromazine voltammetric sensor based on graphene oxide modified glassy carbon electrode | |
| Fekry et al. | A novel electrochemical nicotine sensor based on cerium nanoparticles with anionic surfactant | |
| de Oliveira et al. | Mercury nanodroplets supported at biochar for electrochemical determination of zinc ions using a carbon paste electrode | |
| Gevaerd et al. | Evaluation of antimony microparticles supported on biochar for application in the voltammetric determination of paraquat | |
| Sopha et al. | A New Type of Bismuth Electrode for Electrochemical Stripping Analysis Based on the Ammonium Tetrafluorobismuthate Bulk‐Modified Carbon Paste | |
| Afzali et al. | Gold nanoparticles modified carbon paste electrode for differential pulse voltammetric determination of eugenol | |
| Abramova et al. | Solid contact ion sensor with conducting polymer layer copolymerized with the ion-selective membrane for determination of calcium in blood serum | |
| Herrero et al. | Simultaneous determination of Pb2+, Cd2+ and Zn2+ by adsorptive stripping voltammetry using Clioquinol as a chelating-adsorbent agent | |
| del Pozo et al. | The use of cucurbit [8] uril host–guest interactions in the development of an electrochemical sensor: characterization and application to tryptophan determination | |
| Stoica et al. | Ion selective electrodes for protonable nitrogen containing analytes: Metallacarboranes as active membrane components | |
| Fathirad et al. | Conductive polymeric ionic liquid/Fe3O4 nanocomposite as an efficient catalyst for the voltammetric determination of amlodipine besylate | |
| Rabie et al. | A Novel Electrochemical Sensor Based on Modified Carbon Paste Electrode with ZnO Nanorods for the Voltammetric Determination of Indole‐3‐acetic Acid in Plant Seed Extracts | |
| Zaazaa et al. | A novel surfactant silica gel modified carbon paste electrode in micellar media for selective determination of diminazene aceturate in the presence of its stabilizer | |
| Wei et al. | Electrodeposited graphene and gold nanoparticle modified carbon ionic liquid electrode for sensitive detection of rutin | |
| Kamat et al. | Scope of detection and determination of gallium (III) in industrial ground water by square wave anodic stripping voltammetry on bismuth film electrode | |
| Zhao et al. | Simultaneous determination of Pb (II) and Cd (II) using an electrode modified with electropolymerized thiadiazole film | |
| Faridbod et al. | A new metoclopramide potentiometric membrane sensor for analysis in pharmaceutical formulation and urine: concerns to theoretical study | |
| Faridbod et al. | Potentiometric determination of loperamide hydrochloride by loperamide PVC membrane and nano-composite electrodes | |
| Tanuja et al. | Electrochemical studies of mesalazine at sodium dodecyl sulfate modified carbon paste electrode: A cyclic voltammetric study | |
| Ensafi et al. | Potentiometric sensor for the determination of dibucaine in pharmaceutical preparations and electrochemical study of the drug with BSA | |
| Yan et al. | Electrochemical behavior of valsartan and its determination in capsules | |
| KR102075095B1 (en) | Sensor for detecting heavy metal ions and simultaneous detection method of heavy metal ions using the same | |
| Faridbod et al. | Highly selective and sensitive asymmetric lead microsensor based on 5, 5, dithiobis (2-nitrobenzoic acid) as an excellent hydrophobic neutral carrier for nano level monitoring of lead in real samples |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |