CN105004767B - A kind of phenylthiourea solution concentration detector and method - Google Patents

A kind of phenylthiourea solution concentration detector and method Download PDF

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Publication number
CN105004767B
CN105004767B CN201510066317.XA CN201510066317A CN105004767B CN 105004767 B CN105004767 B CN 105004767B CN 201510066317 A CN201510066317 A CN 201510066317A CN 105004767 B CN105004767 B CN 105004767B
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drip chamber
liquid
phenylthiourea
solution
phenylthiourea solution
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CN105004767A (en
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傅均
郑钢英
金姣姣
葛阳杨
惠国华
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Zhejiang Gongshang University
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Zhejiang Gongshang University
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Abstract

The invention discloses a kind of phenylthiourea solution concentration detector and method.The device includes computer, collecting unit and collecting work platform, collecting unit includes cell battery lead plate, SAW resonator and converting unit, collecting work platform includes base, standing groove and lifter are provided with base, drip chamber is provided with above standing groove, drip chamber is connected by bindiny mechanism with lifter, drip chamber bottom is provided with the micro pump connected with drip chamber, micro pump bottom is provided with the liquid droping head connected with micro pump, inlet is provided with the top of drip chamber, wiper mechanism and drainage mechanism are additionally provided with drip chamber, disk is provided with above drip chamber, on disk several liquid storage cylinders are provided with around the center of circle, liquid storage cylinder bottom position corresponding with inlet is provided with liquid outlet, liquid outlet is provided with liquid outlet electromagnetic valve, the motor of driving disk rotational is provided with the top of drip chamber.The present invention is simple in construction, and cost is low, can fast and accurately detect the concentration of phenylthiourea solution.

Description

A kind of phenylthiourea solution concentration detector and method
Technical field
The present invention relates to solution concentration detection technical field, more particularly to a kind of phenylthiourea solution concentration detector and Method.
Background technology
Existing phenylthiourea solution concentration detection technical method has Instrumental Analysis detection method and chemical measure, instrument point It is although simple to operate to analyse detection method, but the defects of big equipment volume, somewhat expensive, low accuracy of detection be present;Chemical measure Cumbersome, the deficiency of poor repeatability be present.
The content of the invention
The purpose of the present invention is to overcome the skill that existing phenylthiourea solution concentration detector cost is high, accuracy of detection is relatively low Art problem, there is provided a kind of phenylthiourea solution concentration detector and method, its is simple in construction, and cost is low, can be quickly accurate The true concentration for detecting phenylthiourea solution.
In order to solve the above problems, the present invention is achieved using following technical scheme:
A kind of phenylthiourea solution concentration detector of the present invention, including computer, collecting unit and collecting work platform, The collecting unit includes cell battery lead plate, SAW resonator and converting unit, and the collecting work platform includes base, institute State and standing groove and lifter are provided with base, be provided with drip chamber above the standing groove, the drip chamber passes through bindiny mechanism Be connected with lifter, the drip chamber bottom is provided with the micro pump that connect with drip chamber, the micro pump bottom provided with it is micro The liquid droping head of pump connection, the drip chamber top are provided with inlet, wiper mechanism and drainage mechanism are additionally provided with the drip chamber, It is provided with disk above the drip chamber, several liquid storage cylinders, the liquid storage cylinder bottom and feed liquor is provided with around the center of circle on the disk Position corresponding to mouthful is provided with liquid outlet, and the liquid outlet is provided with liquid outlet electromagnetic valve, driving disk is provided with the top of the drip chamber The motor of rotation, the SAW resonator electrically connect with cell battery lead plate and converting unit respectively, the computer Electrically connected respectively with converting unit, micro pump, wiper mechanism, drainage mechanism, liquid outlet electromagnetic valve, motor and lifter.
In the technical program, the phenylthiourea solution of various concentrations is obtained in advance, the phenylthiourea of various concentrations is molten Liquid is poured into each liquid storage cylinder on disk respectively, and cell battery lead plate is placed in standing groove, and cell battery lead plate is positioned at drop Below liquid head.Lifter control drip chamber lifting, so as to adjust the position of liquid droping head, makes between liquid droping head and cell battery lead plate Distance is optimum value.
Start the work of phenylthiourea solution concentration detector, computer controls liquid storage cylinder corresponding with drip chamber on disk On liquid outlet electromagnetic valve open (with drip chamber corresponding to liquid outlet on liquid storage cylinder be aligned with the inlet on drip chamber), liquid storage The phenylthiourea solution of intracavitary injects drip chamber by inlet.Then computer controls micro pump work, micro pump control drop At interval of 2.1 seconds dropping liquids once, each dropping liquid amount is 0.05ml to liquid head, dropping liquid 260 times altogether.Phenylthiourea solution in drip chamber Dripped to by liquid droping head on cell battery lead plate, cell battery lead plate produces specific current-responsive, and current-responsive is by surface acoustic wave resonance Device captures and is output to converting unit in the frequency form, converting unit detection frequency signal, and output frequency response curve to calculating Machine.Computer obtains 120 sampled values in the frequency response curve up-sampling received, using sampled value as input data S (t), Input second-order linear system accidental resonance modelIn, And second-order linear system accidental resonance model is resonated, obtain the output signal-to-noise ratio of the phenylthiourea solution
After dropping liquid terminates, drainage mechanism discharges remaining phenylthiourea solution in drip chamber, and wiper mechanism is to drip chamber Carry out cleaning drying.Then, computer drives disk to rotate clockwise certain angle by motor, makes next liquid storage cylinder Position corresponding with drip chamber is turned to, then repeats the above steps and detects the output letter of phenylthiourea solution in the liquid storage cylinder Make an uproar and compare, then drainage mechanism discharges remaining phenylthiourea solution in drip chamber, and wiper mechanism carries out cleaning to drip chamber and blown It is dry.The output signal-to-noise ratio until detecting the phenylthiourea solution on disk in all liquid storage cylinders is so circulated, is obtained in advance The concentration of phenylthiourea solution is respectively k1, k2..., kN, its corresponding output signal-to-noise ratio is respectively SNR1, SNR2..., SNRN, computer is by point (k1, SNR1), (k2, SNR2) ..., (kN, SNRN) fitting it is in alignment, obtained according to the straight line of fitting To the forecast model of phenylthiourea solution:
Detect unknown concentration phenylthiourea solution to be measured when, as long as by phenylthiourea solution to be measured pour into on disk with Corresponding to drip chamber in liquid storage cylinder, repeat the above steps to obtain the output signal-to-noise ratio SNR of the phenylthiourea solution, the output is believed Make an uproar and the forecast model of phenylthiourea solution is substituted into than SNR:It is molten so as to calculate phenylthiourea to be measured The concentration k of liquid.Structure of the present invention is simple, and cost is low, and after the completion of each dropping liquid, wiper mechanism can carry out cleaning drying to drip chamber, The concentration for ensureing to inject the phenylthiourea solution of drip chamber next time will not be disturbed by impurity, improve accuracy of detection, detect Device controls automatic work by computer, and detection speed is fast, improves detection efficiency.
Preferably, the cell battery lead plate includes substrate, the substrate is provided with working electrode, electrode and two is joined Than electrode, the working electrode includes the rounded portions of front end, and the rounded portions are made up of foam copper, and one layer of plating is coated with the foam copper Layer gold, the Gold plated Layer are provided with mouse bacterium shape taste bud taste receptor cells, it is described to the front end of electrode and reference electrode before Hold it is curved be centered around on the outside of rounded portions, the working electrode front end, oil is scribbled to electrode front end and reference electrode front end outer side Lacquer coat.0.5 to 1 centimetre of upper surface of base plate is above to the upper surface of electrode, reference electrode and working electrode, substrate is cut by ST Type quartz is made, and electrode and reference electrode are made up of tungsten, and working electrode is made up of foam copper product, and foam copper is to be uniformly distributed Three-dimensional netted pore structure, it has the network structure of multi-layer stable and is completely embedded, and network structure is unlikely to deform and collapsed, this Cell is enabled to enter foam copper inside configuration so that cell preferably can be attached on electrode, and Gold plated Layer compares foam copper Toxicity is lower, with cells contacting so that cytoactive is more preferable, also make it that detection sensitivity is more preferable.
Preferably, the converting unit includes oscillating circuit and frequency detector, the SAW resonator passes through Oscillating circuit electrically connects with frequency detector, and the frequency detector is with calculating mechatronics.
Preferably, the wiper mechanism includes air inlet and water inlet, the drip chamber by a connecting line with Air inlet connects with water inlet, and the air inlet is connected with air pump, and the water inlet is connected with water pump, the water pump and water tank phase Even, the air inlet is provided with air inlet electromagnetic valve, and the water inlet is provided with entering water electromagnetic valve, the air pump, water pump, air inlet electromagnetic valve With entering water electromagnetic valve respectively with calculating mechatronics.When being cleaned to drip chamber, first close air inlet electromagnetic valve, start water pump, Entering water electromagnetic valve is opened, water pump injected clear water into drip chamber cleans, and then drainage mechanism discharges water, switches off the pump and intakes Magnetic valve, booster air pump, air inlet electromagnetic valve is opened, air pump is passed through air into drip chamber and dries up drip chamber.
Preferably, the wiper mechanism also includes the rabbling mechanism being arranged in drip chamber, the rabbling mechanism includes Horizontally disposed hollow cross bar and longitudinally disposed hollow vertical pole, the bottom in the cross bar stage casing are set in vertical by bearing The top of bar, the cavity in the cross bar connect with the cavity in vertical pole, the leading flank and the cross bar other end of described cross bar one end Trailing flank be provided with several through holes, the through hole connects with cross bar internal cavity, and the vertical pole is arranged on drip chamber bottom, described Cavity in vertical pole is connected by connecting line with air inlet and water inlet.During cleaning, clear water is passed through cross bar from vertical pole, and from horizontal stroke Discharged in the through hole of bar, drive cross bar to rotate when clear water is discharged out of through hole, when clear water reaches a certain amount of in drip chamber, cross bar Stirring clear water is rotated, makes drip chamber cleaning more thorough.After drainage mechanism discharges clear water, air is passed through cross bar, and is arranged from through hole Go out, cross bar rotates, and accelerates the flowing of dropping liquid indoor air flow, accelerates drip chamber rate of drying.Dripped moreover, injecting solution in liquid storage cylinder During liquid room, being passed through air rotates cross bar, and cross bar agitating solution makes air preferably be mixed with solution, increases solution oxygen content, So that the time that cell survival on cell battery lead plate is longer.
Preferably, the wiper mechanism also includes air heater, the air outlet of the air heater and air pump Air inlet connects, and the air heater is with calculating mechatronics.In cleaning, heater work, air pump is into drip chamber Hot-air is passed through, accelerates drip chamber rate of drying, when increasing solution oxygen content in drip chamber, heater does not work, air pump The air being passed through into drip chamber under normal temperature state.
Preferably, the drainage mechanism includes the drainpipe for being arranged on drip chamber bottom, the drainpipe and drip chamber Connection, the drainpipe are provided with drain solenoid valve, and the drain solenoid valve is with calculating mechatronics.
A kind of phenylthiourea solution concentration detection method of the present invention, comprises the following steps:
S1:Phenylthiourea solution to be measured is poured on disk in liquid storage cylinder corresponding with drip chamber, then by liquid storage cylinder Phenylthiourea solution injection drip chamber;
S2:Liquid droping head drips to phenylthiourea solution on cell battery lead plate, and micro pump controls the dropping liquid amount and drop of liquid droping head The liquid time, at interval of 2.1 seconds dropping liquids once, each dropping liquid amount is 0.05ml to liquid droping head, dropping liquid 260 times altogether, after dropping liquid terminates The surplus solution in drip chamber is discharged, and cleaning drying is carried out to drip chamber;
S3:Signal on SAW resonator collection cell battery lead plate is sent to converting unit, converting unit output frequency Rate response curve up-samples to computer, computer in the frequency response curve received, obtains 110-120 sampled value, will Sampled value inputs second-order linear system accidental resonance model as input data S (t) In, and second-order linear system accidental resonance model is resonated,
Wherein, x (t) is the displacement for vibrating particle, and Ω is angular frequency, and r and ω are the attenuation coefficient of setting respectively and linear The frequency of particle is vibrated, c is the signal adjustment coefficient of setting, and b is the quadratic noise ξ of setting2(t) coefficient, ξ (t) are three discriminations Noise, ξ (t) ∈ {-a, 0, a }, a > 0, the dismutation of noise follows Poisson distribution, and its probability distribution is ps(a)=ps(-a) =q, ps(0)=1-2q, wherein 0 < q < 0.5;
Noise average follows with correlation<ξ(t)>=0,<ξ(t)ξ(t+τ)>=2qa2e-λτ,
Wherein λ is correlation ratio, and three discrimination noise ξ (t) glacing flatness is
The output signal-to-noise ratio for obtaining phenylthiourea solution to be measured is
S4:Obtained output signal-to-noise ratio SNR is substituted into phenylthiourea solution concentration forecast model: Calculate the concentration k of phenylthiourea solution to be measured.
Preferably, the phenylthiourea solution concentration forecast model is obtained by following steps:
N1:The phenylthiourea solution of various concentrations is obtained in advance, and the phenylthiourea solution of various concentrations is poured into circle respectively In each liquid storage cylinder on disk;
N2:Phenylthiourea solution injection drip chamber on computer control disk in liquid storage cylinder corresponding with drip chamber, drop Phenylthiourea solution in liquid room is dripped on cell battery lead plate by liquid droping head, and micro pump controls the dropping liquid amount and dropping liquid of liquid droping head Time, at interval of 2.1 seconds dropping liquids once, each dropping liquid amount is 0.05ml to liquid droping head, dropping liquid 260 times altogether;
N3:After dropping liquid terminates, drainage mechanism discharges remaining phenylthiourea solution in drip chamber, and wiper mechanism is to dropping liquid Room carries out cleaning drying;
N4:Signal on SAW resonator collection cell battery lead plate is sent to converting unit, converting unit output frequency Rate response curve up-samples to computer, computer in the frequency response curve received, obtains 110-120 sampled value, will Sampled value inputs second-order linear system accidental resonance model as input data S (t) In, and second-order linear system accidental resonance model is resonated, obtain the phenyl sulphur The output signal-to-noise ratio of urea solution;
N5:Computer controls disk rotational certain angle, and next liquid storage cylinder is turned into position corresponding with drip chamber, Phenylthiourea solution in the liquid storage cylinder is injected into drip chamber, step N2 to step N4 is repeated, obtains in the liquid storage cylinder The output signal-to-noise ratio of phenylthiourea solution, then disk be rotated further by certain angle, detect the phenyl sulphur in next liquid storage cylinder The output of the output signal-to-noise ratio of urea solution, so circulation until detecting the phenylthiourea solution on disk in all liquid storage cylinders is believed Make an uproar ratio;
N6:The concentration of the phenylthiourea solution obtained in advance is respectively k1, k2..., kN, its corresponding output signal-to-noise ratio point Wei not SNR1, SNR2..., SNRN, computer is by point (k1, SNR1), (k2, SNR2) ..., (kN, SNRN) it is fitted to one directly Line, the forecast model of phenylthiourea solution is obtained according to the straight line of fitting:
The present invention substantial effect be:Simple in construction, cost is low, and after the completion of each dropping liquid, wiper mechanism can be to drip chamber Cleaning drying is carried out, the concentration for ensureing to inject the phenylthiourea solution of drip chamber next time will not be disturbed by impurity, improve Accuracy of detection, detection means control automatic work by computer, and detection speed is fast, improves detection efficiency.
Brief description of the drawings
Fig. 1 is a kind of structural representation of the present invention;
Fig. 2 is a kind of structural representation of the disk of the present invention;
Fig. 3 is a kind of circuit theory connection block diagram of the present invention;
Fig. 4 is a kind of structural representation of the cell battery lead plate of the present invention;
Fig. 5 is a kind of structural representation of the cross bar of the present invention;
Fig. 6 is a kind of structural representation of the SAW resonator of the present invention.
In figure:1st, computer, 2, cell battery lead plate, 3, SAW resonator, 4, converting unit, 5, base, 6, place Groove, 7, drip chamber, 8, micro pump, 9, liquid droping head, 10, inlet, 11, disk, 12, liquid storage cylinder, 13, liquid outlet, 14, go out liquid electricity Magnet valve, 15, motor, 16, substrate, 17, work drive motor, 18, to electrode, 19, reference electrode, 20, painting layer, 21, enter Gas port, 22, water inlet, 23, air pump, 24, water pump, 25, air inlet electromagnetic valve, 26, entering water electromagnetic valve, 27, cross bar, 28, vertical pole, 29th, through hole, 30, air heater, 31, drainpipe, 32, drain solenoid valve, 33, piezoelectric substrate, 34, interdigital transducer, 35, anti- Penetrate grid, 36, gain grid, 37, sound absorption part, 38, connection end, 39, adapter sleeve, 40, check valve, the 41, first groove, 42, second is recessed Groove, 43, osculum, 44, positioning pedestal, 45, lifter, 46, voice-output unit.
Embodiment
Below by embodiment, and with reference to accompanying drawing, technical scheme is described in further detail.
Embodiment:A kind of phenylthiourea solution concentration detector of the present embodiment, as shown in Figure 1, Figure 2, Figure 3 shows, including Computer 1, collecting unit and collecting work platform, it is single that collecting unit includes cell battery lead plate 2, SAW resonator 3 and conversion Member 4, collecting work platform includes base 5, and standing groove 6, lifter 45 and voice-output unit 46, standing groove 6 are provided with base 5 Top is provided with drip chamber 7, and drip chamber 7 is connected by bindiny mechanism with lifter 45, and the bottom of drip chamber 7 is provided with to be connected with drip chamber 7 Logical micro pump 8, the bottom of micro pump 8 are provided with the liquid droping head 9 connected with micro pump 8, and the top of drip chamber 7 is provided with inlet 10, dripped Wiper mechanism and drainage mechanism are additionally provided with liquid room 7, the top of drip chamber 7 is provided with disk 11, is provided with disk 11 around the center of circle some Individual liquid storage cylinder 12, the bottom of liquid storage cylinder 12 are provided with liquid outlet 13 with 10 corresponding position of inlet, and liquid outlet 13 is provided with out liquid electricity Magnet valve 14, the top of drip chamber 7 are provided with the motor 15 that driving disk 11 rotates.
Wiper mechanism, which includes air inlet 21, water inlet 22 and the rabbling mechanism being arranged in drip chamber, rabbling mechanism, to be included Horizontally disposed hollow cross bar 27 and longitudinally disposed hollow vertical pole 28, as shown in figure 5, the bottom in the stage casing of cross bar 27 passes through Bearing is set in the top of vertical pole 28, and the cavity in cross bar 27 connects with the cavity in vertical pole 28, the leading flank of the one end of cross bar 27 Several through holes 29 are provided with the trailing flank of the other end of cross bar 27, through hole 29 is connected with the internal cavity of cross bar 27, and vertical pole 28 is arranged on The bottom of drip chamber 7, the cavity in vertical pole 28 are connected by a connecting line with air inlet 21 and water inlet 22, air inlet 21 with Air pump 23 is connected, and water inlet 22 is connected with water pump 24, and water pump 24 is connected with water tank, and air inlet 21 is provided with air inlet electromagnetic valve 25, enters The mouth of a river 22 is provided with entering water electromagnetic valve 26.Drainage mechanism includes the drainpipe 31 for being arranged on the bottom of drip chamber 7, drainpipe 31 and dropping liquid Room 7 connects, and drainpipe 31 is provided with drain solenoid valve 32.
SAW resonator 3 electrically connects with cell battery lead plate 2 and converting unit 4 respectively, and computer 1 is single with conversion respectively Member 4, micro pump 8, motor 15, liquid outlet electromagnetic valve 14, air inlet electromagnetic valve 25, entering water electromagnetic valve 26, drain solenoid valve 32, gas Pump 23, water pump 24, lifter 45 and voice output circuit 46 electrically connect.Converting unit 4 includes oscillating circuit and frequency detector, SAW resonator 3 is electrically connected by oscillating circuit with frequency detector, and frequency detector electrically connects with computer 1.
Standing groove 6 includes the first groove 41 and the second groove 42, and the first groove 41 is located at the lower section of drainpipe 31, the second groove 42 are provided with positioning pedestal 44 in the lower section of liquid droping head 9, the second groove 42, and positioning pedestal 44 is provided with matches somebody with somebody with cell battery lead plate 2 The locating slot of conjunction, the sidewall slope of positioning pedestal 44 are set, and the bottom of the first groove 41 and the bottom of the second groove 42 are designed with draining Hole 43, osculum 43 are connected by discharge pipe line with outside effluent storage device.Connection is arranged with the rotating shaft of motor 15 Set 39, disk 11 is detachably connected with adapter sleeve 39, is easy to disk to pull down cleaning.Air inlet 21 is located at the top of water inlet 22.Even Adapter road is provided with check valve 40, prevents liquid from flowing back.Lifter is used to control drip chamber to lift, so as to which liquid droping head be adjusted to Suitable position.Voice-output unit is used to export voice message and testing result.Gap between drip chamber and disk be present.
As shown in figure 4, cell battery lead plate 2 includes substrate 16, substrate 16 is provided with working electrode 17, to electrode 18 and two Reference electrode 19, working electrode 17 include the rounded portions of front end, and the rounded portions are made up of foam copper, and one layer is coated with the foam copper Gold plated Layer, Gold plated Layer are provided with mouse bacterium shape taste bud taste receptor cells, the front end of front end and reference electrode 19 to electrode 18 It is curved to be centered around on the outside of rounded portions, the front end of working electrode 17, oil is scribbled to the front end of electrode 18 and the front end outer side of reference electrode 19 Lacquer coat 20.0.6 centimetre of 16 upper surface of substrate, base are above to the upper surface of electrode 18, reference electrode 19 and working electrode 17 Plate 16 is made up of ST cut type quartz, and electrode 18 and reference electrode 19 are made up of tungsten, and working electrode 18 is made up of foam copper product, Foam copper is equally distributed three-dimensional netted pore structure, and it has the network structure of multi-layer stable and is completely embedded, network structure It is unlikely to deform and collapses, this enables cell to enter foam copper inside configuration so that cell preferably can be attached on electrode, Gold plated Layer is lower compared to foam Copper electrodissolution, with cells contacting so that cytoactive is more preferable, also make it that detection sensitivity is more preferable.Two There is no voltage difference between reference electrode, equivalent to the region for having a voltage constant between them, whole region is joined as voltage Examine, the favourable stability for improving detection.
As shown in fig. 6, SAW resonator 3 includes 34, two piezoelectric substrate 33, interdigital transducer reflecting gratings 35, set In the both sides of reflecting grating 35 four gain grid 36 and be respectively arranged at the sides of remote interdigital transducer 34 of two reflecting gratings 35 Two sound absorption parts 37, are electrically connected with two connection ends 38 on interdigital transducer 34 respectively to electrode 18 and working electrode 17 Connect, reference electrode 19 is connected by 5V bias direct currents voltage with working electrode 17.
The phenylthiourea solution of various concentrations is obtained in advance, and the phenylthiourea solution of various concentrations is poured on disk respectively Each liquid storage cylinder in, cell battery lead plate is placed in the locating slot of positioning pedestal, now cell battery lead plate is located at liquid droping head Lower section.
Start the work of phenylthiourea solution concentration detector, computer controls liquid storage cylinder corresponding with drip chamber on disk On liquid outlet electromagnetic valve open (with drip chamber corresponding to liquid outlet on liquid storage cylinder be aligned with the inlet on drip chamber), liquid storage The phenylthiourea solution of intracavitary injects drip chamber by inlet.Then computer controls micro pump work, micro pump control drop At interval of 2.1 seconds dropping liquids once, each dropping liquid amount is 0.05ml to liquid head, dropping liquid 260 times altogether.Phenylthiourea in drip chamber is molten Liquid is dripped on cell battery lead plate by liquid droping head, and cell battery lead plate produces specific current-responsive, and current-responsive is by surface acoustic wave Resonator captures and is output to converting unit in the frequency form, converting unit detection frequency signal, and output frequency response curve arrives Computer.Computer up-samples in the frequency response curve received, 120 sampled values is obtained, using sampled value as input data S (t) second-order linear system accidental resonance model, is inputted In, and second-order linear system accidental resonance model is resonated, obtain the output signal-to-noise ratio of the phenylthiourea solution
After dropping liquid terminates, drainage mechanism discharges remaining phenylthiourea solution in drip chamber, and wiper mechanism is to drip chamber Carry out cleaning drying.Then, computer drives disk to rotate clockwise certain angle by motor, makes next liquid storage cylinder Position corresponding with drip chamber is turned to, then repeats the above steps and detects the output letter of phenylthiourea solution in the liquid storage cylinder Make an uproar and compare, then drainage mechanism discharges remaining phenylthiourea solution in drip chamber, and wiper mechanism carries out cleaning to drip chamber and blown It is dry.The output signal-to-noise ratio until detecting the phenylthiourea solution on disk in all liquid storage cylinders is so circulated, is obtained in advance The concentration of phenylthiourea solution is respectively k1, k2..., kN, its corresponding output signal-to-noise ratio is respectively SNR1, SNR2..., SNRN, computer is by point (k1, SNR1), (k2, SNR2) ..., (kN, SNRN) fitting it is in alignment, obtained according to the straight line of fitting To the forecast model of phenylthiourea solution:
Detect unknown concentration phenylthiourea solution to be measured when, as long as by phenylthiourea solution to be measured pour into on disk with Corresponding to drip chamber in liquid storage cylinder, repeat the above steps to obtain the output signal-to-noise ratio SNR of the phenylthiourea solution, the output is believed Make an uproar and the forecast model of phenylthiourea solution is substituted into than SNR:It is molten so as to calculate phenylthiourea to be measured The concentration k of liquid.
Wiper mechanism also includes air heater 30, and the air outlet of air heater 30 connects with the air inlet of air pump 23, Air heater 30 electrically connects with computer 1.After each dropping liquid terminates, drainage mechanism first arranges the surplus solution in drip chamber Go out, then drain solenoid valve is closed, and is cleaned.Close air inlet electromagnetic valve, start water pump, open entering water electromagnetic valve, clear water from Vertical pole is passed through cross bar, and is discharged out of cross bar through hole, drives cross bar to rotate when clear water is discharged out of through hole, when clear in drip chamber When water reaches a certain amount of, cross bar rotates stirring clear water, makes drip chamber cleaning more thorough.Then drainage mechanism discharges water, closes Water pump and entering water electromagnetic valve, booster air pump, air heater, air inlet electromagnetic valve is opened, air pump is passed through hot-air into drip chamber Drip chamber is dried up.After drainage mechanism discharges clear water, hot-air is passed through cross bar, and is discharged from through hole, and cross bar rotates, and accelerates drop Liquid indoor air flow flows, and accelerates drip chamber rate of drying.
When solution is injected drip chamber by liquid storage cylinder, being passed through normal temperature air rotates cross bar, and cross bar agitating solution makes air Preferably mixed with solution, increase solution oxygen content, so that the time that the cell survival on cell battery lead plate is longer.
A kind of phenylthiourea solution concentration detection method of the present embodiment, examined suitable for above-mentioned phenylthiourea solution concentration Device is surveyed, is comprised the following steps:
S1:Cell battery lead plate is put into standing groove, phenylthiourea solution to be measured poured into corresponding with drip chamber on disk Liquid storage cylinder in, then liquid droping head is adjusted to specified location by lifter, then by liquid storage cylinder phenylthiourea solution inject Drip chamber, solution in liquid storage cylinder is all after injection drip chambers, and be passed through normal temperature air rotates cross bar for a period of time, cross bar stirring Solution makes air preferably be mixed with solution, increases solution oxygen content, so that the cell survival on cell battery lead plate is longer Time;
S2:Liquid droping head drips to phenylthiourea solution on cell battery lead plate, and micro pump controls the dropping liquid amount and drop of liquid droping head The liquid time, at interval of 2.1 seconds dropping liquids once, each dropping liquid amount is 0.05ml to liquid droping head, dropping liquid 260 times altogether, after dropping liquid terminates, Drain solenoid valve is opened, the surplus solution in drip chamber is discharged, drain solenoid valve is closed after discharge, then starts water pump, open Open entering water electromagnetic valve and be passed through clear water, drip chamber is cleaned, switched off the pump after cleaning and entering water electromagnetic valve, then open draining electricity Magnet valve discharges water, and then booster air pump, air heater, unlatching air inlet electromagnetic valve, are passed through hot-air and dry up drip chamber, finally Close drain solenoid valve, air pump, air heater and air inlet electromagnetic valve;
S3:Signal on SAW resonator collection cell battery lead plate is sent to converting unit, converting unit output frequency Rate response curve up-samples in the frequency response curve received to computer, computer, obtains 120 sampled values, will sample Value is used as input data S (t), inputs second-order linear system accidental resonance model In, and second-order linear system accidental resonance model is resonated,
Wherein, x (t) is the displacement for vibrating particle, and Ω is angular frequency, and r and ω are the attenuation coefficient of setting respectively and linear The frequency of particle is vibrated, c is the signal adjustment coefficient of setting, and b is the quadratic noise ξ of setting2(t) coefficient, ξ (t) are three discriminations Noise, ξ (t) ∈ {-a, 0, a }, a > 0, the dismutation of noise follows Poisson distribution, and its probability distribution is ps(a)=ps(-a) =q, ps(0)=1-2q, wherein 0 < q < 0.5;
Noise average follows with correlation<ξ(t)>=0,<ξ(t)ξ(t+τ)>=2qa2e-λτ,
Wherein λ is correlation ratio, and three discrimination noise ξ (t) glacing flatness is
The output signal-to-noise ratio for obtaining phenylthiourea solution to be measured is
S4:Obtained output signal-to-noise ratio SNR is substituted into phenylthiourea solution concentration forecast model: Calculate the concentration k of phenylthiourea solution to be measured.
When model resonates, particle produces resonance in some position, this angular frequency Ω, attenuation coefficient r, correlation ratio λ, is Therefore number b, constant a, q are it has been determined that can calculate signal to noise ratio snr.
Phenylthiourea solution concentration forecast model is obtained by following steps:
N1:The phenylthiourea solution of various concentrations is obtained in advance, and the phenylthiourea solution of various concentrations is poured into circle respectively In each liquid storage cylinder on disk, cell battery lead plate is put into standing groove, then liquid droping head is adjusted to specified location by lifter;
N2:Phenylthiourea solution injection drip chamber on computer control disk in liquid storage cylinder corresponding with drip chamber, drop Phenylthiourea solution in liquid room is dripped on cell battery lead plate by liquid droping head, and micro pump controls the dropping liquid amount and dropping liquid of liquid droping head Time, at interval of 2.1 seconds dropping liquids once, each dropping liquid amount is 0.05ml to liquid droping head, dropping liquid 260 times altogether;
N3:After dropping liquid terminates, drainage mechanism discharges remaining phenylthiourea solution in drip chamber, and wiper mechanism is to dropping liquid Room carries out cleaning drying;
N4:Signal on SAW resonator collection cell battery lead plate is sent to converting unit, converting unit output frequency Rate response curve up-samples in the frequency response curve received to computer, computer, obtains 120 sampled values, will sample Value is used as input data S (t), inputs second-order linear system accidental resonance model In, and second-order linear system accidental resonance model is resonated, obtain the phenyl sulphur The output signal-to-noise ratio of urea solution;
N5:Computer controls disk rotational certain angle, and next liquid storage cylinder is turned into position corresponding with drip chamber, Phenylthiourea solution in the liquid storage cylinder is injected into drip chamber, step N2 to step N4 is repeated, obtains in the liquid storage cylinder The output signal-to-noise ratio of phenylthiourea solution, then disk be rotated further by certain angle, detect the phenyl sulphur in next liquid storage cylinder The output of the output signal-to-noise ratio of urea solution, so circulation until detecting the phenylthiourea solution on disk in all liquid storage cylinders is believed Make an uproar ratio;
N6:The concentration of the phenylthiourea solution obtained in advance is respectively k1, k2..., kN, its corresponding output signal-to-noise ratio point Wei not SNR1, SNR2..., SNRN, computer is by point (k1, SNR1), (k2, SNR2) ..., (kN, SNRN) it is fitted to one directly Line, the forecast model of phenylthiourea solution is obtained according to the straight line of fitting:
Step N4 Computers are in the frequency response curve up-sampling received, to being surveyed before liquid droping head during 30 dropping liquids The frequency obtained is without sampling, because being remained on the dropping liquid incipient cell battery lead plate detected to each liquid storage luminal solution There is the last solution detected, after preceding 30 dropping liquids, the solution of last detection is cleaned out on cell battery lead plate, is ensured Accuracy of detection.

Claims (5)

  1. A kind of 1. phenylthiourea solution concentration detector, it is characterised in that:Including computer (1), collecting unit and collection work Make platform, the collecting unit includes cell battery lead plate (2), SAW resonator (3) and converting unit (4), the collection work Making platform includes base (5), and standing groove (6) and lifter (45) are provided with the base (5), is set above the standing groove (6) Have drip chamber (7), the drip chamber (7) is connected by bindiny mechanism with lifter (45), drip chamber (7) bottom be provided with The micro pump (8) of drip chamber (7) connection, micro pump (8) bottom are provided with the liquid droping head (9) connected with micro pump, the drop Inlet (10) is provided with the top of liquid room (7), wiper mechanism and drainage mechanism, the drip chamber are additionally provided with the drip chamber (7) (7) top is provided with disk (11), and several liquid storage cylinders (12), liquid storage cylinder (12) bottom are provided with around the center of circle on the disk (11) Portion position corresponding with inlet (10) is provided with liquid outlet (13), and the liquid outlet (13) is provided with liquid outlet electromagnetic valve (14), institute State the motor (15) that driving disk rotational is provided with the top of drip chamber (7), the SAW resonator (3) respectively with cell Battery lead plate (2) and converting unit (4) electrical connection, the computer (1) respectively with converting unit (4), micro pump (8), cleaning machine Structure, drainage mechanism, liquid outlet electromagnetic valve (14), motor (15) and lifter (45) electrical connection, the wiper mechanism include into Gas port (21) and water inlet (22), the drip chamber (7) are connected by a connecting line and air inlet (21) and water inlet (22) Logical, the air inlet (21) is connected with air pump (23), and the water inlet (22) is connected with water pump (24), the water pump (24) and water Case is connected, and the air inlet (21) is provided with air inlet electromagnetic valve (25), and the water inlet (22) is provided with entering water electromagnetic valve (26), described Air pump (23), water pump (24), air inlet electromagnetic valve (25) and entering water electromagnetic valve (26) electrically connect with computer (1) respectively, described clear Washing machine structure also includes the rabbling mechanism being arranged in drip chamber (7), and the rabbling mechanism includes horizontally disposed hollow cross bar (27) and longitudinally disposed hollow vertical pole (28), the bottom in cross bar (27) stage casing are set in vertical pole (28) by bearing Top, the cavity in the cross bar (27) connect with the cavity in vertical pole (28), the leading flank and horizontal stroke of described cross bar (27) one end The trailing flank of bar (27) other end is provided with several through holes (29), and the through hole (29) connects with cross bar (27) internal cavity, described Vertical pole (28) is arranged on drip chamber (7) bottom, and the cavity in the vertical pole (28) is by connecting line and air inlet (21) and enters The mouth of a river (22) connects, and the wiper mechanism also includes air heater (30), the air outlet and gas of the air heater (30) The air inlet connection of pump (23), the air heater (30) electrically connect with computer (1), and the drainage mechanism includes being arranged on The drainpipe (31) of drip chamber (7) bottom, the drainpipe (31) connect with drip chamber (7), and the drainpipe (31) is provided with Drain solenoid valve (32), the drain solenoid valve (32) electrically connect with computer (1);
    After each dropping liquid terminates, drainage mechanism first discharges the surplus solution in drip chamber, and then drain solenoid valve is closed, and carries out Cleaning;Air inlet electromagnetic valve to be closed, starts water pump, open entering water electromagnetic valve, clear water is passed through cross bar from vertical pole, and from the through hole of cross bar Interior discharge, cross bar is driven to rotate when clear water is discharged out of through hole, when clear water reaches a certain amount of in drip chamber, cross bar rotates stirring Clear water, make drip chamber cleaning more thorough;Then drainage mechanism discharges water, switches off the pump and entering water electromagnetic valve, booster air pump, sky Hot-air heater, air inlet electromagnetic valve is opened, air pump is passed through hot-air into drip chamber and dries up drip chamber;It is clear in drainage mechanism discharge After water, hot-air is passed through cross bar, and is discharged from through hole, and cross bar rotates, and accelerates the flowing of dropping liquid indoor air flow, accelerates drip chamber and dries Speed.
  2. A kind of 2. phenylthiourea solution concentration detector according to claim 1, it is characterised in that:The cell electrode Plate (2) includes substrate (16), and the substrate (16) is provided with working electrode (17), to electrode (18) and two reference electrodes (19), the working electrode (17) includes the rounded portions of front end, and the rounded portions are made up of foam copper, and one layer is coated with the foam copper Gold plated Layer, the Gold plated Layer is provided with mouse bacterium shape taste bud taste receptor cells, described to the front end of electrode (18) and reference electricity The front end of pole (19) is curved to be centered around on the outside of rounded portions, working electrode (17) front end, to electrode (18) front end and reference Electrode (19) front end outer side scribbles painting layer (20).
  3. A kind of 3. phenylthiourea solution concentration detector according to claim 1, it is characterised in that:The converting unit (4) oscillating circuit and frequency detector are included, the SAW resonator (3) is electrically connected by oscillating circuit and frequency detector Connect, the frequency detector electrically connects with computer (1).
  4. A kind of 4. phenylthiourea solution concentration detection method, suitable for one kind described in any claim claim 1-3 Phenylthiourea solution concentration detector, it is characterised in that comprise the following steps:
    S1:Phenylthiourea solution to be measured is poured on disk in liquid storage cylinder corresponding with drip chamber, then by the benzene in liquid storage cylinder Base thiourea solution injects drip chamber;
    S2:Liquid droping head drips to phenylthiourea solution on cell battery lead plate, when micro pump controls the dropping liquid amount and dropping liquid of liquid droping head Between, at interval of 2.1 seconds dropping liquids once, each dropping liquid amount is 0.05ml to liquid droping head, dropping liquid 260 times altogether, and dropping liquid is discharged after terminating Surplus solution in drip chamber, and cleaning drying is carried out to drip chamber;
    S3:Signal on SAW resonator collection cell battery lead plate is sent to converting unit, and converting unit output frequency rings Curve is answered to be up-sampled in the frequency response curve received to computer, computer, obtain 110-120 sampled value, will sample Value is used as input data S (t), inputs second-order linear system accidental resonance model In, and second-order linear system accidental resonance model is resonated,
    Wherein, x (t) is the displacement for vibrating particle, and Ω is angular frequency, and r and ω are attenuation coefficient and the linear oscillator of setting respectively The frequency of particle, c are the signal adjustment coefficients of setting, and b is the quadratic noise ξ of setting2(t) coefficient, ξ (t) are three discrimination noises, ξ (t) ∈ {-a, 0, a }, a > 0, the dismutation of noise follows Poisson distribution, and its probability distribution is ps(a)=ps(- a)=q, ps (0)=1-2q, wherein 0 < q < 0.5;
    Noise average follows with correlation<ξ(t)>=0,<ξ(t)ξ(t+τ)>=2qa2e-λτ,
    Wherein λ is correlation ratio, and three discrimination noise ξ (t) glacing flatness is
    The output signal-to-noise ratio for obtaining phenylthiourea solution to be measured is
    S4:Obtained output signal-to-noise ratio SNR is substituted into phenylthiourea solution concentration forecast model:Meter Calculate the concentration k of phenylthiourea solution to be measured.
  5. A kind of 5. phenylthiourea solution concentration detection method according to claim 4, it is characterised in that:The phenylthiourea Solution concentration forecast model is obtained by following steps:
    N1:The phenylthiourea solution of various concentrations is obtained in advance, and the phenylthiourea solution of various concentrations is poured on disk respectively Each liquid storage cylinder in;
    N2:Phenylthiourea solution injection drip chamber on computer control disk in liquid storage cylinder corresponding with drip chamber, drip chamber Interior phenylthiourea solution is dripped on cell battery lead plate by liquid droping head, when micro pump controls the dropping liquid amount and dropping liquid of liquid droping head Between, at interval of 2.1 seconds dropping liquids once, each dropping liquid amount is 0.05ml to liquid droping head, dropping liquid 260 times altogether;
    N3:After dropping liquid terminates, drainage mechanism discharges remaining phenylthiourea solution in drip chamber, and wiper mechanism enters to drip chamber Row cleaning drying;
    N4:Signal on SAW resonator collection cell battery lead plate is sent to converting unit, and converting unit output frequency rings Curve is answered to be up-sampled in the frequency response curve received to computer, computer, obtain 110-120 sampled value, will sample Value is used as input data S (t), inputs second-order linear system accidental resonance modelIn, and make second-order linear system common at random The model that shakes resonates, and obtains the output signal-to-noise ratio of the phenylthiourea solution;
    N5:Computer controls disk rotational certain angle, next liquid storage cylinder is turned into position corresponding with drip chamber, by this Phenylthiourea solution injection drip chamber in liquid storage cylinder, repeats step N2 to step N4, obtains the phenyl in the liquid storage cylinder The output signal-to-noise ratio of thiourea solution, then disk be rotated further by certain angle, detect that the phenylthiourea in next liquid storage cylinder is molten The output signal-to-noise ratio of liquid, so circulate the output noise until detecting the phenylthiourea solution on disk in all liquid storage cylinders Than;
    N6:The concentration of the phenylthiourea solution obtained in advance is respectively k1, k2..., kN, its corresponding output signal-to-noise ratio is respectively SNR1, SNR2..., SNRN, computer is by point (k1, SNR1), (k2, SNR2) ..., (kN, SNRN) it is fitted in alignment, root The forecast model of phenylthiourea solution is obtained according to the straight line of fitting:
CN201510066317.XA 2015-02-09 2015-02-09 A kind of phenylthiourea solution concentration detector and method Expired - Fee Related CN105004767B (en)

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CN105866202B (en) * 2016-03-29 2018-06-22 天津商业大学 A kind of preparation method of the cell-membrane receptor electrochemistry type sensor based on G-protein signal amplifying system
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CN112760221B (en) * 2020-12-23 2022-11-25 浙江农林大学 Vibrio parahaemolyticus detection device and method

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1524965A (en) * 2003-09-16 2004-09-01 山东省科学院生物研究所 Rapid determination method for vitality of diastatic enzyme
CN101726620A (en) * 2008-10-30 2010-06-09 深圳迈瑞生物医疗电子股份有限公司 Biochemical analyser and fluid element cleaning method thereof
CN103018293A (en) * 2012-10-25 2013-04-03 红塔烟草(集团)有限责任公司 Method for quickly detecting intensity of four basic tastes in liquid food by using electronic tongue
CN103424525A (en) * 2013-03-18 2013-12-04 浙江工商大学 Milk quality detection equipment and method
CN103558351A (en) * 2013-08-01 2014-02-05 浙江工商大学 Green tea beverage quality analysis apparatus based on intelligent electronic nose system, and method
CN104089996A (en) * 2014-01-17 2014-10-08 浙江工商大学 Taste cell sensor using surface acoustic wave resonator and preparation method thereof
CN204044164U (en) * 2014-06-23 2014-12-24 珠海森龙生物科技有限公司 Mini-clinical biochemical analyzer

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040191918A1 (en) * 2003-03-28 2004-09-30 Sandrine Isz Evaluation of bitterness of active drugs

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1524965A (en) * 2003-09-16 2004-09-01 山东省科学院生物研究所 Rapid determination method for vitality of diastatic enzyme
CN101726620A (en) * 2008-10-30 2010-06-09 深圳迈瑞生物医疗电子股份有限公司 Biochemical analyser and fluid element cleaning method thereof
CN103018293A (en) * 2012-10-25 2013-04-03 红塔烟草(集团)有限责任公司 Method for quickly detecting intensity of four basic tastes in liquid food by using electronic tongue
CN103424525A (en) * 2013-03-18 2013-12-04 浙江工商大学 Milk quality detection equipment and method
CN103558351A (en) * 2013-08-01 2014-02-05 浙江工商大学 Green tea beverage quality analysis apparatus based on intelligent electronic nose system, and method
CN104089996A (en) * 2014-01-17 2014-10-08 浙江工商大学 Taste cell sensor using surface acoustic wave resonator and preparation method thereof
CN204044164U (en) * 2014-06-23 2014-12-24 珠海森龙生物科技有限公司 Mini-clinical biochemical analyzer

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