CN108414587A - A kind of preparation method of urease biologic sensor - Google Patents
A kind of preparation method of urease biologic sensor Download PDFInfo
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- CN108414587A CN108414587A CN201810168856.8A CN201810168856A CN108414587A CN 108414587 A CN108414587 A CN 108414587A CN 201810168856 A CN201810168856 A CN 201810168856A CN 108414587 A CN108414587 A CN 108414587A
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- 108010046334 Urease Proteins 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920001661 Chitosan Polymers 0.000 claims abstract description 27
- 238000007650 screen-printing Methods 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 229920000767 polyaniline Polymers 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 58
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 36
- 239000011259 mixed solution Substances 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000002114 nanocomposite Substances 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 238000002484 cyclic voltammetry Methods 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000001548 drop coating Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000052 vinegar Substances 0.000 claims description 4
- 235000021419 vinegar Nutrition 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 230000004044 response Effects 0.000 abstract description 20
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 13
- 238000001514 detection method Methods 0.000 abstract description 12
- 108090000790 Enzymes Proteins 0.000 abstract description 7
- 102000004190 Enzymes Human genes 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004458 analytical method Methods 0.000 abstract description 4
- 229910052697 platinum Inorganic materials 0.000 abstract description 4
- 230000007423 decrease Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 26
- 239000004202 carbamide Substances 0.000 description 26
- 230000002401 inhibitory effect Effects 0.000 description 13
- 239000004753 textile Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000008859 change Effects 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000143432 Daldinia concentrica Species 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000002255 enzymatic effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 210000004243 sweat Anatomy 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001075 voltammogram Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 208000012886 Vertigo Diseases 0.000 description 1
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000006931 brain damage Effects 0.000 description 1
- 231100000874 brain damage Toxicity 0.000 description 1
- 208000029028 brain injury Diseases 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003683 cardiac damage Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 150000005839 radical cations Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- 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
-
- 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
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- 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
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Nanotechnology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention discloses a kind of preparation methods of urease biologic sensor, belong to analysis detection field.The sensor is to utilize screen printing electrode, constructs a kind of biosensor based on polyaniline film and chitosan/platinum carbon ball, realizes the quick detection of heavy metal ion.The urease biologic sensor that technical solution of the present invention is prepared has good reproducibility and time saving, laborsaving, cheap, reduction solvent, pollution etc. of the reduction to environment.Sensor is preserved can be placed in 4 DEG C of refrigerator when not used, and the inner potential response of three weeks does not all decline, is remained to keep the 95% of initial potential response after preserving 30 days, is illustrated that chitosan can effectively keep the activity of urase, and can prevent enzyme from leaking.
Description
The application is：On May 20th, 2016, application No. is：201610340251.3, it is entitled：Based on poly-
Aniline modifies the divisional application of the urease biologic sensor of screen printing electrode and its patent of invention of application.
Technical field
The invention belongs to analyze detection field, and in particular to a kind of preparation method of urease biologic sensor.
Background technology
With popularizing for green consumption idea, ecological textile increasingly becomes the mainstream in market, in recent years, in textile
Index one of of the detection of extractable heavy metal as ecological textile is increasingly taken seriously.Heavy metal is main in textile
The dyestuff and auxiliary agent used in process, such as various premetallized dyes, phthalein mountain valley with clumps of trees and bamboo structure dyestuff, are consolidated medium fuel
Toner, catalyst, fire retardant, post-finishing agent etc. and for soft water hardening, desizing is concise, various in the bleaching processes such as stamp
Metal chelating agent.It is absorption of human body that extractable heavy metal, which can be entered by the sweat of human body inside human skin, in textile,
Can cause health when heavy metal is accumulated to a certain extent in human organ huge in liver, bone, kidney, the heart and brain
Damage.The detection method of extractable heavy metal is mainly GB/T 17593 in the textile of national regulation at present, and which specify spinnings
The test method of the various heavies such as arsenic, cadmium, cobalt, chromium, copper, nickel, lead, antimony in fabric.Main analytical instrument to be used is atom
Absorption spectrum and inductive coupling plasma emission spectrum.
Although existing analysis method precision is good, accuracy is high, and existing analysis method cannot meet time saving, province
Power, cheap, reduction solvent, pollution etc. of the reduction to environment.
Invention content
The present invention be directed to problems of the existing technology to provide a kind of urea based on Polyaniline-modified screen printing electrode
Enzyme biologic sensor and its application.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of urease biologic sensor based on Polyaniline-modified screen printing electrode, the sensor are by the following method
It is prepared：
(1) screen printing electrode electropolymerization polyaniline：Screen printing electrode is placed in the electricity containing hydrochloric acid and aniline first
In polymeric solution, uses cyclic voltammetry to carry out electropolymerization later, obtain PAIN modified electrodes；
(2) platinum/carbon ball nanocomposite：Carbon ball is added in ethylene glycol solution and ultrasonic disperse uniformly obtains carbon
Slurry is slowly added to chloroplatinic acid and is uniformly mixing to obtain mixed liquor in carbon slurry, and the mixed liquor is adjusted to alkalinity using alkaline reagent,
100~150 DEG C of reductase 12~6h are warming up to, later by the washing of obtained black product, drying, obtain the nano combined material of platinum/carbon ball
Material；
(3) urease biologic sensor：The platinum that chitosan and step (2) are prepared/carbon ball nanocomposite is added
To in acetum and being uniformly mixed, chitosan-platinum/carbon ball mixed solution is obtained；By chitosan-platinum/carbon ball mixed solution with
Urase solution is uniformly mixed, and obtains urase-chitosan/platinum/carbon ball mixed solution；In the PAIN modifications that step (1) is prepared
Electrode surface drop coating urase-chitosan/platinum/carbon ball mixed solution, is prepared urease biologic sensor.Drop coating amount is about 15 μ
L/cm2。
A kind of urease biologic sensor preparation method based on Polyaniline-modified screen printing electrode, this method includes following
Step：
(1) screen printing electrode electropolymerization polyaniline：Screen printing electrode is placed in the electricity containing hydrochloric acid and aniline first
In polymeric solution, uses cyclic voltammetry to carry out electropolymerization later, obtain PAIN modified electrodes；
(2) platinum/carbon ball nanocomposite：Carbon ball is added in ethylene glycol solution and ultrasonic disperse uniformly obtains carbon
Slurry is slowly added to chloroplatinic acid and is uniformly mixing to obtain mixed liquor in carbon slurry, and the mixed liquor is adjusted to alkalinity using alkaline reagent,
100~150 DEG C of reductase 12~6h are warming up to, later by the washing of obtained black product, drying, obtain the nano combined material of platinum/carbon ball
Material；
(3) urease biologic sensor：The platinum that chitosan and step (2) are prepared/carbon ball nanocomposite is added
To in acetum and being uniformly mixed, chitosan-platinum/carbon ball mixed solution is obtained；By chitosan-platinum/carbon ball mixed solution with
Urase solution is uniformly mixed, and obtains urase-chitosan/platinum/carbon ball mixed solution；In the PAIN modifications that step (1) is prepared
Electrode surface drop coating urase-chitosan/platinum/carbon ball mixed solution, is prepared urease biologic sensor.
In urease biologic sensor described in technical solution of the present invention and preparation method thereof：The electropolymerization process of step (1)
It being carried out under conditions of nitrogen protection, cyclic voltammetry scanning range is -0.1V~0.7V, the rate of scanning is 40~
60mV/s is always scanned 80~120 times.
In urease biologic sensor described in technical solution of the present invention and preparation method thereof：The electropolymerization solution of step (1)
A concentration of 0.1~3.5mol/L of middle hydrochloric acid, a concentration of 0.1~3mol/L of aniline.
In urease biologic sensor described in technical solution of the present invention and preparation method thereof：The carbon ball of step (2) and chlorine platinum
The mass ratio of acid is 1~3：1.
In urease biologic sensor described in technical solution of the present invention and preparation method thereof：The alkalinity of step (2) refers to mixing
The pH value for closing liquid is 9~11.
In urease biologic sensor described in technical solution of the present invention and preparation method thereof：Chitosan-platinum of step (3)/
The mass fraction of chitosan is 0.1~1% in carbon ball mixed solution, the mass fraction of platinum/carbon ball nanocomposite is 0.5~
1.5%.
In urease biologic sensor described in technical solution of the present invention and preparation method thereof：The urase solution of step (3) is dense
It is 5~15mg/ml to spend, and the volume ratio of chitosan-platinum/carbon ball mixed solution and urase solution is 1~5：1~5.
In urease biologic sensor described in technical solution of the present invention and preparation method thereof：The drop coating amount of step (3) is 10
~30 μ L/cm2。
Application of the aforementioned PAIN modified electrodes in measuring pH value of solution；It is preferred that the inhibition time measured be >=
20min, response time >=2min.
Application of the aforementioned urease biologic sensor in detecting heavy metal ion；It is preferred that being detected in urea liquid
Hg2+And Cd2+In application；Hg in textile is detected more preferably in urea liquid2+And Cd2+Application.The inhibition time of measurement
For >=20min, response time >=2min；It is preferred that the concentration of urea liquid≤selection 40mmol/L.
Beneficial effects of the present invention：
The urease biologic sensor that technical solution of the present invention is prepared have good reproducibility and it is time saving, laborsaving, cheap,
It reduces solvent, reduce the pollution etc. to environment.Sensor is preserved can be placed in 4 DEG C of refrigerator when not used, in three weeks
Potential response does not all decline, remains to keep the 95% of initial potential response after preserving 30 days, illustrates that chitosan can be effectively
The activity of urase is kept, and can prevent enzyme from leaking.
Description of the drawings
Fig. 1 is the voltammogram that 1 aniline monomer of embodiment powers on 100 gained of polymerisation loop in screen printing electrode.
Before and after Fig. 2 is aniline polymerization, the cycle of screen printing electrode is bent over the desk figure.
Fig. 3 is the relational graph of the potential response and solution ph of PAIN modified electrodes.
Fig. 4 is that urease biologic sensor is placed in the potential response of urea liquid and changes with time figure.
Fig. 5 is in Hg2+Or Cd2+In the presence of, inhibiting rate, which changes with time, sees Fig. 5
Fig. 6 is that urease biologic sensor is placed in the solution containing urea, urea concentration and potential change figure.
Fig. 7 is that urease biologic sensor is placed in the solution containing urea, the relational graph of inhibiting rate and heavy metal concentration.
Specific implementation mode
With reference to embodiment, the present invention will be further described, and but the scope of the present invention is not limited thereto：
Carbon ball described in the embodiment of the present invention can be that commercial product is either prepared with the following method：With first
Aldehyde-resorcinol is precursor, is usedMethod, 0.1mL ammonium hydroxide (25w%) are added to 8mL ethyl alcohol and 20mL deionized waters
Mixed solution in, stir 1h after, be added 0.2g resorcinols, stir to being completely dissolved, it is molten that 0.284mL formaldehyde is then added dropwise again
Liquid (37w%), mixed liquor stir for 24 hours at 30 DEG C, then move to mixed liquor in water heating kettle, are reacted at 100 DEG C for 24 hours, mixture
It is centrifuged, dry 48h at 100 DEG C.Next, carry out charing process is heated to 350 with the heating rate of 1 DEG C/min
DEG C, 2h is kept, is then heated to 600 DEG C again with the heating rate of 1 DEG C/min, calcining 4h is retained, then naturally cools to room
Carbon ball is prepared in temperature.
Embodiment 1
Screen printing electrode electropolymerization polyaniline：Screen printing electrode is placed in the electropolymerization containing hydrochloric acid and aniline first
In solution, wherein the molar concentration of HC1 is 1mol/L, and the molar concentration of aniline is 0.5mol/L；Cyclic voltammetry is used later
Electropolymerization is carried out, cyclic voltammetry scanning range is -0.1V~0.7V, sweep speed 50mV/s, is scanned 100 times in total.It is real
Electropolymerization solution need to lead to nitrogen l0min before testing beginning, and entire electropolymerization process is completed under a nitrogen atmosphere.After the completion of electropolymerization, use
1mol/L hydrochloric acid and secondary water are rinsed electrode, dry, and PAIN modified electrodes are made；
Platinum/carbon ball nanocomposite：80mg carbon balls are added in ethylene glycol solution and ultrasonic disperse uniformly obtains carbon
Slurry is slowly added to 42mg chloroplatinic acids in carbon slurry and is uniformly mixing to obtain mixed liquor, the pH of mixed is adjusted using NaOH solution
To 10, it is warming up to 130 DEG C of reduction 3h and obtains platinum/carbon ball nanocomposite later by the washing of obtained black product, drying；
Urease biologic sensor：Platinum/carbon ball nanocomposite that chitosan and step (2) are prepared is added to vinegar
It in acid solution and is uniformly mixed, obtains chitosan-platinum/carbon ball mixed solution, the mass fraction of chitosan is in the mixed liquor
0.5%, the mass fraction of platinum/carbon ball nanocomposite is 1%；It is 1 by volume ratio：1 chitosan-platinum/carbon ball mixing is molten
Liquid is uniformly mixed with a concentration of 10mg/ml urases solution, obtains urase-chitosan/platinum/carbon ball mixed solution；It is made in step (1)
Standby obtained 15 μ L/cm of PAIN modified electrodes surface drop coating2Urase-chitosan/platinum/carbon ball mixed solution, is prepared urase
Biosensor.
Embodiment 2
Screen printing electrode electropolymerization polyaniline：Screen printing electrode is placed in the electropolymerization containing hydrochloric acid and aniline first
In solution, wherein the molar concentration of HC1 is 2mol/L, and the molar concentration of aniline is 1mol/L；Later use cyclic voltammetry into
Row electropolymerization, cyclic voltammetry scanning range are -0.1V~0.7V, sweep speed 40mV/s, are scanned 80 times in total.Experiment is opened
Electropolymerization solution need to lead to nitrogen l0min before beginning, and entire electropolymerization process is completed under a nitrogen atmosphere.After the completion of electropolymerization, 1mol/L is used
Hydrochloric acid and secondary water are rinsed electrode, dry, and PAIN modified electrodes are made；
Platinum/carbon ball nanocomposite：50mg carbon balls are added in ethylene glycol solution and ultrasonic disperse uniformly obtains carbon
Slurry is slowly added to 42mg chloroplatinic acids in carbon slurry and is uniformly mixing to obtain mixed liquor, the pH of mixed is adjusted using NaOH solution
To 9, it is warming up to 100 DEG C of reduction 6h and obtains platinum/carbon ball nanocomposite later by the washing of obtained black product, drying；
Urease biologic sensor：Platinum/carbon ball nanocomposite that chitosan and step (2) are prepared is added to vinegar
It in acid solution and is uniformly mixed, obtains chitosan-platinum/carbon ball mixed solution, the mass fraction of chitosan is in the mixed liquor
1%, the mass fraction of platinum/carbon ball nanocomposite is 1.5%；It is 1 by volume ratio：3 chitosan-platinum/carbon ball mixing is molten
Liquid is uniformly mixed with a concentration of 5mg/ml urases solution, obtains urase-chitosan/platinum/carbon ball mixed solution；It is made in step (1)
Standby obtained 10 μ L/cm of PAIN modified electrodes surface drop coating2Urase-chitosan/platinum/carbon ball mixed solution, is prepared urase
Biosensor.
Embodiment 3
Screen printing electrode electropolymerization polyaniline：Screen printing electrode is placed in the electropolymerization containing hydrochloric acid and aniline first
In solution, wherein the molar concentration of HC1 is 3mol/L, and the molar concentration of aniline is 1.5mol/L；Cyclic voltammetry is used later
Electropolymerization is carried out, cyclic voltammetry scanning range is -0.1V~0.7V, sweep speed 60mV/s, is scanned 120 times in total.It is real
Electropolymerization solution need to lead to nitrogen l0min before testing beginning, and entire electropolymerization process is completed under a nitrogen atmosphere.After the completion of electropolymerization, use
1mol/L hydrochloric acid and secondary water are rinsed electrode, dry, and PAIN modified electrodes are made；
Platinum/carbon ball nanocomposite：120mg carbon balls are added in ethylene glycol solution and ultrasonic disperse uniformly obtains carbon
Slurry is slowly added to 42mg chloroplatinic acids in carbon slurry and is uniformly mixing to obtain mixed liquor, the pH of mixed is adjusted using NaOH solution
To 11,150 DEG C of reductase 12 h are warming up to, later by the washing of obtained black product, drying, obtain platinum/carbon ball nanocomposite；
Urease biologic sensor：Platinum/carbon ball nanocomposite that chitosan and step (2) are prepared is added to vinegar
It in acid solution and is uniformly mixed, obtains chitosan-platinum/carbon ball mixed solution, the mass fraction of chitosan is in the mixed liquor
0.4%, the mass fraction of platinum/carbon ball nanocomposite is 1.5%；It is 3 by volume ratio：1 chitosan-platinum/carbon ball mixing
Solution is uniformly mixed with a concentration of 15mg/ml urases solution, obtains urase-chitosan/platinum/carbon ball mixed solution；In step (1)
The 30 μ L/cm of PAIN modified electrodes surface drop coating being prepared2Urase-chitosan/platinum/carbon ball mixed solution, is prepared urea
Enzyme biologic sensor.
Performance detection
The preparation of 1PAIN modified electrodes
Fig. 1 is the voltammogram that 1 aniline monomer of embodiment powers on 100 gained of polymerisation loop in screen printing electrode, is followed
Ring voltammogram shows that its electrode process has invertibity.Spike potential is aoxidized respectively in 0.22V, and reduction spike potential is in 0.08V.The peak
The process of radical cation is oxidized to for the aniline of protonation.With the increase of cycle-index, peak current increases, this is because
Aniline is once in electrode surface polymerization film formation, it may occur that self-catalyzed reaction, while the film thickness of polymer also gradually increases.It prepares
Obtained polyaniline film modified electrode is blue-green.Before and after aniline polymerization, the cycle of screen printing electrode figure of bending over the desk is shown in Fig. 2, bent
Line a is before electropolymerization starts, and the cyclic voltammogram of screen printing electrode, curve b is after the completion of electropolymerization, and polyaniline film covers
The screen printing electrode of lid recycles figure of bending over the desk.Figure it is seen that after electropolymerization, the Polyaniline-modified being prepared is electric
Pole has a pair of apparent redox peaks, peak current to significantly increase, and illustrates that polyaniline film cathode is successfully prepared.
The pH of 2PAIN modified electrodes is responded
PAIN modified electrodes have response to the current potential of solution, the pH value variation for the solution that can be surveyed.The potential response of electrode
It is obtained with the relationship of solution ph by detecting the open circuit potential of itself and Ag/AgC1 reference electrodes.Different pH value solution, can be with
Different potential values is obtained, the results are shown in Figure 3.The response range of this Polyaniline-modified screen printing electrode be pH 1~
PH12, shows preferable linear relationship, linearly dependent coefficient 0.999, and slope is：60.8mV/pH(T：25 DEG C), see Fig. 3.
From the figure 3, it may be seen that polyaniline modified electrode has good potential response.
3 response times and the selection for inhibiting the time
The hydrolysis of urease biologic sensor catalyzing urea needs certain response time, should ensure that when being tested identical
Response time.Urease biologic sensor is placed in urea liquid, its potential response is tested and changes with time, concrete outcome
See Fig. 4, from fig. 4, it can be seen that potential response increase at any time and increase, tend towards stability after the 2 minutes.Therefore in detection electricity
When position, it is 2min to select the response time i.e. time of enzymatic reacting of electrode.
In the presence of having heavy metal ion in the solution, the activity of urase can be suppressed.With the growth of time,
Inhibiting rate can increase, and inhibiting rate reaches balance within a certain period of time.Sensor is placed in containing Hg2+Or Cd2+With the solution of urea
In, inhibiting rate, which changes with time, sees Fig. 5, it can be seen that from 0-20min, with the growth of time, inhibiting rate increases,
After 20min, inhibiting rate reaches a platform, therefore when carrying out heavy metal analysis, and the inhibition time selected is 20min.
The selection of 4 urea concentrations
The urease biologic sensor that embodiment 1 is prepared is placed in the solution containing urea, urase can catalyzing urea
Hydrolysis, generate CO2And NH3, cause the potential change of solution.The concentration of urea liquid can influence the degree of potential change, urea
Concentration is shown in Fig. 6 from the relationship of 10-100mmol/L and potential change.From fig. 6, it can be seen that urea concentration is from 10 to 40mmol/L
When, potential difference is directly proportional to urea concentration, urea concentration from 50mmol/L to 100mmol/L potential difference with urea concentration
Variation, speedup slows down, this is because the fixed enzyme of electrode surface, the urea of catalysis Finite Concentration is only capable of, when urea concentration mistake
Gao Shi, the catalytic capability of enzyme can tend to be saturated.According to Fig.6, the urea liquid of selection≤40mmol/L, the most properly.
5 urease biologic sensors are used for the detection of heavy metal ion
The urease biologic sensor that embodiment 1 is prepared is placed in the urea liquid of 40mmol/L, it is anti-to measure enzymatic
Potential change Δ E caused by answering.The Hg of various concentration is separately added into urea liquid2+(10、50、100、500、1000、2000
μ g/L) and Cd2+(50,100,500,1000,2000,5000 μ g/L) solution, after twenty minutes, the current potential after test inhibition calculates
The potential change Δ E' of enzymatic reaction after inhibition.Heavy metal to the inhibiting rate of urease activity be equal to [(Δ E- Δ E')/Δ E] ×
100%.
The relationship of inhibiting rate and heavy metal concentration is as shown in fig. 7, it can be seen from figure 7 that Hg2+And Cd2+Inhibiting rate
Increase with the increase of concentration, the inhibiting rate of enzymatic activity and the negative logarithm of concentration are in good linear relationship, linear correlation system
Number is in 0.99 or more, Hg2+The range of linearity is 10-2000 μ g/L, Cd2+The range of linearity be 500-5000 μ g/L, calculate detection
It is limited to Hg2+3.89 μ g/L, Cd2+5.41 μ g/L (are calculated) by inhibiting rate 10%.
The reproducibility and stability of 6 urease biologic sensors
The 500 μ g/L Hg of urease biologic sensor pair for selecting embodiment 1 to be prepared2+With 500 μ g/L Cd2+Detection
Relative standard deviation is respectively 7.2%, 8.9%.Show that the sensor has good reproducibility.Sensor can set when not used
It is preserved in 4 DEG C of refrigerator, the inner potential response of three weeks does not all decline, remains to keep initial potential response after preserving 30 days
95%, illustrate that chitosan can effectively keep the activity of urase, and can prevent enzyme from leaking.
Detection of 7 sensors to textile actual sample
The preparation of textile samples solution：Textile samples first shred into 5mm × 5mm fragments, weigh 2g, and 80mL acid is added
Property sweat, be put into thermostatic control oscillator vibration and vibrate after sixty minutes, it is cooling for use.Acidic sweat is according to GB/T17593.2-2007
Requirement prepare.
The urease biologic sensor that embodiment 1 is prepared is selected to carry out mark-on reclaims in textile samples extracting solution,
Calculate its rate of recovery.Particular content is shown in Table 1, as it can be seen from table 1 the rate of recovery range of sample is between 80%-120%, it can
For the detection of actual sample.
The recovery of standard addition of 1 actual sample of table
Claims (3)
1. a kind of preparation method of urease biologic sensor, it is characterised in that：This approach includes the following steps：
(1) screen printing electrode electropolymerization polyaniline：Screen printing electrode is placed in the electropolymerization containing hydrochloric acid and aniline first
In solution, uses cyclic voltammetry to carry out electropolymerization later, obtain PANI modified electrodes；
(2) platinum/carbon ball nanocomposite：Carbon ball is added in ethylene glycol solution and ultrasonic disperse uniformly obtains carbon slurry,
It is slowly added to chloroplatinic acid in carbon slurry and is uniformly mixing to obtain mixed liquor, which is adjusted to alkalinity, heating using alkaline reagent
To 100~150 DEG C of reductase 12~6h, later by the washing of obtained black product, drying, platinum/carbon ball nanocomposite is obtained；
(3) urease biologic sensor：Platinum/carbon ball nanocomposite that chitosan and step (2) are prepared is added to vinegar
It in acid solution and is uniformly mixed, obtains chitosan-platinum/carbon ball mixed solution；By chitosan-platinum/carbon ball mixed solution and urase
Solution is uniformly mixed, and obtains urase-chitosan/platinum/carbon ball mixed solution；In the PANI modified electrodes that step (1) is prepared
Surface drop coating urase-chitosan/platinum/carbon ball mixed solution, is prepared urease biologic sensor；
Wherein：The electropolymerization process of step (1) carries out under conditions of nitrogen protection, cyclic voltammetry scanning range be-
The rate of 0.1V~0.7V, scanning are 40~60mV/s, are always scanned 80~120 times；The alkalinity of step (2) refers to the pH of mixed liquor
Value is 9~11.
2. the preparation method of urease biologic sensor according to claim 1, it is characterised in that：The electropolymerization of step (1)
A concentration of 0.1~3.5mol/L of hydrochloric acid in solution, a concentration of 0.1~3mol/L of aniline；The carbon ball and chloroplatinic acid of step (2)
Mass ratio be 1~3：1；The mass fraction of chitosan is 0.1~1% in chitosan-platinum/carbon ball mixed solution of step (3),
The mass fraction of platinum/carbon ball nanocomposite is 0.5~1.5%.
3. the preparation method of urease biologic sensor according to claim 1, it is characterised in that：The urase of step (3) is molten
The volume ratio of a concentration of 5~15mg/ml of liquid, chitosan-platinum/carbon ball mixed solution and urase solution is 1~5：1~5, drop coating amount
About 10~30 μ L/cm2。
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| CN108490041B (en) * | 2016-05-20 | 2019-02-19 | 江苏出入境检验检疫局工业产品检测中心 | A kind of urease biologic sensor |
| CN109880882B (en) * | 2019-03-29 | 2022-03-25 | 山东时进检测服务有限公司 | Method for detecting lead pollution in marine food |
| CN109880881B (en) * | 2019-03-29 | 2022-03-25 | 山东时进检测服务有限公司 | Method for detecting cadmium pollution in marine food |
| CN111020004B (en) * | 2019-12-28 | 2022-09-30 | 哈尔滨工业大学 | Preparation method of urea sensor with Janus structure artificial cell model |
| CN113484388B (en) * | 2021-06-30 | 2022-04-12 | 山东大学 | Method for screening helicobacter pylori urease inhibitor |
| CN114605046B (en) * | 2022-01-21 | 2023-06-16 | 西安建筑科技大学 | Chitosan reinforced enzyme induced carbonate precipitation curing agent and application method thereof |
| CN114965634A (en) * | 2022-04-14 | 2022-08-30 | 深圳可孚生物科技有限公司 | Preparation method of silk-screen bioelectrochemical sensor |
| CN115266865B (en) * | 2022-07-29 | 2024-04-16 | 北京大学 | Method for improving stability of electrochemical sensor |
| CN115825194A (en) * | 2022-09-01 | 2023-03-21 | 武汉工程大学 | A photoelectrochemical biosensor for detecting urease and its preparation method |
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| CN108490041A (en) | 2018-09-04 |
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