CN104458836B - Examination of glucose concentration device and detection method - Google Patents

Examination of glucose concentration device and detection method Download PDF

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Publication number
CN104458836B
CN104458836B CN201410499359.8A CN201410499359A CN104458836B CN 104458836 B CN104458836 B CN 104458836B CN 201410499359 A CN201410499359 A CN 201410499359A CN 104458836 B CN104458836 B CN 104458836B
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electrode
container
glucose
working electrode
controller
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CN104458836A (en
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惠国华
金姣姣
刘伟
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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 examination of glucose concentration device and detection method, the examination of glucose concentration device is electrically connected with electrochemical workstation;Including controller, memory, fill the container of the upper end opening of liquid, cover board on container, the guide rail in involute shape on cover board lower surface, it in the insertion liquid of guide rail inner end and uses made of alloy platinum material to electrode, the tumbler that can be moved along guide rail on guide rail, the dropping funel for the instillation glucose solution into container for the agitating device of agitated liquid and on cover board in container;The present invention has accuracy of detection high, and speed is fast;Device stability is good, it is reproducible the characteristics of.

Description

Examination of glucose concentration device and detection method
Technical field
It is high more particularly, to a kind of detection accuracy the present invention relates to technical field of food detection, fireballing glucose Concentration detection apparatus and detection method.
Background technology
Existing sugar detection technical method has Instrumental Analysis detection method and chemical measure, although Instrumental Analysis detection method is grasped Make it is simple, but there are accuracy of detection it is low the defects of;There are cumbersome, the deficiencies of poor repeatability for chemical measure.
Chinese patent mandate publication number:CN103528877A authorizes publication date on January 22nd, 2014, discloses a kind of small The online system of detecting concentration of sugar of type biochemical reactor including 1 touch-screen, is responsible for receiving the setting and operation of Field Force;2 Constant flow pump is responsible for being diluted reaction solution;1 online sugar analyzer is responsible for the on-line checking of sugar concentration;1 offline sugar is dense Analyzer is spent, is responsible for the offline inspection of sugar concentration;1 flush bonding module BL2100 as the control unit of system, controls constant current The action of the flow velocity of pump and sugared concentration analyzer gathers the sugared concentration Testing value of online sugar analyzer, collection value is carried out Line corrects, and obtains accurately sugar concentration Testing value, and joining according to the value of offline sugared concentration analyzer to model in biochemical reactor Number is modified.The disadvantage of this invention is that the low deficiency with poor repeatability of accuracy of detection.
The content of the invention
The goal of the invention of the present invention is to overcome detection method accuracy of detection of the prior art low and poor repeatability Deficiency provides a kind of detection accuracy height, fireballing examination of glucose concentration device and detection method.
To achieve these goals, the present invention uses following technical scheme:
A kind of examination of glucose concentration device, the examination of glucose concentration device are electrically connected with electrochemical workstation;Bag Include controller, memory fills the container of the upper end opening of liquid, the cover board on container, on cover board lower surface In the guide rail of involute shape, in the insertion liquid of guide rail inner end and use made of alloy platinum material to electrode, on guide rail The tumbler that can be moved along guide rail, be used in container for the agitating device of agitated liquid and on cover board The dropping funel of glucose solution is instilled into container;The tumbler lower part is equipped in insertion liquid and uses foam copper material Working electrode made of material is connected to electrode by the first motor being arranged on guide rail inner end with guide rail, and agitating device passes through Gas-guide tube is connected with cover board, and gas-guide tube is equipped with air pump;The controller respectively with memory, the first motor, tumbler, Agitating device, air pump and electrochemical workstation electrical connection;Electrode and working electrode are electrically connected respectively with electrochemical workstation.
The setting of the guide rail in involute shape of the present invention makes working electrode and continuously adjustable to the spacing between electrode, The optimum position residing for two electrodes when making highest current density is found convenient for electrochemical workstation, so as to improve accuracy of detection Property.For being stirred to the liquid in container, tumbler is used to that working electrode to be driven to move agitating device.
The present invention obtains the concentration of glucose prediction model of concentration of glucose by detecting known concentration glucose solution, And the concentration of glucose of unknown concentration is detected with concentration of glucose prediction model.
Therefore, the present invention has easy to operate, high degree of automation;Accuracy of detection is high, and speed is fast;Device stability is good, The characteristics of reproducible.
Preferably, the guide rail lower part is equipped with the closed plate for rail closure;The guide rail includes top plate and is arranged on Two baffles of top plate both sides, two baffles are equipped with corresponding guide openings;The tumbler include motor fixing seat, The second motor in motor fixing seat, two gears being connected respectively with two shafts of the second motor and it is respectively arranged on two Two extension rods on the outside of a gear, two extension rods are respectively protruding into two guide openings, are all provided in guide rail and closed plate The dual-cavity with two gear cooperations is useful for, concave-concave groove bottom wall is equipped with groove;Second motor is electrically connected with the controller; The working electrode passes through the involute shape opening extended along guide rail being arranged in closed plate to be connected with motor fixing seat.
The setting of guide rail, tumbler and closed plate allows working electrode to be moved along what guide rail was stablized.
Preferably, the agitating device includes the column arranged on container bottom and the T-shaped stirring pipe in column;Institute It states column top edge and is equipped with outwards horizontal-extending flange, the lower edge of T-shaped stirring pipe is equipped with the inside water being adapted with flange The annular edge of flat extension, annular edge upper surface and flange lower surface clearance fit;
Column top is equipped with baffle ring, and baffle ring upper surface is in contact with annular edge lower surface;Column lower part is connected with gas-guide tube It connects;
The outer circumferential surface rear portion of T-shaped stirring pipe one end is equipped with several ventholes, before the outer circumferential surface of the other end of T-shaped stirring pipe Portion is equipped with several ventholes.
Preferably, the cross section of the T-shaped stirring pipe is oval, the outer circumferential surface lower part of T-shaped stirring pipe is equipped with several A venthole.The structure setting of agitating device is stirred the solution in container more uniform.
Preferably, working electrode and to electrode be in bar shaped plate.
A kind of detection method suitable for examination of glucose concentration device includes the following steps:
Sweep interval A, scanning times maximum N are equipped in (6-1) controller, scanning times sequence number i's, i is initial It is worth for 1;
25 to 50ml 0.1M NaOH is taken to be inserted into container, cover board is installed to container finish, makes working electrode and to electricity Pole is stretched into NaOH;
Electrochemical workstation exports the constant voltage of 0.45V to 0.55V to working electrode, and the glucose that adjusting fills 0.1M is molten The piston of the dropping funel of liquid makes dropping funel instill a drop glucose solution into container every time A;
(6-2) dropping funel instilled into container first drop glucose after to instill second drop glucose solution it Before, controller controls agitating device to liquid agitation time B, the B < A in container by air pump;Controller controls the first motor It drives and electrode is rotated horizontally, while control tumbler that working electrode is driven to be moved back and forth along guide rail, electrochemical workstation inspection Current density is surveyed, when the current density of detection reaches maximum, controller control tumbler and the first motor are stopped, Obtain the optimum position to electrode and working electrode;
During being rotated horizontally to electrode and working electrode moves, maximum is remained to electrode and working electrode Relative area;
Controller calculates the concentration of glucose k in current container1, by k1With with k1Corresponding current density S (t) storage Into memory;
(6-3) dropping funel instills i+1 drop glucose solution into container, and controller controls agitating device by air pump To liquid agitation time B, the B < A in container;Electrochemical workstation detects current density, and controller is calculated in current container Concentration of glucose ki+1, by ki+1With with ki+1Corresponding current density S (t) storage is into memory;
(6-4) makes i values increase by 1, is transferred to step (6-3) as i≤N-1;Otherwise, it is transferred to step (6-5);
Obtained N number of current density S (t) is inputted second-order linear system accidental resonance model by (6-5) controller respectivelyIn;And make second-order linear system common at random The model that shakes resonates;
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 follow Poisson distribution, probability distribution ps(a)=ps(-a) =q, ps(0)=1-2q, wherein 0 < q < 0.5;
Noise average is followed with correlation<ξ(t)>=0,<ξ(t)ξ(t+τ)>=2qa2e-λτ
Wherein λ is correlation ratio, and the glacing flatness of three discrimination noise ξ (t) is
Utilize formulaIt calculates and obtains corresponding respectively with N number of current density S (t) Output signal-to-noise ratio SNR1, SNR2..., SNRN
Controller reads the concentration of glucose k in memory1, k2..., kN;Controller utilizes point (k1, SNR1), (k2, SNR2) ..., (kN, SNRN) fitting be in line, concentration of glucose prediction model is drawn according to the straight line of fitting:The liquid of container is poured out, and vessel cleaning is clean;
The detection of the glucose solution W of (6-6) unknown concentration:
25 to 50ml glucose solution W is taken to be inserted into container, cover board is installed to container finish, makes working electrode and right Electrode is stretched into glucose solution, and is made working electrode and be located at optimum position determined by step (6-2) to electrode;Electrochemistry Work station is to the constant voltage of working electrode output 0.45V to 0.55V, electrochemical workstation detection current density S (t), controller S (t) is inputted in second-order linear system accidental resonance model,
And utilize formulaOutput signal-to-noise ratio SNR is calculated and obtained, SNR is substituted intoObtain the concentration k of glucose solution W.
Preferably, alarm is further included, alarm and controller electrical connection;It is further included before step (6-1) as follows Electrode calibration step:
(7-1) takes 25 to 40ml 0.1M NaOH to be inserted into the first beaker, is burnt by working electrode and to electrode insertion first In the NaOH solution of cup, cyclic voltammetry scanning is carried out using electrochemical workstation, make the driving voltage of working electrode- First gradually increase, then be gradually reduced in the range of 0.2V-0.7V, obtains abscissa as driving voltage, and ordinate is current density Curve, the difference g between the maximum and minimum value of calculating current density;
(7-2) takes 0.1M NaOH and 0.1mM glucose to be inserted into the second beaker successively according to 3: 2 ratio, and stirs equal It is even, it is inserted by working electrode and to electrode in the solution of the second beaker, cyclic voltammetry scanning is carried out using electrochemical workstation, Make driving voltage first gradually increase, then be gradually reduced in the range of -0.2V-0.7V of working electrode, obtain abscissa as excitation Voltage, ordinate is the curve of current density, the difference g ' between the maximum and minimum value of calculating current density;
(7-3) controller utilizesCalculation error as e≤5%, is transferred to step (6-1);
Otherwise, controller control alarm equipment alarm, operating personnel are to being surface-treated electrode or being replaced to electrode;It returns Return step (7-1).
Because working electrode made of foam copper product is disposable, examined every time with new working electrode It surveys, but multiple Reusability is wanted to electrode made of alloy platinum material, access times are more, more serious by oxidation corrosion to electrode, So needing to be detected the state to electrode, after calibration, only qualified is just used in electrode detection, it is ensured that inspection Survey the accuracy of result.
Preferably, driving voltage is first gradually increased in the range of -0.2V-0.7V with the speed of 0.05V/s, then with The speed of 0.05V/s is gradually reduced.
Preferably, the area that foam copper and platinum electrode stretch into solution is 0.08cm2To 0.12cm2
Preferably, A is 45 to 55 seconds, N is that 10 to 100, B is 10 to 30 seconds.
Therefore, the present invention has the advantages that:It is easy to operate, high degree of automation;Accuracy of detection is high, and speed is fast; Device stability is good, reproducible.
Description of the drawings
Fig. 1 is a kind of structure diagram of the present invention;
Fig. 2 is a kind of structure diagram of the guide rail of the present invention;
Fig. 3 is a kind of structure diagram of the tumbler of the present invention;
Fig. 4 is a kind of structure diagram of the agitating device of the present invention;
Fig. 5 is a kind of functional block diagram of the present invention;
Fig. 6 is a kind of flow chart of the embodiment of the present invention 1;
Fig. 7 is the cyclic voltammetry calibration result figure of the present invention.
In figure:Electrochemical workstation 1, controller 2, memory 3, container 4, cover board 5, guide rail 6, to electrode 7, tumbler 8th, agitating device 9, dropping funel 10, working electrode 11, the first motor 12, gas-guide tube 13, air pump 14, closed plate 15, baffle 16, Motor fixing seat 17, the second motor 18, shaft 19, gear 20, extension rod 21, dual-cavity 22, column 23, T-shaped stirring pipe 24, gear Circle 25, venthole 26, guide rail inner end 27.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and detailed description.
Embodiment 1
Embodiment as shown in Figure 1 is a kind of examination of glucose concentration device, examination of glucose concentration device and electrochemistry Work station 1 is electrically connected;Including controller 2, memory 3 fills the container 4 of the upper end opening of liquid, the cover board on container 5, the guide rail 6 in involute shape being arranged on cover board lower surface as shown in Figure 2, as shown in Figure 1, inserting arranged on guide rail inner end 27 Enter in liquid and using made of alloy platinum material to electrode 7, on guide rail can be along the tumbler 8 that guide rail moves, arranged on appearance The agitating device 9 as shown in Figure 3 for agitated liquid in device;
As shown in Figure 1, cover board is equipped with to instill the dropping funel 10 of glucose solution into container;Electrode is led to The first motor 12 crossed on guide rail inner end is connected with guide rail, and agitating device is connected by gas-guide tube 13 with cover board, is led Tracheae is equipped with air pump 14;
As shown in figure 5, controller respectively with memory, the first motor, tumbler, agitating device, air pump and electrochemistry Work station is electrically connected;Electrode and working electrode are electrically connected respectively with electrochemical workstation.
As shown in figure 3, tumbler lower part is equipped in insertion liquid and using working electrode 11 made of foam copper product; Guide rail lower part is equipped with the closed plate 15 for rail closure;Guide rail include top plate and two baffles 16 arranged on top plate both sides, two A baffle is equipped with corresponding guide openings;Tumbler includes motor fixing seat 17, second in motor fixing seat Motor 18, two gears 20 being connected respectively with two shafts 19 of the second motor and be respectively arranged on on the outside of two gears two A extension rod 21, two extension rods are respectively protruding into two guide openings, be equipped on guide rail and closed plate for two teeth The dual-cavity 22 of cooperation is taken turns, concave-concave groove bottom wall is equipped with groove;Second motor is electrically connected with the controller;Working electrode is passed through and is arranged on The involute shape opening extended along guide rail in closed plate is connected with motor fixing seat.Cover board uses polytetrafluoroethylene material system Into container is made of glass material.
As shown in figure 4, agitating device includes the column 23 arranged on container bottom and the T-shaped stirring pipe 24 in column; Column top edge is equipped with outwards horizontal-extending flange, and the lower edge of T-shaped stirring pipe is equipped with the inside level being adapted with flange The annular edge of extension, annular edge upper surface and flange lower surface clearance fit;
Column top is equipped with baffle ring 25, and baffle ring upper surface is in contact with annular edge lower surface;Column lower part and gas-guide tube phase Connection;
The outer circumferential surface rear portion of T-shaped stirring pipe one end is equipped with 23 ventholes, the outer circumferential surface forepart of the other end of T-shaped stirring pipe Equipped with 20 ventholes 26.
As shown in Figure 1, the cross section of T-shaped stirring pipe is oval, the outer circumferential surface lower part of T-shaped stirring pipe goes out equipped with several Stomata.Working electrode and to electrode be in bar shaped plate.
As shown in fig. 6, a kind of detection method of examination of glucose concentration device, includes the following steps:
Step 100, sweep interval 50 seconds, scanning times maximum N=10, scanning times sequence number are equipped in controller The initial value of i, i are 1;
The 0.1M NaOH of 30ml is taken to be inserted into container, cover board is installed to container finish, makes working electrode and electrode is stretched Enter in NaOH;
Electrochemical workstation exports the constant voltage of 0.5V to working electrode, adjusts the dropping liquid for the glucose solution for filling 0.1M The piston of funnel makes dropping funel instill a drop glucose solution into container every 50 seconds;
Step 200, optimum position is found and by k1With with k1Corresponding current density S (t) storage is into memory:
After dropping funel instills the first drop glucose into container to before instilling the second drop glucose solution, control Device controls agitating device to the liquid agitation 10 seconds in container by air pump;It is horizontal to electrode that controller controls the first motor to drive Rotation, while control tumbler that working electrode is driven to be moved back and forth along guide rail, electrochemical workstation detection current density works as inspection When the current density of survey reaches maximum, controller control tumbler and the first motor are stopped, and obtain to electrode and work Make the optimum position of electrode;
During being rotated horizontally to electrode and working electrode moves, maximum is remained to electrode and working electrode Relative area;
Controller calculates the concentration of glucose k in current container1(for example, glucose solution is often dripped for 0.05ml, controller Concentration of glucose k is calculated according to the total measurement (volume) of solution in the glucose solution drop number and container instilled in container1), by k1With With k1Corresponding current density S (t) storage is into memory;
Step 300,
Dropping funel instills i+1 drop glucose solution into container, and controller controls agitating device to holding by air pump Liquid agitation in device 10 seconds;Electrochemical workstation detects current density, and controller calculates the concentration of glucose in current container ki+1, by ki+1With with ki+1Corresponding current density S (t) storage is into memory;
Step 400, when i≤9, i values is made to increase by 1, are transferred to step 300;Otherwise, it is transferred to step 500;
Step 500, data processing:
Obtain 10 current density S (t) are inputted second-order linear system accidental resonance model by controller respectivelyIn;And make second-order linear system accidental resonance Model resonates;
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 follow Poisson distribution, probability distribution ps(a)=ps(-a) =q, ps(0)=1-2q, wherein 0 < q < 0.5;
Noise average is followed with correlation<ξ(t)>=0,<ξ(t)ξ(t+τ)>=2qa2e-λτ
Wherein λ is correlation ratio, and the glacing flatness of three discrimination noise ξ (t) is
Utilize formulaIt calculates and obtains corresponding respectively with 10 current density S (t) Output signal-to-noise ratio SNR1, SNR2..., SNR10
Controller reads the concentration of glucose k in memory1, k2..., k10;Controller utilizes point (k1, SNR1), (k2, SNR2) ..., (k10, SNR10) fitting be in line, concentration of glucose prediction model is drawn according to the straight line of fitting:The liquid of container is poured out, and vessel cleaning is clean;
Step 600, the detection of the glucose solution W of unknown concentration:
The glucose solution W of 30ml is taken to be inserted into container, cover board is installed to container finish, makes working electrode and to electrode It stretches into glucose solution, and makes working electrode and optimum position determined by step 200 is located to electrode;Electrochemical workstation To the constant voltage of working electrode output 0.5V, electrochemical workstation detection current density S (t), S (t) is inputted second order by controller In linear system accidental resonance model,
And utilize formulaOutput signal-to-noise ratio SNR is calculated and obtained, SNR is substituted intoObtain the concentration k of glucose solution W.
Embodiment 2
Comprising all structures of embodiment 1 and step part in embodiment 2, alarm, alarm and controller are further included Electrical connection;Following electrode calibration step is further included before step 100:
Step 710, the 0.1M NaOH of 30ml is taken to be inserted into the first beaker, are burnt by working electrode and to electrode insertion first In the NaOH solution of cup, cyclic voltammetry scanning is carried out using electrochemical workstation, make the driving voltage of working electrode- First gradually increase, then be gradually reduced in the range of 0.2V-0.7V, obtains abscissa as driving voltage, and ordinate is current density Curve, the difference g between the maximum and minimum value of calculating current density;
Step 720, according to 3: 2 ratio 0.1M NaOH and 0.1mM glucose is taken to be inserted into the second beaker successively, and stirred It mixes uniformly, is inserted by working electrode and to electrode in the solution of the second beaker, cyclic voltammetry is carried out using electrochemical workstation Scanning makes driving voltage first gradually increase, then be gradually reduced in the range of -0.2V-0.7V of working electrode, and obtaining abscissa is Driving voltage, ordinate is the curve of current density, the difference g ' between the maximum and minimum value of calculating current density;
Step 730, controller utilizesCalculation error as e≤5%, is transferred to step 100;
Otherwise, controller control alarm equipment alarm, operating personnel are to being detected electrode, in the present embodiment, discovery pair Electrode surface has defect, to being replaced to electrode;Return to step 710.
Fig. 7 is the cyclic voltammetry calibration testing result figure shown on electrochemical workstation, by that can be drawn in figure, G '=6.8V, g '=6.6V,Therefore it is transferred to step 100.
In the present embodiment, driving voltage is first gradually increased in the range of -0.2V-0.7V with the speed of 0.05V/s, then with The speed of 0.05V/s is gradually reduced.The area that foam copper and platinum electrode stretch into solution is 0.1cm2
It is to be understood that the present embodiment is only illustrative of the invention and is not intended to limit the scope of the invention.In addition, it should also be understood that, After having read the content of the invention lectured, those skilled in the art can make various modifications or changes to the present invention, these etc. Valency form is also fallen within the scope of the appended claims of the present application.

Claims (8)

1. a kind of detection method of examination of glucose concentration device, examination of glucose concentration device and electrochemical workstation (1) electricity Connection;Examination of glucose concentration device includes controller (2), and memory (3) fills the container (4) of the upper end opening of liquid, if In the cover board (5) on container, the guide rail (6) in involute shape on cover board lower surface, arranged on inserting for guide rail inner end (27) Enter in liquid and using made of alloy platinum material to electrode (7), on guide rail can along the tumbler (8) that guide rail moves, if In the agitating device (9) for agitated liquid in container and on cover board for instilling glucose solution into container Dropping funel (10);The tumbler lower part is equipped in insertion liquid and using working electrode made of foam copper product (11), it is connected to electrode by the first motor (12) being arranged on guide rail inner end with guide rail, agitating device passes through gas-guide tube (13) it is connected with cover board, gas-guide tube is equipped with air pump (14);The controller fills respectively with memory, the first motor, rotation It puts, the electrical connection of agitating device, air pump and electrochemical workstation;It is electrically connected respectively with electrochemical workstation to electrode and working electrode It connects;Working electrode and to electrode be in bar shaped plate;It is characterized in that include the following steps:
Sweep interval A, scanning times maximum N are equipped in (1-1) controller, the initial value of scanning times sequence number i, i are 1;
25 to 50ml 0.1M NaOH is taken to be inserted into container, cover board is installed to container finish, makes working electrode and electrode is stretched Enter in NaOH;
Electrochemical workstation exports the constant voltage of 0.45V to 0.55V to working electrode, and adjusting fills the glucose solution of 0.1M The piston of dropping funel makes dropping funel instill a drop glucose solution into container every time A;
(1-2) to before instilling the second drop glucose solution, is controlled after dropping funel instills the first drop glucose into container Device processed controls agitating device to liquid agitation time B, the B < A in container by air pump;Controller controls the drive pair of the first motor Electrode rotates horizontally, while controls tumbler that working electrode is driven to be moved back and forth along guide rail, electrochemical workstation detection electric current Density, when the current density of detection reaches maximum, controller control tumbler and the first motor are stopped, and obtain pair The optimum position of electrode and working electrode;
During being rotated horizontally to electrode and working electrode moves, the opposite of maximum is remained to electrode and working electrode Area;
Controller calculates the concentration of glucose k in current container1, by k1With with k1The storage of corresponding current density S (t) is to depositing In reservoir;
(1-3) dropping funel instills i+1 drop glucose solution into container, and controller controls agitating device to holding by air pump Liquid agitation time B, B < A in device;Electrochemical workstation detects current density, and controller calculates the grape in current container Sugared concentration ki+1, by ki+1With with ki+1Corresponding current density S (t) storage is into memory;
(1-4) makes i values increase by 1, is transferred to step (1-3) as i≤N-1;Otherwise, it is transferred to step (1-5);
Obtained N number of current density S (t) is inputted second-order linear system accidental resonance model by (1-5) controller respectivelyIn;And just second-order linear system accidental resonance Model resonates;
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 follow Poisson distribution, probability distribution ps(a)=ps(- a)=q, ps (0)=1-2q, wherein 0 < q < 0.5;
Noise average is followed with correlation<ξ(t)>=0,<ξ(t)ξ(t+τ)>=2qa2e-λτ,<ξ(t)>For the integral mean of ξ (t) Value,<ξ(t)ξ(t+τ)>For the integral mean of ξ (t) ξ (t+ τ);
Wherein λ is correlation ratio, and the glacing flatness of three discrimination noise ξ (t) is
Controller utilizes formulaIt calculates and obtains corresponding respectively with N number of current density S (t) Output signal-to-noise ratio SNR1, SNR2..., SNRN
Controller reads the concentration of glucose k in memory1, k2..., kN;Controller utilizes point (k1, SNR1), (k2, SNR2) ..., (kN, SNRN) fitting be in line, concentration of glucose prediction model is drawn according to the straight line of fitting:The liquid of container is poured out, and vessel cleaning is clean;
The detection of the glucose solution W of (1-6) unknown concentration:
25 to 50ml glucose solution W is taken to be inserted into container, cover board is installed to container finish, makes working electrode and to electrode It stretches into glucose solution, and makes working electrode and optimum position determined by step (1-2) is located to electrode;Electrochemical operation The constant voltage stood to working electrode output 0.45V to 0.55V, electrochemical workstation detection current density S (t), controller is by S (t) input in second-order linear system accidental resonance model,
And utilize formulaOutput signal-to-noise ratio SNR is calculated and obtained, SNR is substituted intoObtain the concentration k of glucose solution W.
2. the detection method of examination of glucose concentration device according to claim 1, it is characterized in that, the guide rail lower part is set It is useful for the closed plate (15) of rail closure;The guide rail include top plate and two baffles (16) arranged on top plate both sides, two Baffle is equipped with corresponding guide openings;The tumbler includes motor fixing seat (17), in motor fixing seat Second motor (18), two gears (20) being connected respectively with two shafts (19) of the second motor and it is respectively arranged on two gears Two extension rods (21) on outside, two extension rods are respectively protruding into two guide openings, are equipped in guide rail and closed plate For the dual-cavity (22) with two gear cooperations, concave-concave groove bottom wall is equipped with groove;Second motor is electrically connected with controller It connects;The working electrode passes through the involute shape opening extended along guide rail being arranged in closed plate to be connected with motor fixing seat.
3. the detection method of examination of glucose concentration device according to claim 1, it is characterized in that, the agitating device bag Include the column (23) arranged on container bottom and the T-shaped stirring pipe (24) in column;The column top edge is equipped with outside water The flange of flat extension, the lower edge of T-shaped stirring pipe are equipped with the inside horizontal-extending annular edge being adapted with flange, in annular edge Surface and flange lower surface clearance fit;
Column top is equipped with baffle ring (25), and baffle ring upper surface is in contact with annular edge lower surface;Column lower part is connected with gas-guide tube It connects;
The outer circumferential surface rear portion of T-shaped stirring pipe one end is equipped with several ventholes, and the outer circumferential surface forepart of the other end of T-shaped stirring pipe is set There are several ventholes (26).
4. the detection method of examination of glucose concentration device according to claim 3, it is characterized in that, the T-shaped stirring pipe Cross section it is oval, the outer circumferential surface lower part of T-shaped stirring pipe is equipped with several ventholes.
5. the detection method of examination of glucose concentration device according to claim 1, it is characterized in that, alarm is further included, Alarm and controller electrical connection;Following electrode calibration step is further included before step (1-1):
(5-1) takes 25 to 40ml 0.1M NaOH to be inserted into the first beaker, and the first beaker is inserted by working electrode and to electrode In NaOH solution, cyclic voltammetry scanning is carried out using electrochemical workstation, makes the driving voltage of working electrode in -0.2V- First gradually increase, then be gradually reduced in the range of 0.7V, obtains abscissa as driving voltage, and ordinate is the curve of current density, Difference g between the maximum and minimum value of calculating current density;
(5-2) takes 0.1M NaOH and 0.1mM glucose to be inserted into the second beaker successively according to 3: 2 ratio, and stirs evenly, It is inserted by working electrode and to electrode in the solution of the second beaker, carries out cyclic voltammetry scanning using electrochemical workstation, make The first gradually increase, then be gradually reduced in the range of -0.2V-0.7V of the driving voltage of working electrode obtains abscissa as excitation electricity Pressure, ordinate is the curve of current density, the difference g ' between the maximum and minimum value of calculating current density;
(5-3) controller utilizesCalculation error as e≤5%, is transferred to step (1-1);
Otherwise, controller control alarm equipment alarm, operating personnel are to being surface-treated electrode or being replaced to electrode;Return to step Suddenly (5-1).
6. the detection method of examination of glucose concentration device according to claim 5, it is characterized in that, driving voltage- First gradually increased with the speed of 0.05V/s in the range of 0.2V-0.7V, then be gradually reduced with the speed of 0.05V/s.
7. the detection method of examination of glucose concentration device according to claim 5, it is characterized in that, foam copper and platinum electrode The area for stretching into solution is 0.08cm2To 0.12cm2
8. the detection method of the examination of glucose concentration device according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7, special Sign is that A is 45 to 55 seconds, and N is that 10 to 100, B is 10 to 30 seconds.
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