CN104458866A - Device and method for detecting concentration of D-fructose solution - Google Patents

Abstract

The invention discloses a device and method for detecting concentration of a D-fructose solution. The device comprises a computer and a data acquisition device, wherein the data acquisition device comprises an electrochemical workstation, a container, a working electrode and a counter electrode, a cover plate is arranged at the top of the container, the working electrode and the counter electrode are oppositely arranged below the cover plate, a guide slot is formed in the cover plate, a conveying mechanism is arranged in the guide slot, the guide slot comprises an involute-shaped through slot and a groove in head-to-tail connection with the through slot, the top of the working electrode is connected with a first connection column, the first connection column penetrates through the cover plate and is positioned at the center of an involute base circle of the through slot, the top of the counter electrode is connected with a second connection column, the second connection column is fixed on the conveying mechanism and penetrates through the through slot, the top end of the first connection column is fixedly connected with the top end of the second connection column through a telescopic rod, the cover plate is connected with a lifter for driving the cover plate to move up and down, and a stirring mechanism is arranged at the bottom of the container. By adopting the device and method disclosed by the invention, the concentration of the D-fructose solution can be rapidly and accurately detected.

Description

A kind of apparatus and method detecting D-Fructose solution concentration

Technical field

The present invention relates to solution concentration detection technical field, particularly relate to a kind of apparatus and method detecting D-Fructose solution concentration.

Background technology

Existing D-Fructose solution concentration detection technical method has instrumental analysis detection method and chemical measure, although instrumental analysis detection method is simple to operate, there is the defect that accuracy of detection is low; There is complex operation in chemical measure, the deficiency of poor repeatability.

China Patent Publication No. CN103528877, publication date on January 22nd, 2014, the name of invention is called the online system of detecting concentration of sugar of a kind of miniature biochemical reactor, this application case discloses the online system of detecting concentration of sugar of a kind of miniature biochemical reactor, it is primarily of compositions such as flush bonding module, touch-screen, constant flow pump, online sugared concentration analyzer and off-line sugar concentration analyzers, wherein, touch-screen is man-machine interface, accepts setting and the operation of field staff; Flush bonding module is as the control module of system, control the flow velocity of constant flow pump and the action of sugared concentration analyzer, gather the sugared Concentration Testing value of online glycan analysis instrument, on-line correction is carried out to collection value, to obtain in biochemical reactor sugared Concentration Testing value accurately, and can revise model parameter according to the value of off-line sugar concentration analyzer.Its weak point is, the accuracy of detection of sugared concentration analyzer is lower.

Summary of the invention

The object of the invention is to overcome the technical matters that the accuracy of detection of existing D-Fructose solution concentration detector is lower, provide a kind of apparatus and method detecting D-Fructose solution concentration, it can detect the concentration of D-Fructose solution fast and accurately.

In order to solve the problem, the present invention is achieved by the following technical solutions:

A kind of device detecting D-Fructose solution concentration of the present invention, comprise computing machine and data collector, described data collector comprises electrochemical workstation, container, working electrode and to electrode, described container top is provided with cover plate, described working electrode and to electrode just to being arranged on below cover plate, described cover plate is provided with gathering sill, the conveying mechanism that can move along gathering sill is provided with in described gathering sill, described gathering sill comprises groove in involute shape and groove end to end with groove, described working electrode top is connected with the first joint pin, described first joint pin passes cover plate and is positioned at the involute urve basic circle center of groove, described first joint pin and cover plate are rotationally connected, described second joint pin is connected with to top of electrodes, described second joint pin is fixed on the conveyor and is passed groove, described first joint pin top is fixedly connected with the second joint pin top by expansion link, described cover plate is connected with the lifter driving cover plate to move up and down, described lifter is fixedly connected with container side wall by web member, described container bottom is provided with rabbling mechanism, described computing machine respectively with electrochemical workstation, conveying mechanism, rabbling mechanism and lifter electrical connection, described electrochemical workstation is also electrically connected with working electrode with to electrode respectively.

In the technical program, the 0.1mol/L NaOH solution of getting 25ml adds in container, and electrochemical operation stands in working electrode and the constant voltage to applying+0.5V between electrode.The 0.1mol/L D-Fructose solution getting 0.05ml adds in container, solution stirs by rabbling mechanism work, computing machine is driven by conveying mechanism and moves along groove to electrode, adjustment is to the distance between electrode and working electrode, simultaneous computer detects current density value when being positioned at diverse location to electrode by electrochemical workstation, make to rest on position corresponding to maximum current density value to electrode, then computing machine drives cover plate to move up and down by lifter, thus adjustment working electrode and the degree of depth to solution in electrode immersion container, testing electrode and to electrode immerse solution different depth time current density, finally making working electrode and immersing the degree of depth of solution to electrode is that current density is in maximal value place, and record the D-Fructose concentration X of solution in this current density value S (t) and container.

Groove is involute shape, to electrode along involute motion, increases gradually the distance between electrode and working electrode.The groove of involute shape is conducive to controlling the distance between electrode and working electrode more accurately.First joint pin top is fixedly connected with the second joint pin top by expansion link, when electrode is moved along groove, expansion link free-extension, simultaneous retractable bar drives the first joint pin to rotate, first joint pin drives working electrode synchronous axial system, thus make to remain just to setting to electrode and working electrode, ensure the accuracy detected.

Then, to add in container at interval of the 0.1mol/L D-Fructose solution getting 0.05ml for 55 seconds and stir, computing machine detects primary current density by electrochemical workstation, cycle detection like this 9 times, and the D-Fructose concentration X of solution in the container recording current density value S (t) that detects each time and correspondence thereof.

10 current density values S (t) detected are substituted into second-order linear system accidental resonance model by computing machine respectively, calculate 10 signal to noise ratio (S/N ratio) eigenwert SNR _feature, in conjunction with the D-Fructose concentration X of solution in 10 corresponding containers, linear fit obtains concentration computing formula: SNR _feature=0.75027+3.88974X.

Then, cleaning container is clean, and add in container by D-Fructose solution to be measured, computing machine detects primary current density by electrochemical workstation, current density value S (t) detected is substituted into second-order linear system accidental resonance model, calculates signal to noise ratio (S/N ratio) eigenwert SNR _feature, by signal to noise ratio (S/N ratio) eigenwert SNR _featuresubstitute into concentration computing formula: SNR _feature=0.75027+3.88974X, calculates the concentration of D-Fructose solution.

As preferably, described working electrode is foam copper electrode, and described is platinum plate electrode to electrode.

As preferably, described conveying mechanism comprises travelling belt and drives the driving mechanism of conveyer belt, and described travelling belt is set on the madial wall of groove and the madial wall of groove, and described driving mechanism is electrically connected with computing machine.Conveyer belt drives electrode along involute motion.

As preferably, described travelling belt surface is provided with tooth bar, and described driving mechanism comprises the drive motor rotated with tooth bar meshed gears and driven wheel, and described drive motor is electrically connected with computing machine.Conveyer belt is driven by pinion rotation.

As preferably, described rabbling mechanism comprises the stirring vane being arranged on container bottom and the servomotor driving stirring vane to rotate, and described servomotor is electrically connected with computing machine.

As preferably, described cover plate is provided with through hole.Be convenient to add solution in container.

A kind of method detecting D-Fructose solution concentration of the present invention, comprises the following steps:

S1: the 0.1mol/LNaOH solution getting 25ml adds in container, electrochemical operation stands in working electrode and the constant voltage to applying+0.5V between electrode;

S2: the 0.1mol/L D-Fructose solution getting 0.05ml to add in container and stirs, then computing machine is driven by conveying mechanism and moves along groove to electrode, adjustment is to the distance between electrode and working electrode, simultaneous computer detects current density value when being positioned at diverse location to electrode by electrochemical workstation, make to rest on position corresponding to maximum current density value to electrode, then computing machine drives cover plate to move up and down by lifter, thus adjustment working electrode and the degree of depth to solution in electrode immersion container, testing electrode and to electrode immerse solution different depth time current density, finally making working electrode and immersing the degree of depth of solution to electrode is that current density is in maximal value place, and record the D-Fructose concentration X of solution in this current density value S (t) and container,

S3: to add in container at interval of the 0.1mol/L D-Fructose solution getting 0.05ml for 55 seconds and stir, computing machine detects primary current density by electrochemical workstation, cycle detection like this 9 times, and the D-Fructose concentration X of solution in the container recording current density value S (t) that detects each time and correspondence thereof;

S4: 10 current density values S (t) detected are carried out same data processing by computing machine, calculate 10 signal to noise ratio (S/N ratio) eigenwerts, comprise the following steps the data processing that each current density value S (t) is carried out:

Substitute into second-order linear system accidental resonance model $\frac{d^{2}x\left(t\right)}{{\mathrm{dt}}^2}+[2r+\mathrm{\ξ}\left(t\right)+b{\mathrm{\ξ}}^2\left(t\right)]\frac{\mathrm{dx}\left(t\right)}{\mathrm{dt}}+{\mathrm{\ω}}^{2}x\left(t\right)=A\cos \left(\mathrm{\Ωt}\right)+\mathrm{cS}\left(t\right)$ In, and second-order linear system accidental resonance model is resonated,

Wherein, x (t) is the displacement of vibration particle, and Ω is angular frequency, r and ω is the attenuation coefficient of setting and the frequency of linear oscillator particle respectively, S (t) is the current density detected, and c is the signal adjustment coefficient of setting, and b is the quadratic noise ξ of setting ²t the coefficient of (), ξ (t) is three discrimination noises, and { dismutation of noise follows Poisson distribution to ξ (t) ∈ for-a, 0, a}, a > 0, and its probability distribution is p _s(a)=p _s(-a)=q, p _s(0)=1-2q, wherein 0 < q < 0.5,

Noise average and correlativity follow < ξ (t) >=0, < ξ (t) ξ (t+ τ) >=2qa ²e ^{-λ τ},

Wherein λ is correlation ratio, and the flatness of three discriminations noise ξ (t) is

Utilize formula $\mathrm{SNR}=\frac{\mathrm{r\&lambda;\&Omega;}+2q{a}^2\mathrm{bc}({\mathrm{\&Omega;}}^3-\mathrm{\&Omega;})}{1+{2\mathrm{qa}}^{2}b+5r-a^2},$ Calculate signal to noise ratio (S/N ratio) eigenwert SNR _feature;

S5: according to 10 signal to noise ratio (S/N ratio) eigenwert SNR _featureand the D-Fructose concentration x-ray matching of solution obtains concentration computing formula in 10 of correspondence containers: SNR _feature=0.75027+3.88974X;

S6: cleaning container is clean, D-Fructose solution to be measured is added in container, computing machine detects primary current density by electrochemical workstation, current density value S (t) detected is substituted into second-order linear system accidental resonance model, calculates signal to noise ratio (S/N ratio) eigenwert SNR _feature, by signal to noise ratio (S/N ratio) eigenwert SNR _featuresubstitute into concentration computing formula: SNR _feature=0.75027+3.88974X, calculates the concentration of D-Fructose solution.

As preferably, first testing electrode and whether qualified to electrode before described step S1 performs, if defective, change working electrode and to electrode, testing electrode and the method whether qualified to electrode comprise the following steps:

N1: the 0.1mol/LNaOH solution getting 25ml to add in container and stirs, electrochemical operation stands in working electrode and voltage range is-0.2V-0.7V, the scanning voltage of sweep velocity 0.05V/S scans to applying between electrode, electrochemical workstation detects current density, and send it to computing machine, computing machine obtains current density maxima and current density minimum value, and calculates the difference A1 between current density maxima and current density minimum value;

N2: cleaning container is clean, the 0.1mmol/L D-Fructose solution of the 0.1mol/L NaOH solution and 10ml of getting 15ml to add in container and stirs, electrochemical operation stands in working electrode and voltage range is-0.2V-0.7V, the scanning voltage of sweep velocity 0.05V/S scans to applying between electrode, electrochemical workstation detects current density, and send it to computing machine, computing machine obtains current density maxima and current density minimum value, and calculates the difference A2 between current density maxima and current density minimum value;

N3: if then computing machine judges working electrode and is qualified to electrode, if then computing machine judges working electrode or defective to electrode.

If COMPUTER DETECTION is to working electrode or defective to electrode, also one of them electrode replaceable, then detects again, if also defective, then changes another electrode, so operation until detect qualified.

Substantial effect of the present invention is: the concentration that can detect D-Fructose solution fast and accurately, simple to operate.

Accompanying drawing explanation

Fig. 1 is a kind of structural representation of the present invention;

Fig. 2 is that a kind of circuit theory of the present invention connects block diagram;

Fig. 3 is the structural representation of cover plate of the present invention;

Fig. 4 is the sectional view of travelling belt of the present invention.

In figure: 1, computing machine, 2, electrochemical workstation, 3, container, 4, working electrode, 5, to electrode, 6, cover plate, 7, groove, the 8, first joint pin, 9, the second joint pin, 10, expansion link, 11, conveying mechanism, 12, rabbling mechanism, 13, stirring vane, 14, lifter, 15, web member, 16, groove, 17, travelling belt, 18, tooth bar, 19, gear, 20, the first proximity switch, the 21, second proximity switch, 22, through hole.

Embodiment

Below by embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is described in further detail.

Embodiment: a kind of device detecting D-Fructose solution concentration of the present embodiment, as Fig. 1, Fig. 2, shown in Fig. 3, comprise computing machine 1 and data collector, data collector comprises electrochemical workstation 2, container 3, working electrode 4 and to electrode 5, container 3 top is provided with cover plate 6, working electrode 4 and to electrode 5 just to being arranged on below cover plate 6, cover plate 6 is provided with gathering sill, the conveying mechanism 11 that can move along gathering sill is provided with in gathering sill, gathering sill comprises groove 7 in involute shape and groove 16 end to end with groove 7, working electrode 4 top is connected with the first joint pin 8, first joint pin 8 passes cover plate 6 and is positioned at the involute urve basic circle center of groove 7, first joint pin 8 is rotationally connected with cover plate 6, second joint pin 9 is connected with to electrode 5 top, second joint pin 9 to be fixed on conveying mechanism 11 and through groove 7, first joint pin 8 top is fixedly connected with the second joint pin 9 top by expansion link 10, rabbling mechanism 12 is provided with bottom container 3, cover plate 6 sidewall is connected with the lifter 14 driving cover plate 6 to move up and down, lifter 14 is fixedly connected with container 3 sidewall by web member 15, computing machine 1 respectively with electrochemical workstation 2, conveying mechanism 11, rabbling mechanism 12 and lifter 14 are electrically connected, electrochemical workstation 2 is also electrically connected with working electrode 4 with to electrode 5 respectively.

Rabbling mechanism 12 comprises the stirring vane 13 be arranged on bottom container 3 and the servomotor driving stirring vane 13 to rotate, and servomotor is electrically connected with computing machine 1.Lifter 14 to move up and down the degree of depth regulating working electrode 4 and electrode 5 is immersed to solution in container 3 by driving cover plate 6.Working electrode is foam copper electrode, is platinum plate electrode to electrode.Container 3 is made up of transparent material, and container 3 surface is provided with scale mark.Working electrode 4 and the first joint pin 8 removably connect, and removably connect to electrode 5 and the second joint pin 9.

As shown in Figure 3, Figure 4, the driving mechanism that conveying mechanism 11 comprises travelling belt 17 and drives travelling belt 17 to move, travelling belt 17 is set on the madial wall of groove 7 and the madial wall of groove 16, travelling belt 17 surface is provided with tooth bar 18, driving mechanism comprises the drive motor rotated with tooth bar 18 meshed gears 19 and driven wheel 19, and drive motor is electrically connected with computing machine 1.Moved by gear 19 rotating drive travelling belt 17, thus drive electrode 5 along involute motion.

The front-end and back-end of groove 7 are respectively equipped with the first proximity switch 20 and the second proximity switch 21, first proximity switch 20 and the second proximity switch 21 and are electrically connected with computing machine 1 respectively.When moving to the front end of groove 7 to electrode 5, first proximity switch 20 detects and exports trigger pip to computing machine 1, when moving to the rear end of groove 7 to electrode 5, second proximity switch 21 detects and exports trigger pip to computing machine 1, can prevent travelling belt 17 from driving and cause damage to electrode 5 hyperkinesia.

Cover plate 6 is provided with through hole 22, is convenient to add solution in container 3.The 0.1mol/LNaOH solution getting 25ml adds in container 3, electrochemical workstation 2 working electrode 4 and to electrode 5 between apply the constant voltage of+0.5V.The 0.1mol/L D-Fructose solution getting 0.05ml adds in container 3, solution stirs by rabbling mechanism work for 10 seconds, then computing machine 1 is driven by conveying mechanism 11 and moves along groove 7 to electrode 5, adjustment is to the distance between electrode 5 and working electrode 4, simultaneous computer 1 detects current density value when being positioned at diverse location to electrode by electrochemical workstation 2, make to rest on position corresponding to maximum current density value to electrode 5, then computing machine 1 drives cover plate 6 to move up and down by lifter 14, thus adjustment working electrode 4 and electrode 5 is immersed to the degree of depth of solution in container 3, testing electrode 4 and current density when solution different depth immerses to electrode 5, finally make working electrode 4 and be that current density is in maximal value place to the degree of depth that electrode 5 immerses solution, and record the D-Fructose concentration X of solution in this current density value S (t) and container.

Groove 7 is in involute shape, and the first joint pin 8 is positioned at the involute urve basic circle center of groove 7, to electrode 5 along involute motion, increases gradually the distance between electrode 5 and working electrode 4.The groove of involute shape is conducive to controlling the distance between electrode 5 and working electrode 4 more accurately.First joint pin 8 top is fixedly connected with the second joint pin 9 top by expansion link 10, when electrode 5 is moved along groove 7, expansion link 10 free-extension, simultaneous retractable bar 10 drives the first joint pin 8 to rotate, first joint pin 8 drives working electrode 4 synchronous axial system, thus make to remain just to setting to electrode 5 and working electrode 4, ensure the accuracy detected.

Then, to add in container 3 at interval of the 0.1mol/L D-Fructose solution getting 0.05ml for 55 seconds and stir, computing machine 1 detects primary current density by electrochemical workstation 2, cycle detection like this 9 times, and the D-Fructose concentration X of solution in the container recording current density value S (t) that detects each time and correspondence thereof.

10 current density values S (t) detected are substituted into second-order linear system accidental resonance model by computing machine 1 respectively, calculate 10 signal to noise ratio (S/N ratio) eigenwert SNR _feature, in conjunction with the D-Fructose concentration X of solution in 10 corresponding containers, linear fit obtains concentration computing formula: SNR _feature=0.75027+3.88974X.

Then, cleaned up by container 3, add in container 3 by D-Fructose solution to be measured, computing machine 1 detects primary current density by electrochemical workstation 2, current density value S (t) detected is substituted into second-order linear system accidental resonance model, calculates signal to noise ratio (S/N ratio) eigenwert SNR _feature, by signal to noise ratio (S/N ratio) eigenwert SNR _featuresubstitute into concentration computing formula: SNR _feature=0.75027+3.88974X, calculates the concentration of D-Fructose solution.

A kind of method detecting D-Fructose solution concentration of the present embodiment, is applicable to the device of above-mentioned detection D-Fructose solution concentration, comprises the following steps:

S1: the 0.1mol/LNaOH solution getting 25ml adds in container, electrochemical operation stands in working electrode and the constant voltage to applying+0.5V between electrode;

S2: the 0.1mol/L D-Fructose solution getting 0.05ml adds in container, solution stirs by rabbling mechanism work for 10 seconds, then computing machine is driven by conveying mechanism and moves along groove to electrode, adjustment is to the distance between electrode and working electrode, simultaneous computer detects current density value when being positioned at diverse location to electrode by electrochemical workstation, make to rest on position corresponding to maximum current density value to electrode, then computing machine drives cover plate to move up and down by lifter, thus adjustment working electrode and the degree of depth to solution in electrode immersion container, testing electrode and to electrode immerse solution different depth time current density, finally making working electrode and immersing the degree of depth of solution to electrode is that current density is in maximal value place, and record the D-Fructose concentration X of solution in this current density value S (t) and container,

Conveying mechanism drives and moves along groove to electrode, adjustment is to the distance between electrode and working electrode, often move a certain distance, detect primary current density value, computing machine compares the current density value detecting and obtain, obtain maximum current density value, and the position that will electrode be moved to corresponding to maximum current density value.Then, computing machine is by adjustable cap plate height adjustment working electrode and the contact area to solution in electrode and container, and the current density value detected when cover plate is positioned at differing heights, compare and obtain maximum current density value, and cover plate is adjusted to the height corresponding to maximum current density value.The current density value detected is maximum, illustrates that the result obtained is detected in the detection position be positioned at electrode and working electrode the most remarkable, is conducive to improving accuracy of detection.

S3: to add in container at interval of the 0.1mol/L D-Fructose solution getting 0.05ml for 55 seconds and stir, computing machine detects primary current density by electrochemical workstation, cycle detection like this 9 times, and the D-Fructose concentration X of solution in the container recording current density value S (t) that detects each time and correspondence thereof;

S4: 10 current density values S (t) detected are carried out same data processing by computing machine, calculate 10 signal to noise ratio (S/N ratio) eigenwerts, comprise the following steps the data processing that each current density value S (t) is carried out:

Substitute into second-order linear system accidental resonance model $\frac{d^{2}x\left(t\right)}{{\mathrm{dt}}^2}+[2r+\mathrm{\&xi;}\left(t\right)+b{\mathrm{\&xi;}}^2\left(t\right)]\frac{\mathrm{dx}\left(t\right)}{\mathrm{dt}}+{\mathrm{\&omega;}}^{2}x\left(t\right)=A\cos \left(\mathrm{\&Omega;t}\right)+\mathrm{cS}\left(t\right)$ In, and second-order linear system accidental resonance model is resonated,

Wherein, x (t) is the displacement of vibration particle, and Ω is angular frequency, r and ω is the attenuation coefficient of setting and the frequency of linear oscillator particle respectively, S (t) is the current density detected, and c is the signal adjustment coefficient of setting, and b is the quadratic noise ξ of setting ²t the coefficient of (), ξ (t) is three discrimination noises, and { dismutation of noise follows Poisson distribution to ξ (t) ∈ for-a, 0, a}, a > 0, and its probability distribution is p _s(a)=p _s(-a)=q, p _s(0)=1-2q, wherein 0 < q < 0.5,

Noise average and correlativity follow < ξ (t) >=0, < ξ (t) ξ (t+ τ) >=2qa ²e ^{-λ τ},

Wherein λ is correlation ratio, and the flatness of three discriminations noise ξ (t) is

Utilize formula $\mathrm{SNR}=\frac{\mathrm{r\&lambda;\&Omega;}+2q{a}^2\mathrm{bc}({\mathrm{\&Omega;}}^3-\mathrm{\&Omega;})}{1+{2\mathrm{qa}}^{2}b+5r-a^2},$ Calculate signal to noise ratio (S/N ratio) eigenwert SNR _feature;

S5: according to 10 signal to noise ratio (S/N ratio) eigenwert SNR _featureand the D-Fructose concentration x-ray matching of solution obtains concentration computing formula in 10 of correspondence containers: SNR _feature=0.75027+3.88974X;

Each signal to noise ratio (S/N ratio) eigenwert SNR _featurepoint (X, SNR is formed with the D-Fructose concentration X of solution in the container of its correspondence _feature), according to 10 points (X, SNR _feature) linear fit obtains concentration computing formula: SNR _feature=0.75027+3.88974X.

S6: cleaning container is clean, D-Fructose solution to be measured is added in container, computing machine detects primary current density by electrochemical workstation, current density value S (t) detected is substituted into second-order linear system accidental resonance model, calculates signal to noise ratio (S/N ratio) eigenwert SNR _feature, by signal to noise ratio (S/N ratio) eigenwert SNR _featuresubstitute into concentration computing formula: SNR _feature=0.75027+3.88974X, calculates the concentration of D-Fructose solution.

First testing electrode and whether qualified to electrode before step S1 performs, if defective, change working electrode and to electrode, testing electrode and the method whether qualified to electrode comprise the following steps:

N1: the 0.1mol/LNaOH solution getting 25ml to add in container and stirs, electrochemical operation stands in working electrode and voltage range is-0.2V-0.7V, the scanning voltage of sweep velocity 0.05V/S scans to applying between electrode, electrochemical workstation detects current density, and send it to computing machine, computing machine obtains current density maxima and current density minimum value, and calculates the difference A1 between current density maxima and current density minimum value;

N2: cleaning container is clean, the 0.1mmol/L D-Fructose solution of the 0.1mol/L NaOH solution and 10ml of getting 15ml to add in container and stirs, electrochemical operation stands in working electrode and voltage range is-0.2V-0.7V, the scanning voltage of sweep velocity 0.05V/S scans to applying between electrode, electrochemical workstation detects current density, and send it to computing machine, computing machine obtains current density maxima and current density minimum value, and calculates the difference A2 between current density maxima and current density minimum value;

N3: if then computing machine judges working electrode and is qualified to electrode, if then computing machine judges working electrode or defective to electrode.

If COMPUTER DETECTION is to working electrode or defective to electrode, also one of them electrode replaceable, then detects again, if also defective, then changes another electrode, so operation until detect qualified.

Claims (8)

1. one kind is detected the device of D-Fructose solution concentration, it is characterized in that: comprise computing machine (1) and data collector, described data collector comprises electrochemical workstation (2), container (3), working electrode (4) and to electrode (5), described container (3) top is provided with cover plate (6), described working electrode (4) and to electrode (5) just to be arranged on cover plate (6) below, described cover plate (6) is provided with gathering sill, the conveying mechanism (11) that can move along gathering sill is provided with in described gathering sill, described gathering sill comprise groove (7) in involute shape and with groove (7) end to end groove (16), described working electrode (4) top is connected with the first joint pin (8), described first joint pin (8) is through cover plate (6) and be positioned at the involute urve basic circle center of groove (7), described first joint pin (8) and cover plate (6) are rotationally connected, described second joint pin (9) is connected with to electrode (5) top, described second joint pin (9) is fixed on conveying mechanism (11) and goes up and pass groove (7), described first joint pin (8) top is fixedly connected with the second joint pin (9) top by expansion link (10), described cover plate (6) is connected with the lifter (14) driving cover plate (6) to move up and down, described lifter (14) is fixedly connected with container (3) sidewall by web member (15), described container (3) bottom is provided with rabbling mechanism (12), described computing machine (1) respectively with electrochemical workstation (2), conveying mechanism (11), rabbling mechanism (12) and lifter (14) electrical connection, described electrochemical workstation (2) is also electrically connected with working electrode (4) with to electrode (5) respectively.

2. a kind of device detecting D-Fructose solution concentration according to claim 1, is characterized in that: described working electrode (4) is foam copper electrode, and described is platinum plate electrode to electrode (5).

3. a kind of device detecting D-Fructose solution concentration according to claim 1 and 2, it is characterized in that: the driving mechanism that described conveying mechanism (11) comprises travelling belt (17) and drives travelling belt (17) to move, described travelling belt (17) is set on the madial wall of groove (7) and the madial wall of groove (16), and described driving mechanism is electrically connected with computing machine (1).

4. a kind of device detecting D-Fructose solution concentration according to claim 3, it is characterized in that: described travelling belt (17) surface is provided with tooth bar (18), described driving mechanism comprises the drive motor rotated with tooth bar (18) meshed gears (19) and driven wheel (19), and described drive motor is electrically connected with computing machine (1).

5. a kind of device detecting D-Fructose solution concentration according to claim 1 and 2, it is characterized in that: described rabbling mechanism comprises the stirring vane (13) being arranged on container (3) bottom and the servomotor driving stirring vane (13) to rotate, and described servomotor is electrically connected with computing machine (1).

6. a kind of D-Fructose solution concentration detector according to claim 1 and 2, is characterized in that: described cover plate (6) is provided with through hole (22).

7. detect a method for D-Fructose solution concentration, it is characterized in that, comprise the following steps:

S1: the 0.1mol/LNaOH solution getting 25ml adds in container, electrochemical operation stands in working electrode and the constant voltage to applying+0.5V between electrode;

S2: the 0.1mol/L D-Fructose solution getting 0.05ml to add in container and stirs, then computing machine is driven by conveying mechanism and moves along groove to electrode, adjustment is to the distance between electrode and working electrode, simultaneous computer detects current density value when being positioned at diverse location to electrode by electrochemical workstation, make to rest on position corresponding to maximum current density value to electrode, then computing machine drives cover plate to move up and down by lifter, thus adjustment working electrode and the degree of depth to solution in electrode immersion container, testing electrode and to electrode immerse solution different depth time current density, finally making working electrode and immersing the degree of depth of solution to electrode is that current density is in maximal value place, and record the D-Fructose concentration X of solution in this current density value S (t) and container,

S3: to add in container at interval of the 0.1mol/L D-Fructose solution getting 0.05ml for 55 seconds and stir, computing machine detects primary current density by electrochemical workstation, cycle detection like this 9 times, and the D-Fructose concentration X of solution in the container recording current density value S (t) that detects each time and correspondence thereof;

S4: 10 current density values S (t) detected are carried out same data processing by computing machine, calculate 10 signal to noise ratio (S/N ratio) eigenwerts, comprise the following steps the data processing that each current density value S (t) is carried out:

Substitute into second-order linear system accidental resonance model $\frac{d^{2}x\left(t\right)}{{\mathrm{dt}}^2}+[2r+\mathrm{\&xi;}\left(t\right)+b{\mathrm{\&xi;}}^2\left(t\right)]\frac{\mathrm{dx}\left(t\right)}{\mathrm{dt}}+{\mathrm{\&omega;}}^{2}x\left(t\right)=A\cos \left(\mathrm{\&Omega;t}\right)+\mathrm{cS}\left(t\right)$ In, and second-order linear system accidental resonance model is resonated,

Wherein, x (t) is the displacement of vibration particle, and Ω is angular frequency, r and ω is the attenuation coefficient of setting and the frequency of linear oscillator particle respectively, S (t) is the current density detected, and c is the signal adjustment coefficient of setting, and b is the quadratic noise ξ of setting ²t the coefficient of (), ξ (t) is three discrimination noises, and { dismutation of noise follows Poisson distribution to ξ (t) ∈ for-a, 0, a}, a > 0, and its probability distribution is p _s(a)=p _s(-a)=q, p _s(0)=1-2q, wherein 0 < q < 0.5,

Noise average and correlativity follow < ξ (t) >=0, < ξ (t) ξ (t+ τ) >=2qa ²e ^{-λ τ},

Wherein λ is correlation ratio, and the flatness of three discriminations noise ξ (t) is

Utilize formula $\mathrm{SNR}=\frac{\mathrm{r\&lambda;\&Omega;}+2q{a}^2\mathrm{bc}({\mathrm{\&Omega;}}^3-\mathrm{\&Omega;})}{1+{2\mathrm{qa}}^{2}b+5r-a^2},$ Calculate signal to noise ratio (S/N ratio) eigenwert SNR _feature;

S5: according to 10 signal to noise ratio (S/N ratio) eigenwert SNR _featureand the D-Fructose concentration x-ray matching of solution obtains concentration computing formula in 10 of correspondence containers: SNR _feature=0.75027+3.88974X;

S6: cleaning container is clean, D-Fructose solution to be measured is added in container, computing machine detects primary current density by electrochemical workstation, current density value S (t) detected is substituted into second-order linear system accidental resonance model, calculates signal to noise ratio (S/N ratio) eigenwert SNR _feature, by signal to noise ratio (S/N ratio) eigenwert SNR _featuresubstitute into concentration computing formula: SNR _feature=0.75027+3.88974X, calculates the concentration of D-Fructose solution.

8. a kind of method detecting D-Fructose solution concentration according to claim 7, it is characterized in that: first testing electrode and whether qualified to electrode before described step S1 performs, if defective, change working electrode and to electrode, testing electrode and the method whether qualified to electrode comprise the following steps:

N1: the 0.1mol/LNaOH solution getting 25ml to add in container and stirs, electrochemical operation stands in working electrode and voltage range is-0.2V-0.7V, the scanning voltage of sweep velocity 0.05V/S scans to applying between electrode, electrochemical workstation detects current density, and send it to computing machine, computing machine obtains current density maxima and current density minimum value, and calculates the difference A1 between current density maxima and current density minimum value;

N2: cleaning container is clean, the 0.1mmol/L D-Fructose solution of the 0.1mol/L NaOH solution and 10ml of getting 15ml to add in container and stirs, electrochemical operation stands in working electrode and voltage range is-0.2V-0.7V, the scanning voltage of sweep velocity 0.05V/S scans to applying between electrode, electrochemical workstation detects current density, and send it to computing machine, computing machine obtains current density maxima and current density minimum value, and calculates the difference A2 between current density maxima and current density minimum value;

N3: if then computing machine judges working electrode and is qualified to electrode, if then computing machine judges working electrode or defective to electrode.