CN109342530A - The method of porphyrin sensitizer and multi-walled carbon nanotube nanocomposite preparation method and non-enzymatic electrochemical sensor detection ascorbic acid - Google Patents
The method of porphyrin sensitizer and multi-walled carbon nanotube nanocomposite preparation method and non-enzymatic electrochemical sensor detection ascorbic acid Download PDFInfo
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Abstract
The present invention discloses the preparation method and non-enzymatic electrochemical sensor of porphyrin sensitizer and multi-walled carbon nanotube nanocomposite, the preparation of functionalized multi-wall carbonnanotubes mixed liquor；The preparation of four n-octyl ammonium bromide mixed liquors；The preparation of porphyrin sensitizer mixed liquor；The preparation of porphyrin sensitizer and multi-walled carbon nanotube nanocomposite.Using ascorbic acid as test object, the sensor is had studied to the catalytic capability and electrochemical behavior of AA by cyclic voltammetry and chronoamperometry, TOAB/YD/MC/GCE composite modified non-enzyme sensor is to the catalysis of AA in the 3.3-1853.5 μM of range of linearity, high sensitivity is limited to 0.124 μM up to 19.16 μ A/mM, detection.Moreover, because the hydrophobicity of TOAB, sensor performance stabilization, reproducibility and selectivity are good, it is made to have biggish application potential in actual sample, food, clinical diagnosis and medicine and other fields.
Description
Technical field
The present invention relates to electrochemical sensor technology fields.Specifically porphyrin sensitizer and multi-walled carbon nanotube nanometer
The preparation method and non-enzymatic electrochemical sensor of composite material.
Background technique
Enzyme electrochemical sensor is a kind of biosensor, the sensitivity with higher of its electrochemical electrode and selection
Property, it can directly be measured in sample mixing.But enzyme sensor do not get rid of enzyme intrinsic unstable disadvantage, such as pH, temperature, wet
Degree and to the dependence of oxygen, to limit enzyme electrochemical sensor in the application range of every field, while also influencing to pass
The accuracy of service life and the result detection of sensor.Therefore, the research and application of non-enzymatic electrochemical sensor become a coke
The non-enzymatic electrochemical sensor of point, especially current mode.Carbon nanotube (carbon nanotubes, CNTs) is a kind of important
Inorganic nano-particle, including single-walled carbon nanotube (SWCNTs) and multi-walled carbon nanotube (MWCNTs).MWCNTs has biggish ratio
Surface area, rapidly mass transfer ability and excellent electron-transport function, it is with its unique structure, characteristic electron, mechanicalness
One of global research hotspot can be become with one time of chemical stability.But due to MWCNTs with huge molecular weight and very
Strong chemical inertness makes it difficult to other molecule stable and uniforms compound.We then pass through organic covalently chemical functionalized and have
The method of machine non-covalent chemical modification makes its structure change, and then generates some active functional groups.Porphyrin sensitization
Agent (YD2-o-C8 is abbreviated as YD) is a kind of substance being widely present in organism, because having special structure, is easily occurred aerobic
Change reduction reaction, complex reaction, ligand exchange reaction etc. shows it in the intracorporal catalysis reaction of simulation biology excellent
Catalytic performance, and then become hot spot in the research field for realizing simulation biocatalysis.
In order to improve the dynamic process of electron transmission, enhance the responsiveness of electrochemical sensor, it is many novel to receive
Rice material is widely used.MWCNTs is a kind of good novel electrode decorative material, has superior electronics and mechanical performance,
High thermal coefficient and special surface area.YD then chemical stability with higher and adjustable structure performance, in electricity
It has a wide range of applications in son conversion, but due to being limited by insoluble characteristic, YD is difficult to realize that electrochemistry is anti-in aqueous solution
It answers and is rarely applied to electrochemical sensor field.
The present invention cultivates project (91643113) in state natural sciences fund primary study plan, Fuyang municipal government-mound
Positive college of education's Horizontal Cooperation project (XDHX201701, XDHX201704), Anhui Province's Natural Science Fund In The Light
(1708085MB43), the outstanding youth talent's support plan key project (gxyqZD2016193) of Anhui Universities, Anhui Province are high
Under the supports of projects such as equal schools' quality engineering teaching research key project (2016jyxm0749), to porphyrin sensitizer and multi wall
Application of the carbon nanotube composite materials in non-enzymatic electrochemical sensor is studied.
Summary of the invention
For this purpose, technical problem to be solved by the present invention lies in provide a kind of porphyrin that can be used in ascorbic acid detection
Sensitizer detects ascorbic acid with multi-walled carbon nanotube nanocomposite preparation method and using non-enzymatic electrochemical sensor
Method.
In order to solve the above technical problems, the invention provides the following technical scheme:
The preparation method of porphyrin sensitizer and multi-walled carbon nanotube nanocomposite, includes the following steps:
(1) prepared by functionalized multi-wall carbonnanotubes MC mixed liquor: functionalized multi-wall carbonnanotubes MC is added to distilled water
In, ultrasound is until functionalized multi-wall carbonnanotubes MC is uniformly mixed with distilled water；
The preparation of (2) four n-octyl ammonium bromide TOAB mixed liquors: four n-octyl ammonium bromide TOAB are taken, are dissolved in toluene；
(3) prepared by porphyrin sensitizer YD mixed liquor: taking porphyrin sensitizer YD to be dissolved in toluene, and is stored in brown reagent
In bottle；
(4) step (1), step (2) and step the preparation of porphyrin sensitizer and multi-walled carbon nanotube nanocomposite: are taken
(3) functionalized multi-wall carbonnanotubes MC mixed liquor, four n-octyl ammonium bromide TOAB mixed liquors and the porphyrin sensitizer YD prepared is mixed
It closes liquid to be placed in centrifuge tube, ultrasonic disperse obtains porphyrin sensitizer and multi-walled carbon nanotube nanocomposite.
The preparation method of above-mentioned porphyrin sensitizer and multi-walled carbon nanotube nanocomposite, in step (4), carboxylated
Multi-walled carbon nanotube MC mixed liquor, four n-octyl ammonium bromide TOAB mixed liquors and porphyrin sensitizer YD mixed liquor, ultrasonic disperse
Time is 30min.
The preparation method of above-mentioned porphyrin sensitizer and multi-walled carbon nanotube nanocomposite, in step (4), after mixing
Functionalized multi-wall carbonnanotubes MC concentration be 0.54-5.4mg/mL；The concentration of four n-octyl ammonium bromide TOAB is after mixing
0.54-4.9mg/mL；The concentration of porphyrin sensitizer YD is 0.32-0.97mg/mL after mixing.
The preparation method of above-mentioned porphyrin sensitizer and multi-walled carbon nanotube nanocomposite, in step (4), after mixing
Functionalized multi-wall carbonnanotubes (MC) concentration be 0.54mg/mL；The concentration of mixed four n-octyls ammonium bromide TOAB is
2.7mg/mL；The concentration of mixed porphyrin sensitizer YD is 0.52mg/mL.
The method that non-enzymatic electrochemical sensor detects ascorbic acid, includes the following steps:
(2-1) prepares electrochemical sensor using above-mentioned porphyrin sensitizer and multi-walled carbon nanotube nanocomposite；
Electrochemical sensor prepared by step (2-1) is placed in electrolyte solution by (2-2), using cyclic voltammetry and
Chronoamperometry Ascorbic Acid AA is detected.
The method of above-mentioned enzyme electrochemical sensor detection ascorbic acid takes above-mentioned prepared porphyrin in step (2-1)
Sensitizer and 10 μ L of multi-walled carbon nanotube nanocomposite, modify treated glass-carbon electrode by the way of drop coating
It on GCE, dries at room temperature, obtains TOAB/YD/MC/GCE electrochemical sensor；The processing method of glass-carbon electrode GCE are as follows: use grain
Degree is 0.05 μm of polishing powder Al2O3 polishing glass-carbon electrode GCE, is cleaned until surface polishing is at mirror surface, then with ultrapure water；So
Afterwards by electrode successively in volume fraction be 50% aqueous solution of nitric acid, dehydrated alcohol, respective ultrasound 30 seconds in ultrapure water, then with largely
Ultrapure water；Finally, with electrode surface is dried with nitrogen, for use.
The method of above-mentioned non-enzymatic electrochemical sensor detection ascorbic acid, in step (2-2), the electrolyte solution is
PBS solution, HAC-AC buffer, sodium citrate solution, Tris-HCl or Klorvess Liquid it is one or more；The electrolyte
The pH value of solution is 4-9.03.
The method of above-mentioned non-enzymatic electrochemical sensor detection ascorbic acid, the electrolyte solution is PBS solution, and pH is
7.0, the concentration of PBS solution is 0.1mol/L.
The method of above-mentioned non-enzymatic electrochemical sensor detection ascorbic acid, in step (2-2), the cyclic voltammetry
Potential range is -1.3-1.0V, sweep speed 0.04V/s-0.30V/s；The chronoamperometry is using current potential
0.04V-0.60V。
The method of above-mentioned non-enzymatic electrochemical sensor detection ascorbic acid, the chronoamperometry are using current potential
0.40V。
Technical solution of the present invention achieves following beneficial technical effect:
The present invention cultivates project (91643113) in state natural sciences fund primary study plan, Fuyang municipal government-mound
Positive college of education's Horizontal Cooperation project (XDHX201701, XDHX201704), Anhui Province's Natural Science Fund In The Light
(1708085MB43), the outstanding youth talent's support plan key project (gxyqZD2016193) of Anhui Universities, Anhui Province are high
Under the supports of projects such as equal schools' quality engineering teaching research key project (2016jyxm0749), to porphyrin sensitizer and multi wall
Application of the carbon nanotube composite materials in non-enzymatic electrochemical sensor is studied；Utilize mediator among a kind of electronics
TOAB is composite modified on electrode, being built into a kind of novel electrochemical sensor by MWCNTs and YD, is desirably to obtain fax sense
For example biggish electrode specific surface area of the properties of device, excellent electrode conductivuty, biggish electron transport rate and electrode
Reactivity, and then preferably help us to non-enzymatic sensors Quality Research.
Using four n-octyl ammonium bromides (TOAB) by functionalized multi-wall carbonnanotubes (MWCNT-COOH is abbreviated as MC) and porphin
Quinoline sensitizer (YD2-o-C8 is abbreviated as YD) is compound and modifies in glassy carbon electrode surface, is prepared into a kind of non-enzymatic electrochemical sensing
Device (TOAB/YD/MC/GCE).With ascorbic acid (AA) for test object, had studied by cyclic voltammetry and chronoamperometry
The sensor specifies YD in the redox mechanism on modified electrode surface the catalytic capability and electrochemical behavior of AA, it was demonstrated that
The sensor Ascorbic Acid has good catalytic capability.TOAB/YD/MC/GCE composite modified non-enzyme sensor urges AA
Change in the 3.3-1853.5 μM of range of linearity, high sensitivity is limited to 0.124 μM up to 19.16 μ A/mM, detection.Moreover, because TOAB
Hydrophobicity, the sensor performance is stable, reproducibility and selectivity are good, makes it in actual sample, food, clinical diagnosis and medicine
Equal fields have biggish application potential.
Detailed description of the invention
Each modification rank of electrode prepared by Fig. 1 porphyrin sensitizer of the present invention and multi-walled carbon nanotube nanocomposite
Cyclic voltammetry curve of the glass-carbon electrode of section in 0.1M PBS solution；
The ultraviolet light of electrode prepared by Fig. 2 (A) porphyrin sensitizer of the present invention and multi-walled carbon nanotube nanocomposite
Spectrogram；
The fluorescence light of electrode prepared by Fig. 2 (B) porphyrin sensitizer of the present invention and multi-walled carbon nanotube nanocomposite
Spectrogram；
The infrared light of electrode prepared by Fig. 2 (C) porphyrin sensitizer of the present invention and multi-walled carbon nanotube nanocomposite
Spectrogram；
Fig. 3 (A) porphyrin sensitizer of the present invention is swept with multi-walled carbon nanotube nanocomposite electrochemical sensor in difference
The lower cyclic voltammogram of speed, (sweep it is fast from inside to outside successively 0.04,0.06,0.08,0.1,0.14,0.18,0.22,0.26,
0.30V/s)；
Fig. 3 (B) porphyrin sensitizer of the present invention is swept with multi-walled carbon nanotube nanocomposite electrochemical sensor in difference
Cyclic voltammogram under speed is peak current and the subduplicate relation curve (the first redox peaks) for sweeping speed；
Fig. 3 (C) porphyrin sensitizer of the present invention is swept with multi-walled carbon nanotube nanocomposite electrochemical sensor in difference
Cyclic voltammogram under speed is peak current and the subduplicate relation curve (the second redox peaks) for sweeping speed；
Fig. 4 (A) porphyrin sensitizer of the present invention is different from multi-walled carbon nanotube nanocomposite electrochemical sensor addition
The cyclic voltammogram of the TOAB of concentration；(a-4.9b-3.8c-2.7d-1.6e-0.54mg/mL)；
Fig. 4 (B) porphyrin sensitizer of the present invention is different from multi-walled carbon nanotube nanocomposite electrochemical sensor addition
The cyclic voltammogram of the YD of concentration；(a-0.97b-0.72c-0.52d-0.32mg/mL)；
Fig. 4 (C) porphyrin sensitizer of the present invention is different from multi-walled carbon nanotube nanocomposite electrochemical sensor addition
The cyclic voltammogram of the MC of concentration；(a-0.54b-1.6c-2.7d-3.8e-4.9f-5.4mg/mL)；
Cyclic voltammogram of Fig. 5 (A) TOAB/YD/MC/GCE electrochemical sensor of the present invention in different electrolyte solutions；
Cyclic voltammetric of Fig. 5 (B) TOAB/YD/MC/GCE electrochemical sensor of the present invention in the PBS buffer solution of different pH
Figure；
Fig. 6 TOAB/YD/MC/GCE electrochemical sensor of the present invention is continuously added to various concentration in 0.1M PBS solution
Ascorbic acid i-t curve；
It is anti-bad that concentration is added in TOAB/YD/MC/GCE electrochemical sensor Fig. 7 (A) of the invention in 0.1M PBS solution
The cyclic voltammetric response diagram (a-0.198mM, b-0.582mM, c-1.132mM, d-1.812mM) of hematic acid；
TOAB/YD/MC/GCE electrochemical sensor Fig. 7 (B) of the invention is continuously added to difference in 0.1M PBS solution
The i-t curve of the ascorbic acid of concentration and the calibration curve of ascorbic acid；
TOAB/YD/MC/GCE electrochemical sensor Fig. 8 (A) of the invention is continuously added to difference in 0.1M PBS solution
(current potential 0.40V sequentially adds 6.67 μM of AA, 20 μM of CaCl to Ampere currents-time graph of substance-measuring2、20μM
MgCl2、20μM NH4Cl、20μM NaNO2、6.67μM AA、20μM Na2CO3、20μM Na2SO4、20μM NaF、20μM
KBr、20μM KIO3、20μM Na2SO3,20μM NaNO3,6.67μM AA)；
TOAB/YD/MC/GCE electrochemical sensor Fig. 8 (B) of the invention is continuously added to difference in 0.1M PBS solution
Substance-measuring Ampere currents-time graph (current potential 0.40V, sequentially add 6.67 μM of AA, acetic acid, ethyl alcohol, glucose,
6.67 μM of AA, hydrogen peroxide, hydroxylamine hydrochloride, uric acid, dopamine, 6.67 μM of AA)；
TOAB/YD/MC/GCE electrochemical sensor Fig. 9 (A) of the invention detects in 0.1M PBS solution to Vitamin C
The i-t curve graph (current potential 0.40V, Single lead reproducibility) of acid catalyzed reproducibility；
TOAB/YD/MC/GCE electrochemical sensor Fig. 9 (B) of the invention detects in 0.1M PBS solution to Vitamin C
The i-t curve graph (current potential 0.40V, more electrode reproducibility) of acid catalyzed reproducibility；
TOAB/YD/MC/GCE electrochemical sensor Figure 10 (A) of the invention detects in 0.1M PBS solution to Vitamin C
The i-t curve graph of acid catalyzed operational stability；
TOAB/YD/MC/GCE electrochemical sensor Figure 10 (B) of the invention detects in 0.1M PBS solution to Vitamin C
The i-t curve graph of acid catalyzed storage stability；
TOAB/YD/MC/GCE electrochemical sensor Figure 11 (A) of the invention is under the current potential of 0.40V to 3.00mL 0.1M
(ascorbic additional amount is 38.19 μm of ol/ to the ampere curve of addition vitamin c solution and ascorbic acid solution in PBS solution
L, ascorbic acid additional amount are 66.23 μm of ol/L)；
TOAB/YD/MC/GCE electrochemical sensor Figure 11 (B) of the invention is under the current potential of 0.40V to 3.00mL 0.1M
(ascorbic additional amount is 43.44 μm of ol/ to the ampere curve of addition vitamin c solution and ascorbic acid solution in PBS solution
L, ascorbic acid additional amount are 66.23 μm of ol/L)；
TOAB/YD/MC/GCE electrochemical sensor Figure 11 (C) of the invention is under the current potential of 0.40V to 3.00mL 0.1M
(ascorbic additional amount is 39.49 μm of ol/ to the ampere curve of addition vitamin c solution and ascorbic acid solution in PBS solution
L, ascorbic acid additional amount are 66.23 μm of ol/L).
Specific embodiment
One, experimental section
1. the processing of glass-carbon electrode
Firstly, being 0.05 μm of polishing powder (Al with granularity2O3) polishing glass-carbon electrode (GCE), until surface polishing is at mirror surface
Only, then with a large amount of ultrapure waters it cleans.Then this electrode is successively respective in aqueous solution of nitric acid (1:1), dehydrated alcohol, ultrapure water
Ultrasound 30 seconds, then with a large amount of ultrapure waters.Finally, with electrode surface is dried with nitrogen, for use.
2. the preparation of solution and the preparation of modified electrode
(1) functionalized multi-wall carbonnanotubes (MC) mixed liquor prepare: weigh MC and be added in distilled water, ultrasound until MC with
Water is uniformly mixed, this is mixed liquor 1；
The preparation of (2) four n-octyl ammonium bromide (TOAB) mixed liquors: TOAB is separately taken, is made it dissolve in toluene, this is mixed
Close liquid 2；
(3) prepared by porphyrin sensitizer (YD) mixed liquor: taking YD, also makes it dissolve in toluene and be stored in brown reagent bottle
In, this is mixed liquor 3；
(4) preparation of porphyrin sensitizer and multi-walled carbon nanotube nanocomposite: above-mentioned mixed liquor 1,2,3 is extracted respectively
It is put into a 2.00mL centrifuge tube, then ultrasonic disperse 30min；
Such as: it weighs 0.0054g MC and is added in the distilled water of 2.00mL, until MC is uniformly mixed with water, this is ultrasound
Mixed liquor 1；0.0109g TOAB separately is taken, is made it dissolve in 1.00mL toluene, this is mixed liquor 2；0.004g YD is taken again,
It makes it dissolve in 1.00mL toluene and is stored in brown reagent bottle, this is mixed liquor 3.Above-mentioned mixed liquor 1,2,3 is extracted respectively
It is put into a 2.00mL centrifuge tube for 200.00mL, 100.00mL, 100.00mL, then ultrasonic disperse 30min.
(5) 10.00 μ L three's mixed solutions are taken, is modified by the way of drop coating on above-mentioned glass-carbon electrode, is dried in the air at room temperature
It is dry, obtain TOAB/YD/MC/GCE electrochemical sensor.
In step (4):
The concentration of mixed functionalized multi-wall carbonnanotubes MC be respectively 0.54mg/mL, 1.6mg/mL, 2.7mg/mL,
3.8mg/mL and 5.4mg/mL；
After mixing the concentration of four n-octyl ammonium bromide TOAB be respectively 0.54mg/mL, 1.6mg/mL, 2.7mg/mL,
3.8mg/mL and 4.9mg/mL；
The concentration of porphyrin sensitizer YD is respectively 0.32mg/mL, 0.52mg/mL, 0.72mg/mL and 0.97mg/ after mixing
mL。
Two, experimental result and discussion
Electrochemical Characterization on 1.TOAB/YD/MC/GCE modified electrode
As shown in Figure 1, the cyclic voltammetry curve of the electrochemical sensor for different modifying object, it may be seen that: TOAB/
YD/MC/GCE modified electrode and TOAB/YD/GCE compared to other three kinds composite modified (TOAB/GCE modified electrodes, TOAB/
MC/GCE modified electrode and TD/MC/GCE modified electrode) responsiveness for, redox reversible is preferable, Er Qiefeng
Electric current is larger.Pass through the comparison of the peak current of the Ith redox peaks and the IIth redox peaks in Fig. 1, TOAB/YD/MC/
The peak current of GCE sensor is compared with the big 3.5mA and 5.6mA of TOAB/YD/GCE difference.So as to obtain TOAB/YD/MC/GCE
It is more preferable therefore of the invention that most sensitive and redox reversible is responded in the peak current of the cyclic voltammetry curve of 0.1M PBS solution
Research is the electrochemical sensor based on the building of TOAB, YD and MC compound.
The spectral characterization of 2.MC, YD and MC/YD mixture
Certain spies in the ultra-violet absorption spectrum of the substance incident light that has substantially been exactly molecule and the Atomic absorption in substance
The long light energy of standing wave, correspondingly has occurred the result of molecular vibrational energy order transition and transition of electronic energy.Have in porphyrin more
The big pi bond system that a double bond and height are conjugated, has intensity absorption to visible light.π-π*Energy level is approximately located i 400nm-700nm pairs
The limit of visible spectrum answered, so that special uv-visible absorption spectra is formed, after MC is added into YD in Fig. 2 (A), wave
It is long to be moved to 203nm from 206nm, blue-shifted phenomenon is generated, this is because YD and MC is formd again by pi-pi accumulation or hydrogen bond action
Close object；Porphyrin compound has preferable fluorescence property, and electron donating group can increase fluorescence intensity on the phenyl ring of porphyrin, such as schemes
2 (B), fluorescence intensity reduces after MC is added in porphyrin monomer as seen from the figure, also demonstrates YD and MC and forms compound；Infrared spectroscopy
Also belong to absorption spectrum, be caused due to the electromagnetic wave of the group absorptions specific wavelength in compound molecule it is intramolecular certain
Vibration, spectrogram obtained from the variation with the corresponding absorbance of instrument record.It can see from Fig. 2 (C), 3434cm-1-
3445cm-1It is since there are the frequency spectrums of the stretching vibration of O-H base, MC/YD system to be shown in 2919cm-1Absorption peak be by
The extension vibration of C-H base, 1565cm in YD-1And 1165cm-1The absorption peak of left and right display be the extension of C-O-C base in YD with
And C=O base, the stretching action of C=C base, YD is equally also demonstrated well and MC is combined into a kind of stable compound.
The electrochemical measurement of 3.TOAB/YD/MC/GCE sensor
As shown in Fig. 3 (A) to Fig. 3 (C), the glass-carbon electrode of TOAB/YD/MC modification sweeps the cyclic voltammetric under speed in difference
Behavior.Such as Fig. 3 (A), potential range setting is in -1.3~1.0V, when sweep speed is increased to by 0.04V/s the process of 0.30V/s
In, each oxidation peak and reduction spike potential are held essentially constant, and peak current is gradually increased.It is demonstrated experimentally that in the case where difference sweeps speed, if
Peak current is directly proportional to sweep speed, then illustrates the electrode reaction carried out on modified electrode for the control of surface reaction process；If
Peak current is directly proportional to the square root for sweeping speed, then illustrates the electrode reaction carried out on modified electrode for diffusion process control.Pass through
Fig. 3 (A) obtains Fig. 3 (B) and Fig. 3 (C), it can be seen that reduction peak current and oxidation peak current under different scanning rates, with
The square root of speed is swept in good linear relationship (related coefficient RB=0.9980, RB=0.9987), illustrates TOAB/YD/MC
It is diffusion process that three, which mixes the electrode reaction carried out on modified electrode,.
4. the optimization of experiment condition
The optimization of the amount of 4.1 modifiers
The amount of decorative material has a degree of influence to its appearance on sensor, right respectively by cyclic voltammetry here
The not same amount of tri- kinds of modifier modifications of TOAB, YD, MC on the electrode is measured.Fig. 4 (A) shows to be added dropwise in electrode surface
The dosage of TOAB suspension, when as can be seen from the figure TOAB concentration changes to c from a, the peak current of redox peaks gradually increases
Big and redox reversible turns for the better；When concentration changes to e from c, although peak current is increasing obvious it can be seen that aoxidizing
It restores invertibity to be deteriorated, so that we show that when TOAB concentration is 2.7mg/mL after step (4) mixing be optium concentration.Fig. 4
(B) for the different amounts of the suspension YD of cyclic voltammetry CV curve when, Fig. 4 (C) is the quantization figure of MC, passes through class
With above-mentioned analysis, it can be deduced that effect is best when YD concentration is 0.52mg/mL after step (4) mixing, after step (4) mixing
It is 0.54mg/mL that MC, which chooses its optimal amount,.
The selection of 4.2 electrolyte solutions
Different electrolyte solutions, its different pH values of same electrolyte solution have very big shadow to the peak current and current potential of electrode
It rings.Electricity of the present invention to electrode in PBS solution, HAC-AC buffer, sodium citrate solution, Tris-HCl, Klorvess Liquid
Chemical response is studied, such as Fig. 5 (A), the results showed that electrochemistry of the electrode in PBS solution is most sensitive, also most stable.
Influence of the PBS solution that Fig. 5 (B) is different pH to the electrochemical response of electrode, the results showed that electrochemistry is rung in pH=7.00
It should be most strong.Therefore electrolyte solution of the PBS buffer solution of this experimental selection pH=7.00 as follow-up study.
The optimization of 4.3 application current potentials
The ampere curve determination of TOAB/YD/MC/GCE sensor Ascorbic Acid catalysis, using the selection of current potential to it
Catalytic response has a great impact.The sensor is placed in 0.1M PBS solution, and is continuously added to 10.00 μ L concentration to it and is
The ascorbic acid of 30mM obtains following ampere curve graph 6 (changing it using current potential, other conditions are consistent).When application current potential from
When 0.04V increases to 0.40V, the catalytic response degree of the electrode system Ascorbic Acid is gradually increased；Current potential continues to increase to
When 0.60V, hence it is evident that it can be seen that catalytic response is unstable, and then obtain its catalytic response effect when application current potential is 0.40V
It is most obvious and very stable, therefore we select 0.40V to apply current potential as follow-up study.
Three, the electro-catalysis experiment of sensor Ascorbic Acid
As shown in Fig. 7 (A), TOAB/YD/MC/GCE sensor is continuously added to the anti-of various concentration in 0.1M PBS solution
Bad hematic acid, from the figure we can see that the peak current of the reduction peak at peak I reduces, and the peak current of oxidation peak is being gradually increased,
Illustrate that the sensor Ascorbic Acid has oxidation catalytic action.Connect as Fig. 7 (B) show the sensor in 0.1M PBS solution
The calibration curve that the ampere curve of the continuous ascorbic acid that various concentration is added and the sensor thus made are catalyzed AA, from
It can be seen that electric current linearly increases with the increase of AA concentration in figure, in 3.3 μM of -1853.5 μM of ranges of linearity, sensitivity
Up to 19.1615 μ A/mM, detection are limited to 1.24 × 10-4MM better illustrates the sensor and shows well to the catalysis of AA
Response.
Four, the performance measurement of sensor
The selectivity of 1.TOAB/YD/MC/GCE modified electrode Ascorbic Acid catalysis
TOAB/YD/MC/GCE sensor has selectivity to the catalysis of different material, to the electrolytic cell of 0.1M PBS solution
In sequentially add different material and carry out ampere curve determination, the addition for observing which substance will appear current-responsive.Such as Fig. 8 institute
Show, when 6.67 μM of AA is added thereto, more sensitive response occurs in sensor, as addition Mg2+、Ca2+、NH4 +、CO32-、
NO2 -、F-、Br-、IO3 -、SO3 2-、NO3 -、SO4 2-, acetic acid, ethyl alcohol, glucose, hydrogen peroxide, hydroxylamine hydrochloride, uric acid, dopamine object
Matter without being catalyzed and not generating interference to the response of AA, has further related to TOAB/YD/MC/GCE sensor Ascorbic Acid
Selective catalytic action.
The reproducibility of 2.TOAB/YD/MC/GCE modified electrode Ascorbic Acid catalysis
It is 3.31mM/mL's that concentration is added in the electrode system that 3.00mL0.1M PBS is modified to TOAB/YD/MC solution
Ascorbic acid is detected, and is exchanged the step of PBS solution repeats just for after having reacted and is detected parallel 4 times, reaction result
As shown in Fig. 9 (A), ascorbic acid 4 times i-t curves are slightly fluctuated as we know from the figure, but show urging for Ascorbic Acid
Change effect, by calculating, relative error is -4.7%, illustrates the reproducibility of TOAB/YD/GCE modified electrode Ascorbic Acid
Preferably；Fig. 9 (B) is the reproducibility lab diagram of more electrodes, and calculating its relative error by experimental result is -3.8%, equally
The reproducibility for illustrating that the sensor is catalyzed AA is preferable.
The stability of 3.TOAB/YD/MC/GCE modified electrode Ascorbic Acid catalysis
Shown in following Figure 10 (A), in 0.1M PBS solution, the survey of ampere curve is carried out to TOAB/YD/MC/GCE sensor
It is fixed, it is firstly added the 20.00 μ L of ascorbic acid of 10mM, sensor has more sensitive response to it.As the sensor continuously makes
After 1h, the ascorbic acid of equivalent is added, sensor, which still has, to be obvious responsed to, and reproducibility is preferable.It can be seen that TOAB/
The catalysis of YD/MC/GCE sensor Ascorbic Acid has good operational stability.As shown in the following figure (B), TOAB/YD/MC/
GCE sensor carries out ampere curve determination in PBS solution, and the 10.00 μ L of ascorbic acid of 30mM is added in when 100s, and sensor goes out
Now obvious response to.The electrode washing is clean, the measurement of the above ampere curve is repeated after placing 20 days, by Figure 10 (A) and Figure 10
(B) as can be seen that the sensor Ascorbic Acid has always obvious catalytic response, and relative average debiation is obtained by calculation and is
2.8%, illustrate that the sensor has good storage stability.
Five, the detection of actual sample
Take 3 medical VITAMIN C TABLETs, after grinding uniformly its quality is referred to as 0.2914g, be dissolved in 4.00mL ultrapure water
In, it is centrifuged after 15min with 7500r/min and takes 1.00mL supernatant that 4.00mL ultrapure water is added to dilute.Vitamin C after taking dilution is molten
Liquid 0.50mL adds 1.50mL ultrapure water to continue to dilute, and acquired solution is with spare.Successively add into the PBS solution of 3.00mL0.1M
Vitamin c solution after entering the 10.00 above-mentioned dilutions of μ L, 10.00 μ L 20mM ascorbic acid solutions, obtains Figure 11 (A)-Figure 11 (C)
(measuring three times in parallel).It is measured using chronoamperometry, the variation of record current value utilizes linear relationship equation calculation
Its additional amount calculates the rate of recovery of ascorbic acid accordingly, and the results are shown in Table 1.The rate of recovery of the method measurement ascorbic acid exists
Between 95%~105%, it is well demonstrated that TOAB/YD/MC/GCE modified electrode can be used for ascorbic acid in actual sample
Measurement.
The determination of recovery rates of 1 ascorbic acid of table
The present invention cultivates project (91643113) in state natural sciences fund primary study plan, Fuyang municipal government-mound
Positive college of education's Horizontal Cooperation project (XDHX201701, XDHX201704), Anhui Province's Natural Science Fund In The Light
(1708085MB43), the outstanding youth talent's support plan key project (gxyqZD2016193) of Anhui Universities, Anhui Province are high
Under the supports of projects such as equal schools' quality engineering teaching research key project (2016jyxm0749), to porphyrin sensitizer and multi wall
Application of the carbon nanotube composite materials in non-enzymatic electrochemical sensor is studied；Prepared TOAB/YD/MC/
GCE sensor can be used for the detection of ascorbic acid AA, and detection range is wide, high sensitivity, and the sensor performance is stable, reproducibility
It is good with selectivity, make it that there is biggish application potential in actual sample, food, clinical diagnosis and medicine and other fields.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes among still in present patent application scope of protection of the claims.
Claims (10)
1. the preparation method of porphyrin sensitizer and multi-walled carbon nanotube nanocomposite, which comprises the steps of:
(1) prepared by functionalized multi-wall carbonnanotubes MC mixed liquor: functionalized multi-wall carbonnanotubes MC being added in distilled water, is surpassed
Sound is until functionalized multi-wall carbonnanotubes MC is uniformly mixed with distilled water；
The preparation of (2) four n-octyl ammonium bromide TOAB mixed liquors: four n-octyl ammonium bromide TOAB are taken, are dissolved in toluene；
(3) prepared by porphyrin sensitizer YD mixed liquor: taking porphyrin sensitizer YD to be dissolved in toluene, and is stored in brown reagent bottle
In；
(4) step (1), step (2) and step (3) preparation of porphyrin sensitizer and multi-walled carbon nanotube nanocomposite: are taken
The functionalized multi-wall carbonnanotubes MC mixed liquor of preparation, four n-octyl ammonium bromide TOAB mixed liquors and porphyrin sensitizer YD mixed liquor
It is placed in centrifuge tube, ultrasonic disperse, obtains porphyrin sensitizer and multi-walled carbon nanotube nanocomposite.
2. the preparation method of porphyrin sensitizer and multi-walled carbon nanotube nanocomposite according to claim 1, special
Sign is, in step (4), functionalized multi-wall carbonnanotubes MC mixed liquor, four n-octyl ammonium bromide TOAB mixed liquors and porphyrin
Sensitizer YD mixed liquor, the time of ultrasonic disperse are 30min.
3. the preparation method of porphyrin sensitizer and multi-walled carbon nanotube nanocomposite according to claim 2, special
Sign is, in step (4), the concentration of mixed functionalized multi-wall carbonnanotubes MC is 0.54-5.4mg/mL；Four after mixing
The concentration of n-octyl ammonium bromide TOAB is 0.54-4.9mg/mL；The concentration of porphyrin sensitizer YD is 0.32-0.97mg/ after mixing
mL。
4. the preparation method of porphyrin sensitizer and multi-walled carbon nanotube nanocomposite according to claim 3, special
Sign is, in step (4), the concentration of mixed functionalized multi-wall carbonnanotubes (MC) is 0.54mg/mL；Mixed four
The concentration of n-octyl ammonium bromide TOAB is 2.7mg/mL；The concentration of mixed porphyrin sensitizer YD is 0.52mg/mL.
5. the method for non-enzymatic electrochemical sensor detection ascorbic acid, which comprises the steps of:
(2-1) is using any porphyrin sensitizer of claim 1-4 and multi-walled carbon nanotube nanocomposite preparation electricity
Chemical sensor；
Electrochemical sensor prepared by step (2-1) is placed in electrolyte solution by (2-2), using cyclic voltammetry and timing
Current method Ascorbic Acid AA is detected.
6. the method for non-enzymatic electrochemical sensor detection ascorbic acid according to claim 5, which is characterized in that in step
In (2-1), claim 1-4 any prepared porphyrin sensitizer and 10 μ L of multi-walled carbon nanotube nanocomposite are taken, is adopted
It is modified on treated glass-carbon electrode GCE with the mode of drop coating, is dried at room temperature, obtain TOAB/YD/MC/GCE electrochemistry
Sensor；The processing method of glass-carbon electrode GCE are as follows: using granularity is 0.05 μm of polishing powder Al2O3Polish glass-carbon electrode GCE, until table
Until face is polished to mirror surface, then cleaned with ultrapure water；Then by electrode successively in volume fraction be 50% aqueous solution of nitric acid, anhydrous
Respective ultrasound 30 seconds in ethyl alcohol, ultrapure water, then with a large amount of ultrapure waters；Finally, with electrode surface is dried with nitrogen, for use.
7. the method for non-enzymatic electrochemical sensor detection ascorbic acid according to claim 5, which is characterized in that in step
In (2-2), the electrolyte solution is that PBS solution, HAC-AC buffer, sodium citrate solution, Tris-HCl or potassium chloride are molten
Liquid it is one or more；The pH value of the electrolyte solution is 4-9.03.
8. the method for non-enzymatic electrochemical sensor detection ascorbic acid according to claim 7, which is characterized in that the electricity
Electrolyte solution is PBS solution, and pH 7.0, the concentration of PBS solution is 0.1mol/L.
9. the method for non-enzymatic electrochemical sensor detection ascorbic acid according to claim 5, which is characterized in that in step
In (2-2), the potential range of the cyclic voltammetry is -1.3-1.0V, sweep speed 0.04V/s-0.30V/s；The meter
When current method application current potential be 0.04V-0.60V.
10. the method for non-enzymatic electrochemical sensor detection ascorbic acid according to claim 9, which is characterized in that described
The application current potential of chronoamperometry is 0.40V.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111141802A (en) * | 2019-12-31 | 2020-05-12 | 中国水产科学研究院 | Nano material and preparation method and application thereof |
| CN112978787A (en) * | 2021-03-22 | 2021-06-18 | 上海健康医学院 | Tin sulfide carbon nanotube composite material for electrochemical sensor and preparation method thereof |
| CN114636741A (en) * | 2022-03-18 | 2022-06-17 | 南通大学 | MXene-SWCNTs nanocomposite modified GCE electrode |
| CN114839244A (en) * | 2022-05-05 | 2022-08-02 | 济南大学 | Hydrogen peroxide electrochemical sensor based on covalent organic framework-multi-walled carbon nanotube |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980078A (en) * | 2014-05-08 | 2014-08-13 | 中山大学 | Method for preparing lactone through catalyzing oxidation of ketone compound, and its special catalyst |
| CN105348291A (en) * | 2015-09-25 | 2016-02-24 | 江苏大学 | Tin-porphyrin axial covalent functionalization multiwalled-carbon-nanotube nonlinear optical material and preparing method thereof |
| CN107167502A (en) * | 2017-05-22 | 2017-09-15 | 阜阳师范学院 | The construction method of non-enzymatic electrochemical sensor based on CNT fullerene complex and application |
| CN108508068A (en) * | 2018-03-27 | 2018-09-07 | 长沙理工大学 | Method and the application of HER2 gene particular sequences are detected based on anion porphyrin-carbon nano tube modified electrode |
-
2018
- 2018-10-12 CN CN201811187570.0A patent/CN109342530A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980078A (en) * | 2014-05-08 | 2014-08-13 | 中山大学 | Method for preparing lactone through catalyzing oxidation of ketone compound, and its special catalyst |
| CN105348291A (en) * | 2015-09-25 | 2016-02-24 | 江苏大学 | Tin-porphyrin axial covalent functionalization multiwalled-carbon-nanotube nonlinear optical material and preparing method thereof |
| CN107167502A (en) * | 2017-05-22 | 2017-09-15 | 阜阳师范学院 | The construction method of non-enzymatic electrochemical sensor based on CNT fullerene complex and application |
| CN108508068A (en) * | 2018-03-27 | 2018-09-07 | 长沙理工大学 | Method and the application of HER2 gene particular sequences are detected based on anion porphyrin-carbon nano tube modified electrode |
Non-Patent Citations (4)
| Title |
|---|
| HAI WU等: "A nanohybrid based on porphyrin dye functionalized graphene oxide for the application in non-enzymatic electrochemical sensor", 《ELECTROCHIMICA ACTA》 * |
| HAI WU等: "Synergistic-Effect-Controlled Tetraoctylammonium Bromide/Multi-Walled Carbon Nanotube@Hemin Hybrid Material for Construction of Electrochemical Sensor", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
| JIE ZHU等: "Preparation of non-covalent Metalloporphyrin/C60 Composite and its Electrocatalysis to Hydrogen Peroxide", 《ELECTROANALYSIS》 * |
| 高云飞等: "自组装模拟酶研究进展", 《广州化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111141802A (en) * | 2019-12-31 | 2020-05-12 | 中国水产科学研究院 | Nano material and preparation method and application thereof |
| CN112978787A (en) * | 2021-03-22 | 2021-06-18 | 上海健康医学院 | Tin sulfide carbon nanotube composite material for electrochemical sensor and preparation method thereof |
| CN114636741A (en) * | 2022-03-18 | 2022-06-17 | 南通大学 | MXene-SWCNTs nanocomposite modified GCE electrode |
| CN114839244A (en) * | 2022-05-05 | 2022-08-02 | 济南大学 | Hydrogen peroxide electrochemical sensor based on covalent organic framework-multi-walled carbon nanotube |
| CN114839244B (en) * | 2022-05-05 | 2023-09-15 | 济南大学 | Hydrogen peroxide electrochemical sensor based on covalent organic skeleton-multiwall carbon nano tube |
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