WO2023167644A1 - Impedimetric electrochemical sensor and electrode production method - Google Patents
Impedimetric electrochemical sensor and electrode production method Download PDFInfo
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- WO2023167644A1 WO2023167644A1 PCT/TR2022/050332 TR2022050332W WO2023167644A1 WO 2023167644 A1 WO2023167644 A1 WO 2023167644A1 TR 2022050332 W TR2022050332 W TR 2022050332W WO 2023167644 A1 WO2023167644 A1 WO 2023167644A1
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- impedimetric
- electrochemical sensor
- biodegradable
- gelatin
- detection
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000004458 analytical method Methods 0.000 claims abstract description 18
- 230000007613 environmental effect Effects 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 235000013305 food Nutrition 0.000 claims abstract description 6
- 239000012472 biological sample Substances 0.000 claims abstract description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 32
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- 238000001514 detection method Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 108010010803 Gelatin Proteins 0.000 claims description 22
- 239000008273 gelatin Substances 0.000 claims description 22
- 229920000159 gelatin Polymers 0.000 claims description 22
- 235000019322 gelatine Nutrition 0.000 claims description 22
- 235000011852 gelatine desserts Nutrition 0.000 claims description 22
- 244000005700 microbiome Species 0.000 claims description 12
- 230000035945 sensitivity Effects 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 102000004190 Enzymes Human genes 0.000 claims description 8
- 108090000790 Enzymes Proteins 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 108090000623 proteins and genes Proteins 0.000 claims description 8
- 102000004169 proteins and genes Human genes 0.000 claims description 8
- 108020004414 DNA Proteins 0.000 claims description 7
- 239000000090 biomarker Substances 0.000 claims description 7
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 5
- 241001465754 Metazoa Species 0.000 claims description 5
- 239000012805 animal sample Substances 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 claims description 4
- 229960001051 dimercaprol Drugs 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 229910021654 trace metal Inorganic materials 0.000 claims description 4
- GVJXGCIPWAVXJP-UHFFFAOYSA-N 2,5-dioxo-1-oxoniopyrrolidine-3-sulfonate Chemical compound ON1C(=O)CC(S(O)(=O)=O)C1=O GVJXGCIPWAVXJP-UHFFFAOYSA-N 0.000 claims description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000003651 drinking water Substances 0.000 claims description 3
- 235000020188 drinking water Nutrition 0.000 claims description 3
- 230000002068 genetic effect Effects 0.000 claims description 3
- 230000003993 interaction Effects 0.000 claims description 3
- 238000002331 protein detection Methods 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- VUFNRPJNRFOTGK-UHFFFAOYSA-M sodium;1-[4-[(2,5-dioxopyrrol-1-yl)methyl]cyclohexanecarbonyl]oxy-2,5-dioxopyrrolidine-3-sulfonate Chemical compound [Na+].O=C1C(S(=O)(=O)[O-])CC(=O)N1OC(=O)C1CCC(CN2C(C=CC2=O)=O)CC1 VUFNRPJNRFOTGK-UHFFFAOYSA-M 0.000 claims description 3
- 238000004457 water analysis Methods 0.000 claims description 3
- LQILVUYCDHSGEU-UHFFFAOYSA-N 4-[(2,5-dioxopyrrol-1-yl)methyl]cyclohexane-1-carboxylic acid Chemical compound C1CC(C(=O)O)CCC1CN1C(=O)C=CC1=O LQILVUYCDHSGEU-UHFFFAOYSA-N 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 claims description 2
- 230000000975 bioactive effect Effects 0.000 claims description 2
- 230000014670 detection of bacterium Effects 0.000 claims description 2
- 239000003550 marker Substances 0.000 claims 1
- 239000012491 analyte Substances 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 2
- 229910052785 arsenic Inorganic materials 0.000 description 10
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 10
- 235000018102 proteins Nutrition 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000001277 hydride generation atomic absorption spectroscopy Methods 0.000 description 4
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 230000009897 systematic effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000001736 differential pulse polarography Methods 0.000 description 2
- 238000000673 graphite furnace atomic absorption spectrometry Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 108091093037 Peptide nucleic acid Proteins 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
- 238000003968 anodic stripping voltammetry Methods 0.000 description 1
- -1 antibody Proteins 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 231100000739 chronic poisoning Toxicity 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000003947 neutron activation analysis Methods 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
-
- 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
-
- 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
- G01N33/1806—Biological oxygen demand [BOD] or chemical oxygen demand [COD]
-
- 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—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
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
- G01N33/54366—Apparatus specially adapted for solid-phase testing
- G01N33/54373—Apparatus specially adapted for solid-phase testing involving physiochemical end-point determination, e.g. wave-guides, FETS, gratings
- G01N33/5438—Electrodes
Definitions
- the present invention relates to biodegradable impedimetric electrochemical sensor and electrode production method which is developed to conduct analysis of heavy metal in water, to monitor water quality, to conduct analysis for trace metal and anions in environmental samples, to determine metal concentration in human and animal samples; to detect bio-markers, microorganisms, DNA, proteins and enzymes in human and animal fluid samples; to detect microorganisms and biological/chemical markers in liquid, food and environmental samples in all institutions and businesses that conduct water analysis.
- HGAAS hydride generation atomic absorption spectrometry
- GFAAS graphite furnace atomic absorption spectrometry
- NAA neutron activation analysis
- HPLC high pressure liquid chromatography
- ASV anodic stripping voltammetry
- DPP differential pulse polarography
- ICPMS inductively coupled plasma mass spectrometry
- ICPOES inductively coupled plasma optical emission spectroscopy
- HGAAS hydride generation atomic absorption spectrometry
- ICPMS inductively coupled plasma mass spectrometry
- Chinese Utility Model no CN211955198 U an application known in the state of the art, discloses a device for detecting the arsenic content of a water source.
- the said device is comprised of a body internally provided with a 4G module, a fdter tank, an LED light source, and a CCD image sensor.
- a 4G module a 4G module
- a fdter tank a fdter tank
- LED light source an LED light source
- CCD image sensor CCD image sensor
- the main objective of the present invention is to provide a real-time, fast, high sensitivity and low cost impedimetric electrochemical sensor which is employed on-site.
- the sensor achieved as a result of the present invention, it is aimed to perform heavy metal analysis in drinking water, to monitor water quality, to perform trace metal and anion analysis in environmental samples, to determine metal concentration, to perform biosensing, and to monitor biomolecular interactions in human and animal samples, to detect biomarkers, microorganisms, DNA, proteins and enzymes in human and animal liquid samples; to detect microorganisms, biological/chemical markers in liquid, food and environmental samples, and to perform quantitative detection of bacteria and biomarkers and determination of DNA.
- Figure 1 is a schematic view of measurement system.
- the present invention relates to biodegradable impedimetric electrochemical sensor (2) and electrode production method which is developed to conduct analysis of heavy metals in water, to monitor water quality, to conduct analysis for trace metal and anions in environmental samples, to determine metal concentration in human and animal samples; to detect bio-markers, microorganisms, DNA, proteins and enzymes in human and animal fluid samples; to detect microorganisms and biological/chemical markers in liquid, food and environmental samples in all institutions and businesses that conduct water analysis. Selecting a good electrolyte is of great importance to increase the electrochemical performance of the said impedimetric electrochemical sensors.
- Gelatin has excellent chemical properties and biocompatibility.
- the sensor of the present invention comprises distilled water, gelatin, glycerol and binding agent.
- the sensor preferably comprises 10-100 mb of distilled water, 0.1- 10 g of gelatin, 0.1-10 g of glycerol, 15 pL-1.5 mb of binding agent in its structure.
- the preferred binding agent is 2-Mercaptoethanol (ME).
- dimercaprol BAL
- 2- Mercaptoethanol ME
- (3 Mercaptopropyl) trimethoxysilane MPS
- 4-(N- Maleimidomethyl)cyclohexane- 1 -carboxylic acid 3 -sulfo-N-hydroxysuccinimide ester sodium salt Sulfo-SMCC
- EDC/NHS N- ethyl-N'-(3- (dimethylamino)propyl)carbodiimide/N genetic detection receptors and/or protein detection receptors
- the concentration of the binding agent used can range from 0.01 M to 5 M.
- the said gelatin is dissolved in distilled water.
- glycerol, and the binding agent for crosslinking preferably 2-Mercaptoethanol (ME)
- ME 2-Mercaptoethanol
- Chemical crosslinking is used to control hardness to improve brittle mechanical property.
- Hydrophilic groups in membranes comprised of natural polymers such as gelatin increase the ionic conductivity.
- the hydroxyl groups on the gelatin are used both for binding 2-Mercaptoethanol (ME) and for the formation of plasticization.
- the 3 hydroxyl groups in glycerol give condensation reaction with the hydroxyl groups located at different points on 3 different gelatin molecules, thereby forming a layer in the coating process.
- a measurement system suitable for performing measurement comprises a biodegradable impedimetric electrochemical sensor (2), an impedance analyzer (3) with an analysis range of 0.1 Hz - 10 MHz, and a portable device or smartphone (4) comprising a microcontroller.
- immobilization was carried out with chemi cal/biological receptors comprising thiol group used for crosslinking on the surface in biosensor applications.
- the purpose of using these receptors is to provide the desired pH and to create a suitable sensor surface to which the analyte will bind.
- detections are made with an impedance analyzer (3) with an analysis range of 0.1 Hz - 10 MHz and portable devices or smartphones (4) comprising a microcontroller.
- the size of the biodegradable impedimetric electrochemical sensor (2) of the present invention can be shaped according to the nature of the application, expected sensitivity and frequency range.
- the biodegradable impedimetric electrochemical sensor (2) is used to monitor water quality, to analyze trace metals and anions in environmental samples; to determine metal concentration in human and animal samples; to detect biomarkers, microorganisms, DNA, proteins and enzymes in human and animal fluid samples; to detect microorganisms and biological/chemical markers in liquid, food and environmental samples, and experimental processes performed for these purposes can be carried out in different conditions such as environments with high pH, liquid environments. Depending on the application, specific to the analyte structure, there may be changes in the ambient conditions in which the detection will be made.
- the size of the biodegradable impedimetric electrochemical sensor (2) may vary depending on the nature of the said application. Similarly, considering that detection of multiple structures such as markers, enzymes, proteins, DNA/RNA, microorganisms, cells, bacteria and metals will be made in biological samples, the expected sensitivity range may be in the range of femtogram/milliliter and microgram/milliliter.
- the frequency range of the biodegradable impedimetric electrochemical sensor (2) is between 0.1 Hz - 10 MHz. By making changes in this frequency range, it becomes easier to examine the changes that will occur in the three-dimensional structure of the electrode and thus in its electrical properties as a result of the physical and/or chemical binding of the analyte to be detected and analyzed. As a result, by means of the changes in the frequency range, the changes in the structure of the electrode by the binding of the target analyte and in the modification of the sensor surface made for detection (chemical and physical change of the electrode) can be seen.
- Electrochemical sensing platform for the determination of arsenite and arsenate using electroactive nanocomposite electrode Chemical Engineering Journal, 351, 319-327.
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Molecular Biology (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Electrochemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biodiversity & Conservation Biology (AREA)
- Biomedical Technology (AREA)
- Emergency Medicine (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The present invention relates to biodegradable impedimetric electrochemical sensor (2) and electrode production method developed in order to detect the analyte in all institutions and organizations that perform analysis on liquid, environmental, food and biological samples. The main objective of the present invention is to provide an impedimetric electrochemical sensor which is employed on-site, which is real-time, fast, high-sensitivity, low-cost, easy to design and use, which enables early, reliable, portable transportation especially in water management plants in a period of 5 to 30 minutes such that non-specific connection will not be made.
Description
IMPEDIMETRIC ELECTROCHEMICAL SENSOR AND ELECTRODE PRODUCTION METHOD
Field of the Invention
The present invention relates to biodegradable impedimetric electrochemical sensor and electrode production method which is developed to conduct analysis of heavy metal in water, to monitor water quality, to conduct analysis for trace metal and anions in environmental samples, to determine metal concentration in human and animal samples; to detect bio-markers, microorganisms, DNA, proteins and enzymes in human and animal fluid samples; to detect microorganisms and biological/chemical markers in liquid, food and environmental samples in all institutions and businesses that conduct water analysis.
Background of the Invention
It is known that methods such as hydride generation atomic absorption spectrometry (HGAAS) and graphite furnace atomic absorption spectrometry (GFAAS), which are widely used in the determination of arsenic, are reliable laboratory methods for arsenic detection and quantification, but the use of extra materials are required to increase sensitivity and prevent interference in these methods. On the other hand, when developing electrochemical and optical methods such as neutron activation analysis (NAA), high pressure liquid chromatography (HPLC), anodic stripping voltammetry (ASV), differential pulse polarography (DPP), inductively coupled plasma mass spectrometry (ICPMS) and inductively coupled plasma optical emission spectroscopy (ICPOES) are examined, it is understood that measurements with these methods can be performed quickly and with higher sensitivity compared to current methods. However, these methods require highly skilled personnel and expensive and complex instrumentation. However, it is seen that these methods are difficult to adapt to a fast and systematic analysis, and specificity is compromised. However, in this technical field, real-time, fast, on-site detection of arsenic in small concentrations and its biological monitoring play an important role in the
identification of acute or chronic poisoning and in the treatment of diseases. Standard techniques which are being used in the technical field appear difficult to adapt to a systematic analysis of on-site, real-time, fast, and early detection, particularly in water management plants, and require highly skilled personnel and expensive and complex instrumentation.
In this sense, there is a need to develop alternative methods that can be used instead of hydride generation atomic absorption spectrometry (HGAAS) and inductively coupled plasma mass spectrometry (ICPMS) methods.
The disadvantages caused by the applications in the state of the art regarding the determination of arsenic are briefly listed below:
• Failure to detect with the desired sensitivity,
• The difficulty of adapting real-time, fast, and early detection to a systematic analysis,
• Requirement of highly skilled personnel and expensive and complex instrumentation,
• Long detection time,
• The need to use extra materials to increase sensitivity and reduce interference,
• Not being portable,
• Being affected by interference,
• The detection not having been performed in the frequency range of 0. 1 Hz - 10 MHz in most of the detection processes,
• Having reproducible results only in the laboratory environment,
• Long preparation stage,
• The need for advanced infrastructure such as adequate electrical or optical isolation and appropriate surface functionalization,
• Not using smartphones to view the results obtained.
Chinese Utility Model no CN211955198 U, an application known in the state of the art, discloses a device for detecting the arsenic content of a water source. The said device is comprised of a body internally provided with a 4G module, a fdter tank, an LED light source, and a CCD image sensor. However, there is no mention of an element or feature that allows on-site and fast determination in the document.
Summary of the Invention
The main objective of the present invention is to provide a real-time, fast, high sensitivity and low cost impedimetric electrochemical sensor which is employed on-site. With the sensor achieved as a result of the present invention, it is aimed to perform heavy metal analysis in drinking water, to monitor water quality, to perform trace metal and anion analysis in environmental samples, to determine metal concentration, to perform biosensing, and to monitor biomolecular interactions in human and animal samples, to detect biomarkers, microorganisms, DNA, proteins and enzymes in human and animal liquid samples; to detect microorganisms, biological/chemical markers in liquid, food and environmental samples, and to perform quantitative detection of bacteria and biomarkers and determination of DNA.
The technical advantages provided by the sensor according to the invention are briefly listed below:
• Contrary to the state of the art, performing arsenic detection with an impedimetric electrochemical sensor with gelatin based solid electrolyte enriched with dimercaprol,
• Providing on-site, real-time, fast, and early detection at low detection limits,
• Unlike currently used methods, no requirement of highly skilled personnel and expensive and complex instrumentation,
• High sensitivity, low cost, easy to design and use,
• Allowing to perform an early and reliable detection on-site especially in water management plants by using gelatin and glycerol chemicals in a period of approximately 30 minutes with a sensitivity of 1 ng/mE by
performing impedance monitoring with the impedimetric electrochemical sensor having gelatin based solid electrolyte enriched with ME and an impedance analyzer, which allow portable transportation such that nonspecific connection will not be made.
Detailed Description of the Invention
"IMPEDIMETRIC ELECTROCHEMICAL SENSOR AND ELECTRODE PRODUCTION METHOD” developed to fulfill the objective of the present invention is illustrated in the accompanying figure, in which;
Figure 1 is a schematic view of measurement system.
The components given in the figures are individually numbered where the numbers refer to the following.
1. Sample container
2. Biodegradable impedimetric electrochemical sensor
3. Impedance analyzer
4. Smart phone
The present invention relates to biodegradable impedimetric electrochemical sensor (2) and electrode production method which is developed to conduct analysis of heavy metals in water, to monitor water quality, to conduct analysis for trace metal and anions in environmental samples, to determine metal concentration in human and animal samples; to detect bio-markers, microorganisms, DNA, proteins and enzymes in human and animal fluid samples; to detect microorganisms and biological/chemical markers in liquid, food and environmental samples in all institutions and businesses that conduct water analysis. Selecting a good electrolyte is of great importance to increase the electrochemical performance of the said impedimetric electrochemical sensors. Gelatin has excellent chemical properties and biocompatibility.
The sensor of the present invention comprises distilled water, gelatin, glycerol and binding agent. The sensor preferably comprises 10-100 mb of distilled water, 0.1- 10 g of gelatin, 0.1-10 g of glycerol, 15 pL-1.5 mb of binding agent in its structure. In the said structure, the amounts of which are given, the preferred binding agent is 2-Mercaptoethanol (ME). In the present invention, dimercaprol (BAL), 2- Mercaptoethanol (ME), (3 Mercaptopropyl) trimethoxysilane (MPS), 4-(N- Maleimidomethyl)cyclohexane- 1 -carboxylic acid 3 -sulfo-N-hydroxysuccinimide ester sodium salt (Sulfo-SMCC), EDC/NHS (N- ethyl-N'-(3- (dimethylamino)propyl)carbodiimide/N genetic detection receptors and/or protein detection receptors are used as binding agent in different concentrations. The purpose of preferably using 2-Mercaptoethanol (ME) is to increase surface activation. The concentration of the binding agent used can range from 0.01 M to 5 M.
In the studies carried out within the scope of the invention, samples at different concentrations were prepared and the optimum sensor structure was tried to be determined. As a result of the studies conducted, 15 mb of distilled water, 2 g of gelatin and 1.75 g of glycerol were determined, therefore these concentration values were preferred in the studies at this stage. These determined values may vary depending on the purpose of use of the biodegradable impedimetric electrochemical sensor (2) and the analyte to be detected.
In order to form the bioactive layer of the biosensor and to ensure complete dissolution, in the electrode production method, the said gelatin is dissolved in distilled water. After the dissolution process, glycerol, and the binding agent for crosslinking (preferably 2-Mercaptoethanol (ME)) are added into the gelatin solution so that the gelatin structure gains flexibility and hardness. Chemical crosslinking is used to control hardness to improve brittle mechanical property. Hydrophilic groups in membranes comprised of natural polymers such as gelatin increase the ionic conductivity. The hydroxyl groups on the gelatin are used both for binding 2-Mercaptoethanol (ME) and for the formation of plasticization. In the
process steps performed in the said method, apart from the components dimercaprol (BAL), 2-Mercaptoethanol (ME) and (3 Mercaptopropyl) trimethoxysilane (MPS), 4-(N-Maleimidomethyl)cyclohexane-l -carboxylic acid 3-sulfo-N- hydroxysuccinimide ester sodium salt (Sulfo-SMCC), EDC/NHS (N-etil-N'-(3- (dimetilamino)propil)carbodiimide/N can be used as binding agent; DNA, Peptide Nucleic acid, Locked Nucleic Acid can be used as genetic detection receptor; and protein, antigen, antibody, enzyme can be used as Protein detection receptor.
The 3 hydroxyl groups in glycerol give condensation reaction with the hydroxyl groups located at different points on 3 different gelatin molecules, thereby forming a layer in the coating process.
As a result of the structure formed as a result of the interaction of gelatin and glycerol, the condensation of the free hydroxyl groups on the gelatin molecules with the hydroxyl groups in the 2-Mercaptoethanol (ME) molecules continues and an upper layer consisting of thiol groups is formed on the surface. Thanks to this coating, the environment is prepared for arsenic coating on the surface. As a result of this immobilization, both the desired bonds for the arsenic binding are realized and the gelatin-based solid electrolyte structure is confirmed.
The procedure that gives the most optimal result for impedance monitoring has been determined, and the optimum amount of each parameter has been determined and an impedimetric electrochemical sensor has been prepared. The chemical and morphological properties of the solid electrolyte surface are directly related to the quality and sensitivity of the detection. For this reason, the surface was characterized by FTIR and SEM in the studies carried out within the scope of the invention. After the surface was prepared for arsenic binding, arsenic solution at various concentrations was added to the surface and analyses were carried out first in distilled water and then in drinking water samples. With the measurements made, it has been possible to measure not only qualitatively, but also quantitatively between 0.01 ng and 1 pg. It was quantified in the range of 1 nM to 10‘4 nM.
In Figure 1, the general view of the measurement process performed using the said biodegradable impedimetric electrochemical sensor (2) is given. Accordingly, by means of the biodegradable impedimetric electrochemical sensor (2), detections can be made with an impedance analyzer (3) with an analysis range of0.1 Hz - 10 MHz, portable devices or smartphones (4) comprising a microcontroller . The general view of the said measurement process is given in Figure 1. In this sense, a measurement system suitable for performing measurement comprises a biodegradable impedimetric electrochemical sensor (2), an impedance analyzer (3) with an analysis range of 0.1 Hz - 10 MHz, and a portable device or smartphone (4) comprising a microcontroller.
For the detection processes to be performed with the biodegradable impedimetric electrochemical sensor (2) of the present invention, immobilization was carried out with chemi cal/biological receptors comprising thiol group used for crosslinking on the surface in biosensor applications. The purpose of using these receptors is to provide the desired pH and to create a suitable sensor surface to which the analyte will bind. As a result of this immobilization, not only the desired bonds for detection were made, but also the sensor structure was confirmed. After these processes, detections are made with an impedance analyzer (3) with an analysis range of 0.1 Hz - 10 MHz and portable devices or smartphones (4) comprising a microcontroller.
The size of the biodegradable impedimetric electrochemical sensor (2) of the present invention can be shaped according to the nature of the application, expected sensitivity and frequency range. The biodegradable impedimetric electrochemical sensor (2) is used to monitor water quality, to analyze trace metals and anions in environmental samples; to determine metal concentration in human and animal samples; to detect biomarkers, microorganisms, DNA, proteins and enzymes in human and animal fluid samples; to detect microorganisms and biological/chemical markers in liquid, food and environmental samples, and experimental processes
performed for these purposes can be carried out in different conditions such as environments with high pH, liquid environments. Depending on the application, specific to the analyte structure, there may be changes in the ambient conditions in which the detection will be made. In this sense, the size of the biodegradable impedimetric electrochemical sensor (2) may vary depending on the nature of the said application. Similarly, considering that detection of multiple structures such as markers, enzymes, proteins, DNA/RNA, microorganisms, cells, bacteria and metals will be made in biological samples, the expected sensitivity range may be in the range of femtogram/milliliter and microgram/milliliter. The frequency range of the biodegradable impedimetric electrochemical sensor (2) is between 0.1 Hz - 10 MHz. By making changes in this frequency range, it becomes easier to examine the changes that will occur in the three-dimensional structure of the electrode and thus in its electrical properties as a result of the physical and/or chemical binding of the analyte to be detected and analyzed. As a result, by means of the changes in the frequency range, the changes in the structure of the electrode by the binding of the target analyte and in the modification of the sensor surface made for detection (chemical and physical change of the electrode) can be seen.
The comparison between the sensing mechanisms used in the technical field between the present invention in terms of linear range and detection limit is given in the table below.
REFERENCES
[1]. Wang, L., Xu, X., Niu, X., Pan, J.,2021. Colorimetric detection and membrane removal of arsenate by a multifunctional L-arginine modified FeOOH. Separation and Purification Technology, 258, 118021.
[2]. Rajkumar, M., Thiagarajan, S., Chen, S.M.,2011. Electrochemical detection of arsenic in various water samples, International Journal of Electrochemical Science, 6,3164 - 3177.
[3]. Sonkoue, B. M., Tchekwagep, P. M. S., Nanseu-Njiki, C. P., Ngameni,
E., 2018. Electrochemical determination of arsenic using silver nanoparticles, Electroanalysis, 30, 1 -7.
[4]. Li, D., Li, J., Jia, X., Han, Y., Wang, E., 2012. Electrochemical determination of arsenic(III) on mercaptoethylamine modified Au electrode in neutral media. Analytica Chimica Acta, 733, 23-27.
[5]. Carrera, P., Espinoza-Montero, P. J., Fernandez, L., Romero, H.,
Alvarado, J., 2017. Electrochemical determination of arsenic in natural waters using carbon fiber ultra-microelectrodes modified with gold nanoparticles. Taianta, 166, 198-206.
[6]. Gumpu, M. B., Veerapandian, M., Krishnan, U. M., Rayappan, J. B. B.,
2018. Electrochemical sensing platform for the determination of arsenite and arsenate using electroactive nanocomposite electrode. Chemical Engineering Journal, 351, 319-327.
Claims
CLAIMS A biodegradable impedimetric electrochemical sensor (2) developed to conduct analysis in water for heavy metals in all institutions and businesses that conduct water analysis, characterized in that it comprises distilled water, gelatin, glycerol and binding agent. A biodegradable impedimetric electrochemical sensor (2) according to claim 1, characterized in that it comprises 10-100 mL of distilled water, 0.1- 10 g of gelatin, 0.1-10 g of glycerol, and 15 pL-1.5 mL of binding agent. An electrode production method in order to form bioactive layer of a biodegradable impedimetric electrochemical sensor (2) according to claim 1 and to ensure complete dissolution, characterized in that it comprises the process steps of
• dissolving gelatin in distilled water,
• adding glycerol to the gelatin solution so that the gelatin structure gains flexibility and hardness after the dissolution process,
• adding at least one binding agent to the gelatin solution for crosslinking. A method according to claim 3, characterized in that dimercaprol, 2- Mercaptoethanol, (3 Mercaptopropyl) trimethoxysilane, 4-(N- Maleimidomethyl)cyclohexane- 1 -carboxylic acid 3-sulfo-N- hydroxysuccinimide ester sodium salt (Sulfo-SMCC), EDC/NHS (N- ethyl- N'-(3-(dimethylamino)propyl)carbodiimide/N genetic detection receptors and/or protein detection receptors are used as binding agent. Use of a biodegradable impedimetric electrochemical sensor (2) according to claim 1 in order to perform heavy metal analysis in drinking water, to monitor water quality, to perform trace metal and anion analysis in environmental samples, to determine metal concentration, to perform
biosensing, and to monitor biomolecular interactions in human and animal samples, to detect biomarkers, microorganisms, DNA, proteins and enzymes in human and animal liquid samples; to detect microorganisms, biological/chemical markers in liquid, food and environmental samples, and to perform quantitative detection of bacteria and biomarkers and determination of DNA. A measurement system, characterized in that it comprises
• a biodegradable impedimetric electrochemical sensor (2),
• impedance analyzer (3) with analysis range of 0. 1 Hz - 10 MHz,
• portable device or smartphone (4) comprising microcontroller. A biodegradable impedimetric electrochemical sensor (2) according to Claim 1, the size of which may vary according to the environment and conditions of the processes performed for the detection. A biodegradable impedimetric electrochemical sensor (2) according to Claim 1, which has a sensitivity between femtogram/milliliter and microgram/milliliter in detection processes such as marker, enzyme, protein, DNA/RNA, microorganism, cell, bacteria, metal determination in biological samples and the size of which can vary according to the said sensitivity. A biodegradable impedimetric electrochemical sensor (2) according to Claim 1, which has a frequency range of 0.1 Hz - 10 MHz and the size of which may vary according to the said frequency range.
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| Application Number | Priority Date | Filing Date | Title |
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| TR2022/002989 TR2022002989A2 (en) | 2022-03-01 | IMPEDIMETRIC ELECTROCHEMICAL SENSOR AND ELECTRODE PRODUCTION METHOD | |
| TR2022002989 | 2022-03-01 |
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| WO2023167644A1 true WO2023167644A1 (en) | 2023-09-07 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130319880A1 (en) * | 2012-06-04 | 2013-12-05 | Ching-Chou Wu | Impedimetric Biosensor System With Improved Sensing Efficiency |
| EP3287784A1 (en) * | 2013-07-04 | 2018-02-28 | Universiteit Antwerpen | Electrochemical sensors with a gelatin b matrix |
| CN109142483A (en) * | 2018-07-17 | 2019-01-04 | 上海理工大学 | It is a kind of for detecting the electrochemica biological sensor and detection method of inorganic trivalent arsenic |
| US20190150815A1 (en) * | 2017-11-21 | 2019-05-23 | Jeffrey LaBelle | Biosensor array for the detection of analytes |
-
2022
- 2022-04-14 WO PCT/TR2022/050332 patent/WO2023167644A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130319880A1 (en) * | 2012-06-04 | 2013-12-05 | Ching-Chou Wu | Impedimetric Biosensor System With Improved Sensing Efficiency |
| EP3287784A1 (en) * | 2013-07-04 | 2018-02-28 | Universiteit Antwerpen | Electrochemical sensors with a gelatin b matrix |
| US20190150815A1 (en) * | 2017-11-21 | 2019-05-23 | Jeffrey LaBelle | Biosensor array for the detection of analytes |
| CN109142483A (en) * | 2018-07-17 | 2019-01-04 | 上海理工大学 | It is a kind of for detecting the electrochemica biological sensor and detection method of inorganic trivalent arsenic |
Non-Patent Citations (1)
| Title |
|---|
| KALIMUTHU PALRAJ, GONZALEZ-MARTINEZ JUAN F., RUZGAS TAUTGIRDAS, SOTRES JAVIER: "Highly Stable Passive Wireless Sensor for Protease Activity Based on Fatty Acid-Coupled Gelatin Composite Films", ANALYTICAL CHEMISTRY, AMERICAN CHEMICAL SOCIETY, US, vol. 92, no. 19, 6 October 2020 (2020-10-06), US , pages 13110 - 13117, XP093091156, ISSN: 0003-2700, DOI: 10.1021/acs.analchem.0c02153 * |
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