CN102004126A - Electrochemical biosensor and detecting method thereof - Google Patents

Electrochemical biosensor and detecting method thereof Download PDF

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Publication number
CN102004126A
CN102004126A CN201010171836XA CN201010171836A CN102004126A CN 102004126 A CN102004126 A CN 102004126A CN 201010171836X A CN201010171836X A CN 201010171836XA CN 201010171836 A CN201010171836 A CN 201010171836A CN 102004126 A CN102004126 A CN 102004126A
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biological sensor
voltage
chip electrode
electrochemica biological
control module
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CN201010171836XA
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孟伟丽
宋世平
姜智能
顾睿风
朱欣华
苏岩
樊春海
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Shanghai Institute of Applied Physics of CAS
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Shanghai Institute of Applied Physics of CAS
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Abstract

The invention discloses an electrochemical biosensor and a detecting method thereof. The sensor comprises a multi-channel chip electrode, an electrochemical detecting module and a control module, wherein the multi-channel chip electrode is used as the front end of the electrochemical biosensor and converts chemical signals into electric signals; the electrochemical detecting module comprises a signal conditioning circuit, an A/D (analog/digital) converter and an MCU (micro controller unit); the electrochemical detecting module generates a voltage and inputs the voltage into the chip electrode; the chip electrode generates the corresponding current; the current is converted into the voltage through the signal conditioning circuit; the voltage passes through the A/D converter to obtain the corresponding digital amount and then is processed by the MCU; and the control module is used for taking charge of controlling the testing process, realizing the real-time display, controlling the experiment process and receiving detection data. The invention has the advantages that the electrochemical biosensor is provided with a humanized touch screen type man-machine interaction interface and multiple detecting channels, can be independently used and can be connected with a PC (personal computer); the requirements of the multi-channel rapid detection in relativity and repeatability experiments can be met; and printing electrodes are used in place of the traditional electrodes and the electrochemical biosensor is more suitable for miniaturization.

Description

Electrochemica biological sensor and detection method thereof
Technical field
The present invention relates to the electrochemical analysis technical field, particularly relate to dual-purpose electrochemica biological sensor of a kind of portable multi-channel and detection method thereof.
Background technology
The dual-purpose electrochemica biological sensor of portable multi-channel is the complete electrochemical system check and analysis equipment of a cover, can finish the parameter tracking and the analysis of electrochemical system under the various states.Up to now, many manufacturers both domestic and external have developed multiple electroanalysis device, as potentiostat, polarograph, electrochemical analysis test macro/workstation etc.China has obtained certain achievement since the nineties in 20th century aspect the research and development of electric analysis Instrument, satisfied the needs of research and teaching and analytical applications to a certain extent.But external on the whole like product still has a certain distance, to the improvement of existing product and research and develop new electrochemical analytical instrument and remain a very significant job.
Electrochemical analytical instrument commonly used at present mainly comes from abroad, and the electrochemical workstation of producing with american chemical instrument (CHI) company is an example.No matter be 600B general electrochemical analyser of series or 1200 serial palm electrochemical analysers, all need control, under Windows, work by outer computer.The 600B series instrument is thought highly of and is reached 7Kg, can't satisfy the outdoor on-the-spot portable requirement that detects.Though 1200 serial instrument volumes are little in light weight, add the computing machine of external control, still can't realize real portable.
Common portable electrochemical analyser, for example China Patent No. is 200610113140.5 disclosed a kind of hand-operated electrochemistry analyzers, instrument internal is provided with potentiostat, controller and power supply, and the instrument cover face is provided with liquid crystal display, button and the memory card interface that is connected with described controller; Controller is connected with potentiostat by interface; One end of electrode is connected to potentiostat by lead-in wire, and an other end exposes in the instrument outside.
Above-mentioned CHI1200 series and 200610113140.5 two kinds of instruments all have little, simple in structure, the easy to operate advantage of volume.But both all adopt serial communication, and transmission speed is slower, and adopt single channel to detect, and can't satisfy the demand of multichannel fast detecting in comparative, the repeated experiment.200610113140.5 break away from outer computer control, realized independent detection, but still be single channel, and also underaction of touch-tone input method, thereby above-mentioned electrochemical analytical instrument is used aspect some scientific experiments and production test and is had bigger limitation.
Summary of the invention
The technical problem to be solved in the present invention is to adopt serial communication in order to overcome electrochemical sensor of the prior art, transmission speed is slower, and adopt single channel to detect, can't satisfy the defectives such as demand of multichannel fast detecting in comparative, the repeated experiment, dual-purpose electrochemica biological sensor of a kind of portable multi-channel and detection method thereof are provided.
The present invention solves above-mentioned technical matters by following technical proposals:
A kind of electrochemica biological sensor, its characteristics are that it comprises:
One multi-channel chip electrode is used for the front end as this electrochemica biological sensor, and chemical signal is converted to electric signal;
One Electrochemical Detection module, it comprises signal conditioning circuit, A/D converter and MCU, this Electrochemical Detection module produces voltage, and voltage is input in the chip electrode, chip electrode produces corresponding electric current, electric current is converted to voltage by signal conditioning circuit, and voltage obtains the corresponding digital amount after by A/D converter, handles by MCU again;
One control module is used for being responsible for the control testing process, realizes showing in real time, controlling the experiment process and receive and detect data.
Preferably, this electrochemica biological sensor also comprises a human-computer interaction module, and it comprises touch-screen and mouse, and this human-computer interaction module is used for the user and directly controls experimentation.
Preferably, this multi-channel chip electrode has plural passage.
Preferably, this multi-channel chip electrode is 16 passages.
Preferably, this control module is the control module based on ARM, works in Windows CE operating system.
Preferably, this control module is the control module based on PC, and the user directly controls this electrochemica biological sensor by PC, and this control module works in Windows 2000 or Windows XP operating system.
Preferably, this Electrochemical Detection module also comprises a testing process control module, be used to control electrolytic cell switch, control test process beginning and time-out and experiment parameter correspondent voltage value, sensitivity are set.
Another technical scheme of the present invention is: a kind of detection method of aforesaid electrochemica biological sensor, and its characteristics are that it may further comprise the steps:
S 1, the user is added in drips of solution to be measured on the chip electrode, the Electrochemical Detection module is given control module with the current delivery that chip electrode produces;
S 2, this control module carries out that data are preserved and data processing.
Preferably, step S 1In, the electric current that chip electrode produces is converted to voltage by signal conditioning circuit, and voltage obtains the corresponding digital amount after by A/D converter, handles by MCU again.
Positive progressive effect of the present invention is: the dual-purpose electrochemica biological sensor of portable multi-channel of the present invention, have the touch-screen type human-computer interaction interface of hommization, and the multichannel sense channel can independently use and can connect PC and uses.Satisfy the demand of multichannel fast detecting in comparative, the repeated experiment.And using prints electrode replaces traditional electrode, is more suitable for miniaturization.
Further, combine printing-type chip electrode and this electrochemica biological sensor are effective, adopt the multi-channel electrochemical testing circuit, can realize that 1~16 passage detects simultaneously, more convenient, synchronism is good, has reduced measuring error.When cooperating the printing-type chip electrode to use, whether instrument can detectable correctly be added drop-wise on the chip, to save the meaningless operation of experimenter.
In addition, embedded technology is applied to instruments design, promptly selects for use ARM9 series processors S3C2410,, make up Windows CE operating system,, realize the man-machine interaction of hommization more in conjunction with touch-screen based on ARM in conjunction with peripheral circuit as CPU.In addition, when need not portable use, also can be connected use with PC, operation and deal with data are convenient.Instrument not only can also can upload the data to PC by USB with data storage in USB flash disk and SD card, perhaps upload to network by LAN.
Description of drawings
Fig. 1 is the system chart of electrochemica biological sensor of the present invention.
Fig. 2 is the circuit diagram of potentiostat of the present invention.
Fig. 3 is the circuit diagram of signal conditioning circuit of the present invention.
Fig. 4 is the synoptic diagram of the system control module based on ARM of the present invention.
Fig. 5 is the circuit diagram of mouse interface circuit of the present invention.
Fig. 6 is the schematic diagram of chip electrode of the present invention.
Embodiment
Provide preferred embodiment of the present invention below in conjunction with accompanying drawing, to describe technical scheme of the present invention in detail.
Shown in Fig. 1-5, electrochemica biological sensor of the present invention, comprise: a multi-channel chip electrode, be used for front end as this electrochemica biological sensor, chemical signal is converted to electric signal, its concrete printed circuit board technology that adopts in the present embodiment, the metal electrode material that silicon, gold etc. are commonly used is printed on the pcb board, realizes three-electrode system; One Electrochemical Detection module, it comprises signal conditioning circuit, A/D converter and MCU, this Electrochemical Detection module produces voltage, and voltage is input in the chip electrode, chip electrode produces corresponding electric current, electric current is converted to voltage by signal conditioning circuit, and voltage obtains the corresponding digital amount after by A/D converter, handles by MCU again; One control module is used for being responsible for the control testing process, realizes showing in real time, controlling the experiment process and receive and detect data.
The key technical indexes of the electrochemica biological sensor in the present embodiment is as follows:
(1) port number: 16 passages
(2) constant pressure source output voltage range: ± 10V
(3) constant pressure source output voltage resolution:<1mV
(4) sweep velocity :≤1V/s
(5) sampling rate: 〉=1kSPS/16 passage
(6) current measuring range: ± 100mA
(7) current measurement resolution: 0.1nA
The dual-purpose electrochemica biological sensor software section of portable multi-channel in the present embodiment comprises upper computer software and slave computer software, as shown in Figure 1, host computer procedure runs on the control module based on ARM, and it is in the AVR series monolithic that program of lower computer runs on the testing process control module.Upper computer software is responsible for the control of whole testing process based on Windows CE operating system, can realize real-time demonstration, control experiment process, receive functions such as detecting data.Slave computer software is used for control channel gating and A/D and D/A conversion etc., according to actual needs the respective channel of gating equipment based on the AVR series monolithic.As optional function, when need not portable use, the user can directly control instrument by PC, under this pattern, has designed corresponding upper computer software, can work in Windows2000 or WindowsXP operating system.Each passage of instrument projected current signal from chip electrode, and then obtain and the corresponding magnitude of voltage of electric current by signal conditioning circuit (comprising I/V change-over circuit and filtering circuit), obtain the digital quantity of voltage by A/D converter, this digital quantity is connected to the input end of microprocessor.More specifically, upper computer software sends to slave computer according to customer requirements with control commands corresponding, simultaneously poke, demonstration measurement result etc.Slave computer is according to order gated sweep voltage, and the electrolytic cell opening and closing are selected adequate sensitivity, voltage transitions, data transmission etc.
Upper computer software is responsible for the control of whole testing process, works in Windows CE operating system platform, and those skilled in the art can use the driving of Platform exploitation bottom hardware, eMbedded VisuaC++ developing application.Slave computer software uses AVR Studio development sequence based on the AVR series monolithic, and the GCC compiler compiles, and carries out in-circuit emulation and program download by jtag interface.
Upper computer software realizes that mainly bottom layer driving loads, to the parameter setting of slave computer, and experimentation control and data storage.What deserves to be mentioned is that host computer has added the startup self-detection function, instrument power on after first acquisition system zero-bit, if zero drift more greatly instrument not by self check, can not carry out next step operation.
Slave computer software is mainly realized three affairs: the one, and receive control command and correlation parameter that host computer sends, and the galvanochemistry instrument is carried out the parameter setting; The 2nd, the generation and the current acquisition of realization control waveform; The 3rd, host computer is handled and sent to image data.
In order to realize the optional function of instrument, promptly portable multi-channel electrochemical analyzer can use PC control, has also designed the host computer procedure that works in WindowsXP operating system, uses Visual C++ developing application.
Control module based on ARM is the core of the dual-purpose electrochemica biological sensor of portable multi-channel.Module is a chief component with ARM9 family chip S3C2410, and with respect to other chips, ARM9 series conveniently provides best performance in high-performance and low-power consumption.Its MMU supports main flow embedded OSs such as WindowsCE, Linux; Its MPU supports real time operating system; Support data and instruction Cache.As shown in Figure 4, NandFlash, SDRAM, power supply/crystal oscillator as the hardware ultimate system, have been formed system control module jointly.The mirror image of WindowsCE operating system leaves among the outside NandFlash, and starts from NandFlash, and when processor resets under this start-up mode, code will be loaded into internal SRAM and operation automatically.Afterwards, the boot among the SRAM is loaded into the operating system mirror image among the SDRAM, and operating system just can be moved in SDRAM.
Wherein the ultimate system based on the host computer of ARM comprises NandFlash, SDRAM, power supply, crystal oscillator.In addition, also comprise touch-screen (being used for and user interactions), USB flash disk or SD card (being used to store data), network interface/USB mouth (being used for data transmission).Slave computer mainly comprises AVR single-chip microcomputer, AD converter, filtering circuit, I/V change-over circuit, potentiostat and DA converter.
Wherein the Electrochemical Detection module is the basis of the dual-purpose electrochemica biological sensor of portable multi-channel.Module is chief component with the potentiostat, coordinates other related devices by MCU control, realizes current detecting, shown in Electrochemical Detection module among Fig. 1.The function generator of being made up of D/A produces voltage, through potentiostat voltage is input in the chip electrode, electrode produces corresponding electric current, electric current is converted to voltage by signal conditioning circuit, voltage obtains the corresponding digital amount after changing by 16 road A/D, handles by AVR Series MCU (Mega64) again.Potentiostat circuit shown in Figure 2 adopts by U1 formation and adds and circuit, the feedback signal that makes the contrast electrode current potential is through voltage follower U3 and reference signal uil addition, the effect of voltage follower is the electric current that reduces by contrast electrode, and sort circuit is widely used in electrochemical analyser.In the signal conditioning circuit, input current I InFlow through feedback resistor R f, the low bias current of amplifier A is to electric current I InInfluence very little, can ignore, the output voltage of amplifier is calculated as follows:
V o=-I inR f
So output voltage V oCan be used for measuring input current.Total sensitivity is by feedback resistor R fDecision.Thereby convert current value to magnitude of voltage.
Wherein, the core devices of instrument test process control module is a microprocessor, and according to the instruction of host computer, the beginning and the time-out of the switch of control electrolytic cell, control test process are provided with experiment parameter correspondent voltage value, sensitivity etc.Can carry out the Electrochemical Detection of 1~16 passage simultaneously.
Instrument data transport module in the present embodiment, mainly by SPI, USB, LAN forms.The Electrochemical Detection module of this portable multi-channel electrochemical analyser adopts the SPI interface to link to each other with the host computer that with ARM9 is processor and transmits control command etc., and instrument works in Windows CE operating system.Under this pattern, the user can upload to experimental data network, store in USB flash disk or the SD card by USB by LAN.Another characteristic of this instrument is: when need not portable use, the user can directly control instrument by PC, and instrument transmits control command etc. by USB interface, the experimental data in the process of acceptance test simultaneously.At this moment, PC can work in Windows2000 or Windows XP operating system.Demand easily when portable demand and laboratory were detected when obviously, instrument had satisfied outdoor detection.
The Electrochemical Detection module of the dual-purpose electrochemica biological sensor of this portable multi-channel adopts SPI to link to each other with ARM9, transmission control command and test data, and instrument works in WindowsCE operating system.When need not portable use, the user can directly control instrument by PC.Under this pattern, instrument carries out communication by USB interface, and PC can work in Windows2000, WindowsXP operating system.PC is sent to slave computer by USB with control command, and slave computer is sent to host computer by USB with acquired signal.
The instrument human-computer interaction module is made up of touch-screen and mouse, and the user can also can use instrument by mouse as using the iPhone mobile phone to use instrument by touch-screen.Than the button operation of traditional instrument, hommization more.Human-computer interaction module runs under the Windows CE operating system that the control module based on ARM provides, Windows CE operating system is similar to Windows XP operating system, it carries the driving to mouse and touch-screen, so can directly drive as long as design the relevant hardware circuit.The control that the touch screen interface circuit only need carry ARM is drawn and is got final product, and sees Fig. 5 about the circuit diagram of mouse interface, adopts the USB mouse, only needs 2,3 pin short circuits with J13/J14 among the figure during use, and mouse is inserted on the J15 and can uses.By upper computer software, the user directly controls experimentation, and meanwhile, experimental data will be saved in external USB flash disk of host computer or the SD card, carry out next step data processing to make things convenient for the user.
In addition, 16 passage printing-type chip electrodes have been adopted in the present embodiment with the instrument coupling, with traditional gold electrode, silicon electrode is compared, cheap, the advantages such as operation, multiplexer channel that are easy to carry that chip electrode has, these advantages make uses chip electrode to become a kind of trend of electrochemical analysis gradually.Chip electrode in the present embodiment as substrate, according to existing three-electrode system, plates proof gold in the above with 97% aluminium oxide ceramics.Each circular configuration is system independently, and intermediate point is that working electrode 2, the right point are to electrode 1, as shown in Figure 6 for contrast electrode 3, left side point.
Electrochemica biological sensor of the present invention is when detecting, the user is added in drips of solution to be measured on the printer chip electrode, the current delivery that the Electrochemical Detection module produces chip electrode is given the control module based on ARM, carry out data and preserve and data processing, finally present to the user by interpersonal interactive module.In the present embodiment, the electric current that chip electrode produces is converted to voltage by signal conditioning circuit, and voltage obtains the corresponding digital amount after by A/D converter, handles by MCU again.Electrochemica biological sensor of the present invention can carry out the Electrochemical Detection of 16 passages simultaneously, and whether control test process, ancillary staff's verification reagent drip correctly, are provided with experiment parameter etc.
Electrochemica biological sensor of the present invention also has the startup self-detection function, so that the user can judge whether instrument is working properly under the situation by externally measured system not; Self check is divided into two kinds of startup self-detection and manual self checks.Instrument has the function of automatic adjusting sensitivity, when studying new chemical reagent, has saved the time of groping experiment condition.
That this detecting instrument also has is efficient, quick, inexpensive, characteristics easily, is applicable to that the Electroanalytical Chemistry of using the printing-type chip electrode detects, and promptly is fit to the laboratory scientific research and is fit to outdoor on-the-spot the detection again.Therefore, the present invention has good industrialization prospect, meets present market situation.
Though more than described the specific embodiment of the present invention, it will be understood by those of skill in the art that these only illustrate, protection scope of the present invention is limited by appended claims.Those skilled in the art can make numerous variations or modification to these embodiments under the prerequisite that does not deviate from principle of the present invention and essence, but these changes and modification all fall into protection scope of the present invention.

Claims (9)

1. electrochemica biological sensor is characterized in that it comprises:
One multi-channel chip electrode is used for the front end as this electrochemica biological sensor, and chemical signal is converted to electric signal;
One Electrochemical Detection module, it comprises signal conditioning circuit, A/D converter and MCU, this Electrochemical Detection module produces voltage, and voltage is input in the chip electrode, chip electrode produces corresponding electric current, electric current is converted to voltage by signal conditioning circuit, and voltage obtains the corresponding digital amount after by A/D converter, handles by MCU again;
One control module is used for being responsible for the control testing process, realizes showing in real time, controlling the experiment process and receive and detect data.
2. electrochemica biological sensor as claimed in claim 1 is characterized in that this electrochemica biological sensor also comprises a human-computer interaction module, and it comprises touch-screen and mouse, and this human-computer interaction module is used for the user and directly controls experimentation.
3. electrochemica biological sensor as claimed in claim 1 is characterized in that, this multi-channel chip electrode has plural passage.
4. electrochemica biological sensor as claimed in claim 3 is characterized in that, this multi-channel chip electrode is 16 passages.
5. electrochemica biological sensor as claimed in claim 1 is characterized in that this control module is the control module based on ARM, works in Windows CE operating system.
6. electrochemica biological sensor as claimed in claim 1, it is characterized in that, this control module is the control module based on PC, and the user directly controls this electrochemica biological sensor by PC, and this control module works in Windows 2000 or Windows XP operating system.
7. electrochemica biological sensor as claimed in claim 1, it is characterized in that, this Electrochemical Detection module also comprises a testing process control module, be used to control electrolytic cell switch, control test process beginning and time-out and experiment parameter correspondent voltage value, sensitivity are set.
8. the detection method of an electrochemica biological sensor as claimed in claim 1 is characterized in that, it may further comprise the steps:
S1, user are added in drips of solution to be measured on the chip electrode, and the Electrochemical Detection module is given control module with the current delivery that chip electrode produces;
S2, this control module are carried out data and are preserved and data processing.
9. the detection method of electrochemica biological sensor as claimed in claim 8, it is characterized in that among the step S1, the electric current that chip electrode produces is converted to voltage by signal conditioning circuit, voltage obtains the corresponding digital amount after by A/D converter, handles by MCU again.
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Application publication date: 20110406