CN107500264A - The preparation method of a kind of smallfruit fig leaf based biomass porous carbon and its in protein（Enzyme）Applied in sensor - Google Patents
The preparation method of a kind of smallfruit fig leaf based biomass porous carbon and its in protein（Enzyme）Applied in sensor Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 32
- 239000002028 Biomass Substances 0.000 title claims abstract description 26
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 20
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 20
- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 19
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 32
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002608 ionic liquid Substances 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- 238000001548 drop coating Methods 0.000 claims abstract description 8
- 229920001661 Chitosan Polymers 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 102000001554 Hemoglobins Human genes 0.000 claims abstract description 4
- 108010054147 Hemoglobins Proteins 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000002484 cyclic voltammetry Methods 0.000 claims description 8
- 240000003537 Ficus benghalensis Species 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 241001237160 Kallima inachus Species 0.000 claims description 4
- 230000006399 behavior Effects 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000011160 research Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- INGWEZCOABYORO-UHFFFAOYSA-N 2-(furan-2-yl)-7-methyl-1h-1,8-naphthyridin-4-one Chemical compound N=1C2=NC(C)=CC=C2C(O)=CC=1C1=CC=CO1 INGWEZCOABYORO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000006392 deoxygenation reaction Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000008363 phosphate buffer Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 238000000840 electrochemical analysis Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract 1
- 229920003266 Leaf® Polymers 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000005518 electrochemistry Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- -1 1- hexyl pyridine hexafluorophosphates Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000012417 linear regression Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000003278 haem Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000004885 white matter Anatomy 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
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
Abstract
The invention discloses a kind of preparation method of smallfruit fig leaf based biomass porous carbon, and using smallfruit fig leaf as carbon source, smallfruit fig leaf based biomass porous carbon is made using high temperature cabonization technology；The present invention also disclosed it is a kind of with described smallfruit fig leaf based biomass porous carbon in protein（Enzyme）Application in sensor, by described biomass carbon and hemoglobin（Hb）Mixing is modified in ionic liquid carbon paste electrode（CILE）Surface, drop coating chitosan after drying（CTS）Sealer produces enzyme sensor（CTS/Hb porous carbons/CILE）, described enzyme sensor is to trichloroacetic acid（TCA）With good electro catalytic activity, TCA electrochemical analysis method is established.Biomass carbon of the present invention has the advantages that wide material sources, specific surface area is big, and cost is cheap, is expected to produce preferable economic benefit in terms of porous carbon materials preparation；Described enzyme sensor has the advantages that preparation method is simple, good to TCA electro-catalysis effect, has higher promotional value.
Description
Technical field
The present invention relates to a kind of protein electrochemistry sensor (CTS/Hb/ of the biomass porous carbon material modification of smallfruit fig leaf
Porous carbon/CILE) preparation method and electro-catalysis application, be related to porous carbon materials prepare and electrochemistry protein（Enzyme）Sensor
Field.
Background technology
Carbon material has the advantages that excellent heat resistance, high thermal conductivity coefficient, good chemical inertness, high conductivity, is
Important structural material and functional material.As the aggravation of fossil resource increasingly depleted and problem of environmental pollution, exploitation are renewable
Resource is simultaneously translated into the energy and had important practical significance with environment-friendly materials.Biomass is renewable resource, is carbon material
Important presoma, various carbon materials are prepared using biomass material, carbon material production cost can be reduced, realize carbon material
Sustainable development, meanwhile, biomass carbon material has good optics, electricity, catalysis and other physicochemical properties, photocatalysis,
The fields such as solar cell, electrochemical sensor, catalyst, super ionic material and lithium ion battery have widely should very much
With.Banyan is widely distributed for Hainan Region, and smallfruit fig leaf is cheap and easy to get, can be as the preferred source of biomass carbon material.
Hemoglobin (Hb) is to store oxygen in blood in animal body and transport the major protein of oxygen, iron present in its structure
Porphyrin can participate in the transmission oxygen in organism and transmit the key activities such as electronics, lived in life entity with oxygen molecule Reversible binding
Play the role of in dynamic important.The electrochemical biosensor built based on the Direct Electrochemistry theory of redox protein matter
Device, Physiological Function Mechanism, organism oxidation-reduction process thermodynamics and kineticses in research and probe life entity etc. has
Extremely important meaning.With the ionic liquid carbon paste electrode that graphite powder, hydrophobic adhesives and ionic liquid mix and prepare, tool
Have the advantages that high sensitivity, conductance are high, electrochemical window is wide, it is nontoxic easily make, cost is cheap, surface easily updates, therefore
It is widely used in electrochemical analysis.
The present invention obtains smallfruit fig leaf base porous carbon, ionic liquid carbon paste electrode using smallfruit fig leaf as carbon source using high temperature cabonization legal system
(CILE) it is basal electrode, using drop-coating in its area load smallfruit fig leaf base porous carbon materials and Hb mixed liquors, naturally dry
After be coated chitosan（CTS）Film forming, which is fixed, is made modified electrode (CTS/Hb- porous carbons/CILE), has solved related electrochemistry
Parameter, the modified electrode have good electrochemical catalysis activity to TCA, can be applied to TCA content analysis.
The content of the invention
The present invention relates to a kind of preparation method of smallfruit fig leaf based biomass porous carbon and its in protein（Enzyme）In sensor
Using, it is characterised in that smallfruit fig leaf based biomass porous carbon is made by carbon source of banyan dead leaf；By itself and redox protein matter
（Enzyme）Mix by a certain percentage, take a certain amount of mixed liquor to be coated on basal electrode surface, fixed with chitosan film forming, egg is made
White matter（Enzyme）Sensor, study its electrocatalysis to trichloroacetic acid.
The preparation method of the biomass porous carbon material comprises the following steps：
(1) take banyan dead leaf some, cleaning, drying, be placed in tube furnace, high-temperature calcination carbonization 1-5 is small under inert gas shielding
When and naturally cool to room temperature；
(2) smallfruit fig leaf after carbonization is placed in 1-6 mol/L hydrochloric acid and soaks 3-10 hours to remove impurity；
(3) the smallfruit fig leaf porous carbon after cleaning is placed in baking oven and dried, produce the biomass porous carbon material of smallfruit fig leaf.
Step（1）Described inert gas, including it is not limited to high pure nitrogen, argon gas etc.；
Step（1）The temperature control program of described high-temperature calcination is, with 2-5 DEG C/min programming rate to 300 DEG C, then with 8-
15 DEG C/min programming rate is warming up to 700-900 DEG C, and high temperature is kept for 1-5 hours, then is cooled to 300 with 8-15 DEG C/min
DEG C, rear natural cooling；
Step（3）Described in drying condition be, in 60-80 DEG C of baking oven keep 8-24 hours；
The protein of the smallfruit fig leaf based biomass porous carbon materials modification（Enzyme）The preparation of sensor comprises the following steps：
(1) prepare and contain 10 ~ 20 mg/mL hemoglobins（Hb）With the mixed liquor of 0.5 ~ 1.5 mg/mL porous carbon materials；
(2) the mixed solution drop coating described in 6 ~ 10 μ L steps (1) is taken in ionic liquid carbon paste electrode（CILE）Surface, room temperature
Naturally dry；
(3) 4 ~ 8 μ L chitosans are taken（CTS）Electrode surface of the solution drop coating described in step (2), after room temperature naturally dry,
Produce Electrochemical enzyme biosensor (CTS/Hb- porous carbons/CILE).
The preparation method of the ionic liquid carbon paste electrode is announced with reference to published patent of invention 2016102096493
Technology of preparing, mainly include the following steps that：
(1) mass ratio is weighed as 2:1 graphite powder and 1- hexyl pyridine hexafluorophosphates (HPPF6), it is placed in mortar and mixes simultaneously
Grinding is uniform；
(2) ground mixture is packed into a diameter of 4 mm vitreous electricity pole pipe, interpolation copper wire is as wire, electricity
Solid mixture compacting in pole pipe, produces CILE；
(3) electrode surface is polished smooth to minute surface before using.
A kind of protein based on smallfruit fig leaf based biomass porous carbon materials（Enzyme）Sensor (CTS/Hb- porous carbons/
CILE electro-catalysis application), it is characterised in that the quick analysis applied to trichloroacetic acid (TCA) detects, mainly including following step
Suddenly：
(1) using electrochemical workstation as laboratory apparatus, using CTS/Hb- porous carbons/CILE as working electrode, saturated calomel electrode
（SCE）For reference electrode, platinum electrode is to electrode, forms three-electrode system；
(2) three-electrode system is placed in the phosphate buffer solutions of pH 5.0 (PBS) through nitrogen deoxygenation；
(3) electrochemical behaviors of the cyclic voltammetry research TCA on modified electrode CTS/Hb- porous carbons/CILE is used, is scanned
Speed is 50-100 mV/s.
(4) relation between TCA electro-catalysis peak current and TCA concentration establishes TCA content analysis method.
The beneficial effects of the invention are as follows：
（1）The invention discloses a kind of preparation method using smallfruit fig leaf as the biomass porous carbon material of carbon source；This method has
Carbon source abundance, cost is cheap, and preparation method is simple, and gained porous carbon materials specific surface area is big, good conductivity, bio-compatible
Property the excellent specific property such as good.
（2）The present invention also also disclosed the protein using smallfruit fig leaf as the biomass porous carbon material of carbon source（Enzyme）Electrochemistry
The preparation method of sensor (CTS/Hb- porous carbons/CILE).The transducer production method is simple, test result indicates that modification
Electrode CTS/Hb/ porous carbons/CILE can be applied to the quick electro-catalysis detections of TCA, have catalytic activity high, stability is good, spirit
Sensitivity is high, it is simple to operate many advantages, such as.
Brief description of the drawings
Fig. 1 is the electronic scanner microscope figure of smallfruit fig leaf base porous carbon materials.
Fig. 2 is that different modifying electrode (a) CILE, (b) CTS/CILE, (c) CTS/Hb/CILE, (d) CTS/Hb/ are more
Hole carbon/CILE is respectively in 0.5 mol/L KCl and 1.0 mmol/L K3[Fe(CN)6] cyclic voltammetry curve in mixed solution,
Sweep speed is 100 mV/s.
Fig. 3 is that different modifying electrode (a) CILE, (b) CTS/CILE, (c) CTS/Hb/CILE, (d) CTS/Hb/ are more
Hole carbon/CILE cyclic voltammetry curves in the PBS cushioning liquid of 0.1 mol/L pH=5.0 respectively.
Fig. 4 A are cyclic voltammogram (curve a to ps of the modified electrode CTS/Hb/ porous carbons/CILE under different scanning speed
Respectively 30,50,80,100,150,200,250,300,350,400,450,500,550,600,650,700 mV/s)；Fig. 4 B
Be redox peak current to sweep speed relation curve；Fig. 4 C are relation curve of the redox spike potential to lnv.
Fig. 5 is cyclic voltammetry curve figure (curve as of the modified electrode CTS/Hb/ porous carbons/CILE under different TCA concentration
It is respectively 8.0,8.5,9.0,9.5,10.0,11.0,12.0,13.0,14.0,16.0,17.0,19.0,20.0,21.0 to o,
22.0 mmol/L TCA), embedded figure is the relation curve being catalyzed between reduction peak current and TCA concentration.
Embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
Limit the scope of the invention.
Embodiment 1
The preparation method of ionic liquid carbon paste electrode (CILE) is announced with reference to published patent of invention 2016102096493
Technology of preparing is made.Specially：Weigh 1.6 g graphite powders and 0.8 g ionic liquids HPPF6Mortar is put into mix and grind
It is even, the mixture of milled is inserted in the vitreous electricity pole pipe that internal diameter is 4 mm, insertion copper wire is as wire, by solid mixture pressure
It is real, produce ionic liquid carbon paste electrode (CILE), electrode surface is polished into smooth mirror surface during use.
Embodiment 2
The preparation of smallfruit fig leaf porous carbon materials：Long 4 ~ 6 cm are taken, wide 2 ~ 4 cm banyan dead leaves of uniform size, are placed in tube furnace
In, in a nitrogen atmosphere with 5 DEG C/min programming rate to 300 DEG C, then with 10 DEG C/min programming rate 900 DEG C are warming up to,
And high temperature is kept for 2 hours, then is cooled to 300 DEG C with 10 DEG C/min, after naturally cool to room temperature.It is placed in again in 3 mol/L hydrochloric acid
Soaking and washing is to remove impurity, drying smallfruit fig leaf porous carbon materials.
Embodiment 3
The preparation of CTS/Hb- porous carbons/CILE electrodes：Compound concentration is that 15.0 mg/mL Hb and 1.0 mg/mL smallfruit fig leafs are porous
Carbon material mixed solution, 8.0 μ L drop coatings chitosan solutions of 6 μ L of drop coating 5% again behind CILE surfaces, room temperature naturally dry are taken,
CTS/Hb- porous carbons/CILE modified electrodes are produced after room temperature naturally dry.
Embodiment 4
Fig. 2 show different modifying electrode in 0.5 mol/L KCl and 1.0 mmol/L K3[Fe(CN)6] in mixed solution
Cyclic voltammogram, CILE (curve a) have a pair of peak shapes it is good will definitely inverse redox peaks, (curve b) oxidations are also by CTS/CILE
Parent peak current decay, illustrate that electrode surface CTS hinders electron transmission, resistance increase.(curve c) oxidations are also by CTS/Hb/CILE
Parent peak electric current compared with CTS/CILE (curve b) reduce, this be due to protein hindered in electrode surface the potassium ferricyanide electrode it is anti-
Should.(curve d) redox peak currents significantly increase CTS/Hb- porous carbons/CILE, and this is due to smallfruit fig leaf porous carbon materials
In the presence of the specific surface area and electron transfer pathways that can be effectively increased electrode, electron transfer rate is improved, accelerates the potassium ferricyanide
Electrode reaction.
Embodiment 5
Fig. 3 show cyclic voltammogram of the different modifying electrode in the PBS cushioning liquid of pH 5.0, CILE (curve a) and CTS/
(curve b) redox character peak to CILE does not occur, illustrates that electroactive material is not present in electrode surface.In CTS/Hb/
(there are a pair of obvious redox peaks, illustrates certain electricity be present between electrode surface Hb and CILE in CILE on curve c)
Direct Electrochemistry reaction can occur for son transfer, Hb.In CTS/Hb- porous carbons/CILE, (redox peak current shows on curve d)
Increase is write, illustrates that smallfruit fig leaf porous carbon materials can not only provide larger specific surface area and good biocompatibility micro-loop
Border, and its high conductivity can accelerate electron transmission between prosthetic heme group Fe (III) in protein/Fe (II), have to Hb quickly
Current-responsive, show the characteristic electrochemical behavior of oxidation-reduction pair.
Embodiment 6
Fig. 4 show modified electrode CTS/Hb- porous carbons/CILE and sweeps the electrochemical behavior in fast scope in 30 ~ 700 mV/s.It is real
Test result to show, redox peak current is directly proportional to sweep speed, and equation of linear regression is respectively Ipc(µA)=142.90v
(V/s)+3.81 (n=16, r=0.994) and Ipa(μ A)=- 155.57v (V/s)+3.30 (n=16, r=0.995), shows at this
Electrode process is typical absorption and control process in the range of potential scanning speed.With sweep speed increase, spike potential difference by
It is cumulative big, redox spike potential EpEquation of linear regression with lnv is respectively Epc(V)=-0.04215lnv (V/s)-
0.3221 (n=16, r=0.966) and Epa(V)=0.03885lnv (V/s) -01177 (n=16, r=0.979).According to
Laviron is theoretical, deduces electron transfer number=1.27, electron transmission factor alpha=0.48, reaction rate constant ks=6.31 s-1.Knot
Fruit shows to have the smallfruit fig leaf porous carbon materials of satisfactory electrical conductivity to accelerate between modified electrode surface Hb Fe (III)/Fe (II)
Electronics shifts, and larger specific surface area provides good passage for electric charge transfer.
Embodiment 7
Using CHI 660D types electrochemical workstations as electro-chemical test instrument, using CTS/Hb- porous carbons/CILE as working electrode,
Saturated calomel electrode (SCE) is reference electrode, and platinum electrode is that electrode, the three-electrode system of composition are placed in containing various concentrations
The TCA PBS cushioning liquid of pH 5.0, after 30 min letting nitrogen in and deoxidizing, carry out electro-chemical test, electrochemical window scope for+
0.2V ~ -0.8V (vs. SCE), as a result as shown in figure 5, with the increase of TCA concentration, -0.519V occur one it is new also
Parent peak, and reduction peak current increases with the increase of TCA concentration, and oxidation peak then reduces directly with the increase of TCA concentration
To disappearance.When TCA concentration is in the range of 2.0 ~ 22.0 mmol/L, reduction peak current is with TCA concentration in good linear pass
System, equation of linear regression Ip(μ A)=0.636C (mmol/L)+2.488 (n=15, r=0.978), detection are limited to 0.67
Mmol/L, apparent K_m KM app=2.13 mmol/L, illustrate that modified electrode has good electro catalytic activity, banyan to TCA
Leaf porous carbon materials have good biocompatibility, and the electronics between electrode and Hb can be promoted to shift and strengthen to TCA
Electrocatalytic reaction.
Embodiment 8
Using standard addition method, modified electrode CTS/Hb- porous carbons/CILE is applied to the detection of medical TCA contents, takes 1.5
35% medical TCA of mL be added to the PBS cushioning liquid of pH=5.0 and constant volume to 10 mL as test fluid, as a result as shown in table 1.Survey
Test result shows, modified electrode CTS/Hb/ porous carbons/CILE is applied to TCA assays, the rate of recovery 93.00 ~ 105.40%,
As a result it is satisfied with.
Table35% medical TCA testing result (n=3)
Claims (4)
- A kind of 1. preparation method of smallfruit fig leaf based biomass porous carbon and its in protein（Enzyme）Applied in sensor, its feature exists In using banyan dead leaf as the obtained smallfruit fig leaf based biomass porous carbon of carbon source；By itself and redox protein matter（Enzyme）By a certain percentage Mixing, takes a certain amount of mixed liquor to be coated on basal electrode surface, is fixed with chitosan film forming, and protein is made（Enzyme）Sensing Device, study its electrocatalysis to trichloroacetic acid.
- 2. the preparation method of biomass porous carbon material comprises the following steps described in claims 1：(1) take banyan dead leaf some, cleaning, drying, be placed in tube furnace, high-temperature calcination carbonization 1-5 is small under inert gas shielding When and naturally cool to room temperature；(2) smallfruit fig leaf after carbonization is placed in 1-6 mol/L hydrochloric acid and soaks 3-10 hours to remove impurity；(3) the smallfruit fig leaf porous carbon after cleaning is placed in baking oven and dried, produce the biomass porous carbon material of smallfruit fig leaf.
- 3. step（1）Described inert gas, including it is not limited to high pure nitrogen, argon gas etc.；Step（1）The temperature control program of described high-temperature calcination is, with 2-5 DEG C/min programming rate to 300 DEG C, then with 8- 15 DEG C/min programming rate is warming up to 700-900 DEG C, and high temperature is kept for 1-5 hours, then is cooled to 300 with 8-15 DEG C/min DEG C, rear natural cooling；Step（3）Described in drying condition be, in 60-80 DEG C of baking oven keep 8-24 hours；The protein of the modification of smallfruit fig leaf based biomass porous carbon materials described in claims 1（Enzyme）The system of electrochemical sensor It is standby to comprise the following steps：(1) prepare and contain 10 ~ 20 mg/mL hemoglobins（Hb）With the mixed liquor of 0.5 ~ 1.5 mg/mL porous carbon materials；(2) the mixed solution drop coating described in 6 ~ 10 μ L steps (1) is taken in ionic liquid carbon paste electrode（CILE）Surface, room temperature Naturally dry；(3) 4 ~ 8 μ L chitosans are taken（CTS）Electrode surface of the solution drop coating described in step (2), after room temperature naturally dry, Produce enzyme sensor (CTS/Hb- porous carbons/CILE).
- A kind of 4. protein based on smallfruit fig leaf based biomass porous carbon materials（Enzyme）Electrochemical sensor (CTS/Hb- porous carbons/ CILE electro-catalysis application), it is characterised in that the quick analysis applied to trichloroacetic acid (TCA) detects, mainly including following step Suddenly：(1) using electrochemical workstation as laboratory apparatus, using CTS/Hb- porous carbons/CILE as working electrode, saturated calomel electrode （SCE）For reference electrode, platinum electrode is to electrode, forms three-electrode system；(2) three-electrode system is placed in the phosphate buffer solutions of pH 5.0 (PBS) through nitrogen deoxygenation；(3) electrochemical behaviors of the cyclic voltammetry research TCA on modified electrode CTS/Hb- porous carbons/CILE is used, is scanned Speed is 50-100 mV/s;(4) relation between TCA electro-catalysis peak current and TCA concentration establishes TCA content analysis method.
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