Vitamin B detection method based on potentiostat application platform
Technical field
The invention belongs to technical field of electrochemical detection, are related to a kind of vitamin B inspection based on potentiostat application platform
Survey method has merged electrochemical measuring technique and embedded system portable design method based on three-electrode system, for side
Just, the case where quickly, accurately detecting trace element (especially vitamin B) content in food, and it is strong from design function, it can be with
Other detection system use in conjunction.
Background technique
Vitamin B (VB) is biological oxidation coenzyme important in cell, is that body maintains its normal life institute required
A kind of nutrient.In addition for food vitamins B, especially infant and breast milk food, it is necessary to stringent by detecting
Its additive amount is controlled, so it is very necessary to find a kind of simple, efficient, quick detection method.The analysis method master of vitamin B
There are fluorescence analysis, high efficiency liquid phase chromatographic analysis method, ultraviolet spectrophotometry and electrochemical methods etc..And electrochemical analysis
Method is a kind of analysis method set up according to electrochemical principle and substance electrochemical properties in the solution and its variation,
Be usually taken and fix potential polarization under suitable current potential or carry out electric potential scanning in a wider range, have it is easy to operate, point
The advantages that speed is fast, accuracy is high is analysed, it can be achieved that continuous analysis and field assay, are more and more applied.
In terms of substance qualitative and quantitative analysis, Conventional electrochemical test, electrochemical reaction mechanism, three electrode tests
System suffers from extensive use.However because it is expensive, volume is big, and to cooperate upper computer software just to can be used, make
It is restricted in terms of popularization and application, it more difficult to be applied in portable detection equipment.Potentiostat is various three electrodes
The interface of formula (including working electrode, auxiliary electrode and reference electrode) electrochemical sensor, it is mainly that external drive signal is intimate
It is accurately applied on sensor, electrochemical reaction occurs for driving sample solution, and does to the response signal of generation corresponding pre-
Processing (signal conversion, amplification, filtering).Early stage, potentiostat was mainly by a large amount of since semiconductor integration technology falls behind relatively
The deficiencies of discrete component is constituted, and there are bulky, structure is complicated, permanent potential control difference, limits its scope of application.
It is heavy and be not easy currently, the domestic potentiostat for laboratory electrochemical property test is since its volume is larger
It carries, is not suitable for Practical Project field application.And the potentiostat measurement accuracy of existing practical engineering application is low, control error compared with
Greatly, inconvenient, intelligence degree is lower, is unable to satisfy field electrochemical testing requirement.Also, micro dimension in existing food
Raw element detection technique, there are detection method complexity, detection time is longer, testing cost is higher, is not easy the disadvantages of promoting, Yi Jijian
Device is surveyed using single, is not able to satisfy the actual demands such as food safety.Therefore, it is necessary to design a kind of based on vitamin B detection
Portable potentiostat application platform, efficient quick detection for mcg vitamin B in food and expansible impedance are surveyed
It tries platform and carries out use in conjunction.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of vitamins based on potentiostat application platform
B detection method, it can be used for the detection of mcg vitamin B in food, and can parameters be carried out with long-distance monitor and control and will be examined
Survey signal is sent to remote server and later period and can fit with Platform Alliances application, power supplys such as electrochemical impedance test macros
Orchestration is detachable with apparatus main body, and external three electrode detections platform can be connected with host computer, appearance hommization, portable design,
Have the characteristics that it is small in size, easy to carry, detection quick and precisely, easy to operate, use in conjunction.
To achieve the above object, the technical scheme adopted by the invention is that:
The potentiostat application platform that the present invention uses, by housing unit, RS485 transmission module, external equipment connecting line,
And power module, micro controller module, D/A conversion module, amplifier detection module, A/D conversion in housing unit are set
Module, relay group module, key display module and GPRS wireless communication module composition.The power module connects microcontroller
The power input of device module;The digital quantity of micro controller module is converted into analog quantity and is transmitted to amplifier detection by D/A conversion module
Module;Sampled data in amplifier detection module is converted into digital quantity by analog quantity and is transmitted to microcontroller mould by A/D conversion module
Block is handled;The transformation of pc port low and high level is attracted in micro controller module to control relay group module, to control
The connection status of working electrode in amplifier detection module;Key display module by the parameter of setting be sent to micro controller module into
Row is handled and will be shown from micro controller module received signal and data;RS485 transmission module and micro controller module
Connection, and the signal that will test is transmitted to GPRS wireless communication module.
The housing unit include shell, display screen, front ventilation opening, electromotion pilot lamp, function select button, up and down
Select button, printing-type electrode detection chip card slot, USB interface, external application interface, power switch, power interface, the back side are logical
Air port, signal translation interface and three electrode interfaces.
Display screen, front ventilation opening, electromotion pilot lamp, function select button and the upper select button is arranged at
Outer casing top surface;Plane is at 135 ° where plane where display screen and function select button;Display screen connects internal key and shows mould
Block simultaneously carries out transmission control by micro controller module, can show voltage value, current value and the detection time of setting and detection;Front
Ventilation opening is made of wire netting;Electromotion pilot lamp is connected with the power supply module, and when energization lights;Function select button connects key
Display module, and the information of setting is transferred to micro controller module and is controlled, including voltage, electric current, sweep speed and sensitivity
Four setting buttons;Upper select button is connected with key display module, and the voltage of adjustment function selection knob, is swept electric current
The ascending, descending of speed or sensitivity number.
Printing-type electrode detection chip card slot, USB interface and the external application interface is arranged at shell side;
USB interface and external application interface are all connected with micro controller module;Printing-type electrode detection chip card slot is equipped with two and assigns slot
For assigning printing-type electrode detection chip;Printing-type electrode detection chip card slot connects amplifier detection module.
Power switch, power interface, back side ventilation opening, signal translation interface and three electrode interfaces are arranged at outer
Behind shell;Power interface connects power module, and through power supply adaptor input direct-current voltage;Power switch connect power interface with
Power module controls electric power starting and closing;Back side ventilation opening is made of wire netting;Signal translation interface connects RS485 transmission
Module;Three electrode interfaces are connected with amplifier detection module.
Power supply adaptor, USB connecting line, RS485 patchcord, three electrode connecting lines and the external application connecting line structure
At external equipment connecting line.
The micro controller module uses ATmega16 chip, is connect, is passed through with relay group module by I/O mouthfuls
SPI communication interface is connected with D/A conversion module and A/D conversion module.
The D/A conversion module uses DAC8831 chip.
The A/D conversion module uses AD7705 chip.
This method is specific as follows:
1, electrochemical property test early period
1.1 3 electrode interfaces access electrode, and three interelectrode relationships are equivalent to impedance model, in impedance model, electricity
Hinder RFWWith capacitor CFWAfter parallel connection with resistance RSSeries connection;It is tested for the property using the impedance model, sets resistance RSFor 1K Ω, electricity
Hold CFWFor 50 μ F, resistance RFWResistance value be respectively set as 1,10,30,5,100,200K Ω, concurrently set resistance RFWBoth ends
Different voltages value is respectively 0.100,0.500,1.000,2.000,3.300V, tests the output electricity of the potentiostat application platform
Situation is pressed, so that verifying output voltage follows resistance RFWThe setting voltage change at both ends;
1.2 test the output current conditions of the potentiostat application platform using impedance model;First set resistance RFWElectricity
Resistance value is 1K Ω, changes capacitor CFWCapacitance be respectively 50 μ F, 100 μ F, 150 μ F, set resistance RFWThe different voltages at both ends
Value is respectively 0.1,0.5,1.0,2.0,3.3V, measures the output current value of the potentiostat application platform;Reset capacitor CFW
Capacitance be 100 μ F, change resistance RFWResistance value be respectively 0.5K Ω, 1K Ω, 1.5K Ω, it is same to set resistance RFWTwo
The different voltages value at end is respectively 0.1,0.5,1.0,2.0,3.3V, measures the output current value of the potentiostat application platform,
To which resistance R is worked as in verifyingFWResistance value it is fixed when, the change of capacitor influences less output electric current, defeated when capacitance is fixed
Electric current is linearly reduced with the increase of resistance value out;
2, later period application experiment is tested
2.1 use cyclic voltammetry, in [the Fe (CN) of various concentration6]3-/4-In solution, it is flat to carry out potentiostat application
The measurement of comparison of platform and CHI660C work station is tested: 1) having configured [Fe (CN) of 100mM/L6]3-/4-Solution, with PBS solution point
Be not diluted to concentration be 50mM/L, 25mM/L, 12.5mM/L, 6.75mM/L buffer, 2) carry out cyclic voltammetry test, just
Beginning current potential -0.2V, settling time 2S, electrode sweep speed be respectively 10mV/S, 25mV/S, 50mV/S, 100mV/S, 3) record compare
Redox two peak point currents ip1 and ip2, to verify the buffer of same concentrations, current value with the increase for sweeping speed and
Linearly increasing, identical to sweep under speed, current value is linearly reduced with the reduction of buffer concentration;
2.2 couples of food vitamins content B carry out test experiences, use pH for 4.0 0.1mol/L phthalic acid
Hydrogen potassium buffer is tested on bare electrode and modified electrode as electrolyte, sweep speed 0.1V/s, measures circulation volt
Pacify curve graph, to solve vitamin B content in electrolyte;
Potentiostat application platform and impedance test system use in conjunction, to life of the biomembrane under different vitamine concentrations
The long detection process for attaching situation is specific as follows:
External application interface connects impedance test system, carries out control of Electric potentials to impedance test system and signal monitoring passes
Defeated, RS485 transmission module connection host computer carries out signal control output and handles and show, for detecting adhesion biomembrane not
Feelings that adhesion biofilm development situation changes with vitamine concentration are judged with the area of attachment under vitamine concentration, adhesive force
Condition.
The amplifier detection module includes voltage follower, feed circuit and current follower, voltage follower, feedback
Circuit and current follower include integrated operational amplifier;The model OPA211 of the integrated operational amplifier;Voltage with
Voltage is converted by the electric current that three electrode interfaces transmit respectively with the integrated operational amplifier of device, feed circuit and current follower
Signal is detected, and voltage detection signal is respectively sent into D/A conversion module.
The relay group module uses G6H-2-5VDC relay.
Compared with the prior art, the invention has the advantages that:
1, the suitable Electrochemical Detection of the present invention, for constant potential control errors within mV grades, the lower limit for detecting electric current reaches 10- 6A carries out stable signal detection to sample using three electrode sensings, has high sensitivity, system stabilization, compact overall structure
The advantages that;
2, present invention reduces sample detection times, the detection of mcg vitamin B in food can be easily carried out, than other
Detection method is efficiently quick, and sampling is repeated several times so that detection accuracy, detection it is comprehensive have been improved, reduce detection at
This, can sufficiently meet on-site test demand;
3, it by GPRS wireless communication module, realizes the communication between intelligent controlling device and remote monitoring platform, improves
The operational efficiency of whole system, also saves manpower and material resources.Later period of the invention carries out use in conjunction in combination with other platforms, increases
Added expansion, for example, with impedance test system use in conjunction, feelings are attached to growth of the biomembrane under different vitamine concentrations
The real-time simultaneous of condition detects;GPRS wireless communication module realizes the remote transmission of the long-range control and data of system, believes detection
Number detection control is carried out, the live signal that will test is sent to remote server.It is compatible using transparent transport protocol
MODBUS transport protocol, data transmit simpler convenience.
4, relay group module uses G6H-2-5VDC relay, and the model relay size is smaller, and power consumption is lower, sensitive
Degree is high, and electromagnetic interference is low, can be with high-density installation.
5, RS485 transmission is to send signal using differential level, and jamproof ability is strong, long distance of signal transmission.This hair
Bright to can be applied to engineering site, working environment noise is big, if it is desired to which transmission range is farther out.
6, the nA grade electric current that three electrode sensors input is converted voltage by the integrated operational amplifier of amplifier detection module
Signal is detected, D/A conversion module is sent into, the characteristics of using its high input impedance, high Open loop gain cofficient, low maladjustment voltage, is had
The error of effect control potentiostat.
7, the present invention meets current food safety detection trend, has small in size, easy to carry, prominent function, system
The features such as the operation is stable, intelligence degree are high, man-machine interface is good gathers around and has broad application prospects and practical value, using rising
Come very convenient.
Detailed description of the invention
Fig. 1 is the principle of the present invention block diagram;
Fig. 2 is the perspective view of housing unit in the present invention;
Fig. 3 is the schematic rear view of housing unit in the present invention;
Fig. 4 is triple electrode circuit Simplified equivalent model figure;
Fig. 5 is that the present invention carries out output voltage test experiments data result figure to triple electrode circuit equivalent model;
Fig. 6 is the cyclic voltammetry curve figure that the present invention measures on bare electrode and modified electrode;
Fig. 7 is the present invention and impedance test system use in conjunction schematic diagram.
Specific embodiment
The invention will be further described With reference to embodiment, and protection scope of the present invention is not limited to reality
Apply example, it is all according to the present disclosure or the equivalent replacement of any this field implemented of principle, belong to of the invention
Protection scope.
As shown in Figure 1, potentiostat application platform, by housing unit, RS485 transmission module 9, external equipment connecting line,
And power module 1, micro controller module 2, D/A conversion module 3, amplifier detection module 4, A/D in housing unit are set
Conversion module 5, relay group module 6, key display module 7 and GPRS wireless communication module 10 form.Power module 1 connects micro-
The power input of controller module 2;The digital quantity of micro controller module 2 is converted into analog quantity and is transmitted to fortune by D/A conversion module 3
Put detection module 4;A/D conversion module 5 by the sampled data in amplifier detection module 4 by analog quantity be converted into digital quantity be transmitted to it is micro-
Controller module 2 is handled;The transformation of pc port low and high level is inhaled in micro controller module 2 to control relay group module 6
It closes, to control the connection status of working electrode in amplifier detection module 4;The parameter of setting is sent to by key display module 7
Micro controller module 2 handle and will show from 2 received signal of micro controller module and data;RS485 transmits mould
Block 9 is connect with micro controller module 2, and the signal that will test is transferred to host computer 8 and carries out feedback control, and the letter that will test
Number remote server 11 is sent to by GPRS wireless communication module 10 in real time.
As shown in Figures 2 and 3, housing unit includes shell 12, display screen 13, front ventilation opening 14, electromotion pilot lamp 15, function
It can select button 16, upper select button 17, printing-type electrode detection chip card slot 18, usb 19, external application interface
20, power switch 21, power interface 22, back side ventilation opening 23, signal translation interface 24 and three electrode interfaces 25.
Display screen 13, front ventilation opening 14, electromotion pilot lamp 15, function select button 16 and upper select button 17 are all provided with
It sets in 12 top surface of shell;13 place plane of display screen and 16 place plane of function select button are at 135 °;In display screen 13 connects
Portion's key display module 7 simultaneously carries out transmission control by micro controller module 2, can show voltage value, the current value of setting and detection
And detection time;Front ventilation opening 14 is made of wire netting, increases the circulation of shell inner air and outer air;Electromotion pilot lamp 15 and power supply mould
Block 1 is connected, and when energization lights green;Function select button 16 connects key display module 7, and the information of setting is transferred to
Micro controller module 2 is controlled, including voltage, electric current, sweep speed and four setting buttons of sensitivity;Upper select button 17 with
Key display module 7 is connected, voltage, the electric current, the ascending, descending for sweeping speed or sensitivity number of adjustment function selection knob 16.
Printing-type electrode detection chip card slot 18, usb 19 and external application interface 20 are arranged at 12 side of shell;
Usb 19 and external application interface 20 are all connected with micro controller module 2;There are two printing-type electrode detection chip card slot 18 is set
It assigns slot for assigning printing-type electrode detection chip, is retracted shell when not in use;Printing-type electrode detection chip card slot 18 connects
Connect amplifier detection module 4;Usb 19 can carry out signal transmission by USB connecting line and other equipment;External application interface 20
By external application connecting line can external other equipment carry out use in conjunction, need the portable constant potential instrument control applied to each
The occasion of system such as carries out joint-detection with impedance test system.
Power switch 21, power interface 22, back side ventilation opening 23, signal translation interface 24 and three electrode interfaces 25 are respectively provided with
Behind shell 12;Power interface 22 connects power module 1, and through power supply adaptor input direct-current voltage;Power switch 21 connects
Power interface 22 and power module 1 are connect, electric power starting and closing are controlled;Back side ventilation opening 23 is made of wire netting, increases shell
Inner air and outer air circulation, enhancing heat dissipation;Signal translation interface 24 connects RS485 transmission module 9, and will be believed by RS485 patchcord
It number is transferred to host computer 8 at a distance and is communicated;Three electrode interfaces 25 are connected with amplifier detection module 4, and pass through three electrodes
Connecting line is connected with three electrode detection platforms.
Power supply adaptor, USB connecting line, RS485 patchcord, three electrode connecting lines and external application connecting line constitute external
Interfacility link.
Vitamin B detection method based on potentiostat application platform, including to the potentiostat application platform carry out before
The test of phase performance test and the test of later period application experiment.
1, electrochemical property test early period
1.1 are equivalent to the series-parallel form of resistance, capacitor in electrolytic cell three interelectrode relationships according to circuit equivalent principle
Impedance model can as shown in figure 4, impedance caused by electric double layer capacitance, electrode, solution and electrode reaction is analyzed
Think resistance RSIt is equivalent to working electrode and the resistance to solution between electrode, RFW、CFWIt is that working electrode is being contacted with electrolyte
The equivalent electric double layer impedance generated on face.It is tested for the property using the triple electrode circuit equivalent model, R is set in experimentSFor
1K Ω, CFWFor 50 μ F, RFWResistance value constantly change (1,10,30,5,100,200K Ω), concurrently set the difference of input terminal
Voltage value (voltage value between the both ends WE and RE) is respectively 0.100,0.500,1.000,2.000,3.300V, tests the constant potential
The output voltage situation of instrument application platform.The results are shown in Table 1 for test data of experiment.
Table 1 carries out output voltage test data table using triple electrode circuit equivalent model
Fig. 5 is to carry out output voltage test experiments data result figure to triple electrode circuit equivalent model.Pass through table 1 and Fig. 5
It can be seen that changing RFWResistance value when, output voltage kept stable, RFWThe change of resistance value to output voltage almost without
It influences, output voltage follows setting voltage change.
1.2 test the output current conditions of the potentiostat application platform using triple electrode circuit equivalent model.First set
RFWResistance value be 1K Ω when, change CFWCapacitance be respectively 50 μ F, 100 μ F, 150 μ F, set the different voltages of input terminal
Value (voltage value between the both ends WE and RE) is respectively 0.1,0.5,1.0,2.0,3.3V, measures the defeated of the potentiostat application platform
Current value out;Reset CFWCapacitance be 100 μ F when, change RFWResistance value be respectively 0.5K Ω, 1K Ω, 1.5K Ω, together
The different voltages value (voltage value between the both ends WE and RE) of sample setting input terminal is respectively 0.1,0.5,1.0,2.0,3.3V, measurement
The output current value of the potentiostat application platform, the results are shown in Table 2 for test data of experiment.
Table 2 carries out output testing current tables of data using triple electrode circuit equivalent model
It can be seen from Table 2 that working as RFWResistance value it is fixed when, the change of capacitor slightly influences output current value, but shadow
It rings less, because the electrolytic cell of capacitive can bring faint noise to measurement, table 2 shows outputting current steadily in a certain range
It is interior;When capacitance is fixed, output electric current is linearly reduced with the increase of resistance value, meets theoretical value, measurement data is steady
Qualitative and precision meets requirement of experiment.
2, later period application experiment is tested
2.1 in order to verify and protrude whether performance and application of the invention meet the requirements, using cyclic voltammetry, in difference
The potassium ferricyanide/potassium ferrocyanide solution ([Fe (CN) of concentration6]3-/4-) in, carry out the comparison of the present invention with CHI660C work station
Measurement experiment: 1) [the Fe (CN) of 100mM/L has been configured6]3-/4-Solution, be diluted to respectively with PBS solution concentration be 50mM/L,
The buffer of 25mM/L, 12.5mM/L, 6.75mM/L, 2) carry out cyclic voltammetry test, initial potential -0.2V, settling time
2S, it is respectively 10mV/S, 25mV/S, 50mV/S, 100mV/S that electrode, which sweeps speed, and 3) the more redox two peak value electricity of record
Flow ip1 and ip2.Experimental data is as shown in table 3, wherein is located at the value of front in ip1 and ip2 numerical value for CHI660C work
The measured value stood, subsequent value are measured value of the invention.
Table 3 measures [Fe (CN) 6] using CHI660C and the present invention3-/4-Buffer is in various concentration and sweeps output under speed
Current value
It can be seen from Table 3 that its current value of the buffer of same concentrations is linearly increasing with the increase for sweeping speed, it is identical to sweep
Its lower current value of speed is linearly reduced with the reduction of buffer concentration, and all at substantially linear relationship, it is theoretical to test data fit
As a result.It can be concluded that, the present invention measures stability and reaches requirement, can be accurate to 10 by with commercial CHI660C comparison-6A, symbol
Close actual application requirement.
2.2 present invention are to mcg vitamin B in food2Content carries out test experience, use pH for 4.0 0.1mol/L
Potassium Hydrogen Phthalate buffer is as electrolyte (vitamin B2Concentration be 2 × 10-5Mol/L), sweep speed 0.1V/s,
It is tested on bare electrode and modified electrode, it is as shown in Figure 6 to measure cyclic voltammetry curve figure.As can be seen from Figure 6, bare electrode
On modified electrode, there is a pair of sharp oxidation also almost without peak change, and steadily without any response in the curve measured
Parent peak, spike potential are respectively -0.29V and -0.25V, and corresponding peak point current is respectively 6.8 μ A and -7.1 μ A, according to vitamin
B2Concentration and current peak it is linear, so as to solve vitamin content situation in electrolyte at this time.
3, application platform connection signal situation
Fig. 7 is platform of the present invention and impedance test system use in conjunction schematic diagram.As shown in fig. 7, should be examined based on vitamin B
Survey portable potentiostat application platform 27 external application interface connect impedance test system 26, to impedance test system into
Row control of Electric potentials and signal monitoring transmission, RS485 transmission module 9 connect the progress signal control output of host computer 8 and handle and show
Show, for detecting area of attachment of the adhesion biomembrane (such as certain bacteriums, cell) under different vitamine concentrations, adhesive force
Situations such as judge its upgrowth situation with vitamine concentration situation of change.