A kind of easy photic electrochemical analytical instrument
Technical field
The present invention relates to a kind of photic electrochemical analytical instrument, it is specifically with laser diode and column can be fixed
The working electrode fixed support of electrode and pellet electrode is the photic electrochemical analytical instrument of core component.
Technical background
In current biomedical research and clinical practice, often by means of label will be measured be converted into light, electricity,
The signals such as sound, magnetic, heat and power (or will directly be measured and be converted into the signals such as light, electricity, sound, magnetic, heat and power).With scientific research
With clinical practice deeply, it is necessary to establish more highly sensitive analysis method.Photic electrochemistry is a kind of highly sensitive analysis
Method, photoexcitation process is not carried out from current detecting point in different spaces in its detection, and background signal is low, therefore at this stage
(there is the development of the photic electrochemical analyser of continuous wavelength scanner uni Three Dimensional Spectrum function as the focus of research
(CN201010621180.7)).Current photic electrochemical analytical instrument mainly has the auspicious analytical instrument Limited Liability advanced in years in Xi'an public
The photic electrochemical analyser of MPI-EO types of department, it includes xenon source, steady current source for xenon lamp, electrochemical analyser three parts;
There is patent to propose the photic electrochemical analyser using light source power, xenon source, spectrometer and electrochemical workstation as part
Device (development (CN201010621180.7) with the photic electrochemical analyser of continuous wavelength scanner uni Three Dimensional Spectrum function), this
Two kinds of instruments provide the exciting light in 200~1000nm wave-length coverages, it is possible to achieve the detection that electric current changes with excitation wavelength,
But its is complicated, cumbersome, bulky, cost is high, is not easy to promote.Also patent proposes with light emitting diode
LED is a kind of photic electrochemical source of current detection means (photic electrochemical photocurrent detection device of light source
(CN201310473553.4)), it proposes a kind of optical path direction, light intensity and exciting light spot size and can adjusted as needed
Photic electrochemical source of current detection means, but there is also deficiency:It is nonmonochromatic light that LED, which sends light, can be produced using it as light source
Nonspecific response current, so as to reduce the selectivity of analysis method.Also there is German electrochemical workstation (Zahner
Zennium, Germany) photic electrochemical analysis is carried out, but the instrument can only launch the light of several band wavelengths.
The content of the invention
In view of the shortcomings of the prior art and this area is studied and the demand of application, and it is an object of the invention to provide one kind to tie
The photic electrochemical analytical instrument that structure is simple, cost is cheap.It is by power supply, voltage regulator, voltage-stablizer, power switch, power supply
Indicator lamp;Laser diode storehouse, optical source cover board with holes, electrochemical cell, working electrode fixed support, working electrode, reference electrode,
To electrode, laser diode modulator, laser diode display, magazine;Electrochemical apparatus (or electrochemical workstation) and aobvious
Show that device part forms.
To achieve these goals you, technical scheme is as follows:
A kind of easy photic electrochemical analytical instrument, it is by power supply (1), voltage regulator (2), voltage-stablizer (3), power supply
Switch (4) and power supply indicator (5) composition power-supply system;By laser diode storehouse (6), optical source cover board with holes (7), electrochemical cell
(8), working electrode fixed support (9), working electrode (10), reference electrode (11) and to electrode (12), laser diode modulate
Device (13), laser diode display (14) and magazine (15) form photic electric generation system;By electrochemical apparatus (16) and show
Show device (17) composition data acquisition system.
By the voltage of power supply (1) input after voltage regulator (2) pressure regulation, by stable electricity needed for voltage-stablizer (3) output
Pressure;The laser diode of device lights in output voltage excitation laser diode storehouse (6), and the light sent passes through light source cover with holes
The aperture of plate (7), then the aperture by magazine (15) bottom, it is radiated at by the fixed work electricity of working electrode fixed support (9)
On the working surface of pole (10), so that the photoelectric activity material fixed on working electrode (10) surface is by insertion electrochemistry
The working electrode (10) of the three-electrode system in pond (8), reference electrode (11) and electric current is produced to electrode (12), by electrochemical apparatus
Caused electric current is acquired with display.Power switch (4) is used for controlling the Push And Release of power supply, and power supply indicator (5) is used
To indicate that whether normal power input is, laser diode modulator (13) is used for modulating swashing for device in laser diode storehouse (6)
Optical diode, laser diode display (14), which is used for showing, modulates to obtain wavelength corresponding to laser diode.
A kind of above-mentioned easy photic electrochemical analytical instrument, described laser diode storehouse (6) is characterized by laser
Set laser diode screens in diode storehouse (6), laser diode screens be it is discoid, can be successively along counterclockwise, laser
Laser diode is placed in diode screens, can be filled laser diode storehouse (6) by rotary laser diode modulator (13)
That puts sends the laser diode and circuit communication of different wave length, while adjusts voltage, obtains needed for corresponding laser diode
Voltage, wavelength corresponding to laser diode show by laser diode display (14), while needed for laser diode sends
Light.
A kind of above-mentioned easy photic electrochemical analytical instrument, described working electrode fixed support (9) is characterized by
Its top is hollow stainless steel tube, for fixing column working electrode, so as to via the aperture of optical source cover board with holes (7) and secretly
The light of the aperture of box (15) bottom can be radiated at the working surface of working electrode;Described working electrode fixed support (9) its
It is hollow square stainless steel framework to be characterized as its underpart, for fixing square working electrode, so as to via optical source cover board with holes
(7) aperture and the light of the aperture of magazine (15) bottom can be radiated at the working surface of working electrode.It is this by top to be
Empty stylostome and the working electrode fixed support (9) that bottom is hollow square frame, can realize the electricity that works column as needed
Pole (such as glass-carbon electrode, carbon paste electrode, gold electrode, needle electrode) and pellet electrode (such as ITO electrode, stainless steel pellet electrode,
Nickel foam pellet electrode etc.) it is fixed, so that light can irradiate on the working electrode (s, size is formed every time after changing electrode
The equal hot spot of equal hot spot and light intensity.The hollow space of the hollow stainless steel tube of working electrode fixed support (9) it is straight
Footpath can according to be adjusted using the external diameter of column working electrode;Working electrode fixed support (9) it is hollow it is square not
Become rusty steel framework hollow space length and it is wide can according to be adjusted using the size of post pellet electrode.
A kind of above-mentioned easy photic electrochemical analytical instrument, described optical source cover board with holes (7) contain neck, and it can
Slided with left, center, right.When optical source cover board with holes (7) is slided in centre position, the aperture and magazine of optical source cover board (7) with holes
The apertures align of bottom, light by the aperture of optical source cover board with holes (7), can then pass through the aperture of magazine bottom;When with holes
Optical source cover board (7) is slided at left or right position, and the aperture in the hole and magazine bottom of optical source cover board (7) with holes is completely misaligned,
Light can not pass through the aperture of optical source cover board with holes (7).
The present invention compared with prior art, has the following advantages that and beneficial effect:
1st, present device is simple in construction, easy to operate, and cheap;
2nd, present device is simple to operate easy to learn, without Special Training;
3rd, the present invention can rotary laser diode modulator as needed, obtain needed for wavelength excitation wavelength, without
Beam splitter;
4th, the present invention can fix columnar electrode or pellet electrode as needed, without changing working electrode fixed support;
5th, present device can match link with any electrochemical workstation, realize photic electrochemical analysis, without
Any other auxiliary equipment.
Brief description of the drawings
Fig. 1 is a kind of structural representation of easy photic electrochemical analytical instrument of the present invention, wherein:1 is power supply, 2
For voltage regulator, 3 be voltage-stablizer, 4 be power switch, 5 be power supply indicator, 6 be by laser diode storehouse, 7 be light with holes
Source cover plate, 8 be electrochemical cell, 9 be working electrode fixed support, 10 working electrodes, 11 reference electrodes, 12 be to be to electrode, 13
Laser diode modulator, 14 be laser diode display, 15 be magazine, 16 be electrochemical apparatus, 17 be display.
Fig. 2 is current-vs-time collection of illustrative plates, and abscissa is the time (t), and ordinate is electric current (i)
Fig. 3 is the standard curve of target dna 2, and abscissa is the concentration of target dna 2 (C), and ordinate is electric current (i).
Embodiment
It is specific embodiment of the present invention below, technical scheme is done and is further described, but this
The protection domain of invention is not limited to these embodiments.It is every to be included in without departing substantially from the change of present inventive concept or equivalent substitute
Within protection scope of the present invention.
Reagent used in the present invention:
Caddy (CdCl2 2.5H2O) buy and medical group Solution on Chemical Reagents in Shanghai company is enclosed in, selenium powder (Se,
99.95%, Meixing Chemical Co., Ltd., Shanghai).
DNA is bought by Shanghai Sheng Gong Bioisystech Co., Ltd, and sequence is as follows:
DNA1:3’-NH2-AGT TGG AGT CTG-5’;
DNA2:3’-SH-CAG ACT CCA ACT-5’;
Graphene oxide by improved Hummer methods (Hummers, W.S., Offeman, R.E.,
1958.J.Am.Chem.Soc. 80,1339) synthesis.
CdSe nano-particles synthesize:
In the CdCl containing 2-MEA2In (1.25M) solution, NaHSe (0.1M) solution now matched somebody with somebody is added, is then adjusted
Between section pH to 5.6 to 5.9.Under nitrogen protection, be stirred vigorously 10min., be then heated to reflux 3h obtain it is amido modified
CdSe nano-particles.
Photic Electrochemical Detection DNA:
After 100 μ L CdSe nano-particle solutions are mixed with 100 μ L GO solution, 5 μ L mixed solutions drop coatings are taken in golden electricity
Pole surface, dry at 37 DEG C, obtain CdSe and GO modified gold electrodes (CdSe/GO/GE).10 μ L DNA probes 1 are dripped into Tu in CdSe/
GO/GE surfaces, 30min. is incubated at 37 DEG C.SDS solution with 0.5% and secondary water washing successively, that is, obtain DNA1/CdSe/
GO/GE。
DNA1/CdSe/GO/GE is inserted in the solution containing target dna 2 again, reacts 30min. at 37 DEG C.Then, according to
It is secondary with after 0.5% SDS solution and secondary water washing, by the electrode obtained and reference electrode, 0.1M filled to electrode insertion resisted
In the electrochemical cell of bad hematic acid solution.Turn on the power switch, rotary laser diode modulator, laser diode display is shown
Modulate laser diode wave length is 430nm, open electrochemical apparatus and display and its related software, slide light source with holes
Optical source cover board with holes is slided and slides optical source cover board with holes in behind left or right position, 5s by cover plate behind centre position, 10s
Between position, so can obtain photocurrent-time collection of illustrative plates (Fig. 2), face integrated according to the current strength of current-vs-time collection of illustrative plates or collection of illustrative plates
Product carries out quantitative analysis to test substance.
As a result with discussion:
Current strength increases with the concentration of target dna 2 and gradually increased, and is obtained linearly in 1~200fM concentration range
Respond (Fig. 3), equation of linear regression is that (I is current strength to I=0.594C+0.907, unit nA;C is concentration, unit fM),
Coefficient correlation is 0.9991, and detection is limited to 0.5fM.The RSD of 9 parallel replications is carried out to the target dna 2 that concentration is 10fM
For 3.9%, show that this law has preferable reappearance.