CN104237217B - A kind of various trace heavy metal ion Simultaneous Detections based on visualization technique - Google Patents
A kind of various trace heavy metal ion Simultaneous Detections based on visualization technique Download PDFInfo
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- CN104237217B CN104237217B CN201410314655.6A CN201410314655A CN104237217B CN 104237217 B CN104237217 B CN 104237217B CN 201410314655 A CN201410314655 A CN 201410314655A CN 104237217 B CN104237217 B CN 104237217B
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Abstract
A kind of various trace heavy metal ion Simultaneous Detections based on visualization technique of the present invention, belong to trace heavy metal ion detection technique field.Using porphyrin and pyridylazo class chemo-responsive dyes as visible sensor sensitive material, visible sensor array base palte is by hydrophilic composite fibre ester film, ABS plastic thin plate（Acronitrile-butadiene-styrene）, water proofing property double faced adhesive tape prepare, chemo-responsive dyes point is prepared into visible sensor array on substrate by way of capillary array point sample；The signal of collection be reaction system in react forward and backward visible sensor array R, the difference of G, B color value；Data processing is using the multivariate regression algorithm in Chemical Measurement.This method is capable of achieving to detect there is that testing cost is low, detection time is short, easy to operate, sensitivity is high, reproducible while trace Pb, Cd, Hg heavy metal ion.The test of the present invention can obtain meeting actual effect.
Description
Technical field
The invention belongs to trace heavy metal ion detection technique field, and in particular to be a kind of based on visualization technique
At various trace heavy metal ion Simultaneous Detections, including the preparation of visible sensor array, information gathering and data
Reason.
Background technology
Heavy metal contaminants are difficult to degrade in the environment, can be in animal and plant body accumulation, by the continuous richness of food chain
Collection, concentration can thousands of times of increase, huge potential hazard is caused to health.Therefore, heavy metal is always food
The important Testing index in the fields such as quality control, environmental monitoring.Strong toxic heavy metal（Pb, Cd, Hg etc.）Simultaneous Detection
Research is always study hotspot problem both domestic and external.At present, the detection method of heavy metal mainly has, spectrographic method（Including atom is inhaled
Receive spectrographic method, Inductive coupling plasma-atomic emission spectrometry, atomic fluorescence spectrometry, spectrophotography etc.）, mass spectrography
（Inductively coupled plasma mass spectrometry method etc.）And electrochemical methods（Voltammetry, potentiometry, conductance method etc.）Deng.Spectrographic method,
Mass spectrography generally requires large-scale instrument, and needs special operator；Electrochemical process has a drawback in that test fluid prepares
Complex steps, electrode are costly and reuse more difficulty etc..Accordingly, it would be desirable to developing new detection method realizes many seed scars
Detect while amount heavy metal.
Visualization sensing technology is micro-, trace chemistry composition detection technology in a kind of new sample, and its ultimate principle is
Chemical substance in sample solution is reacted with visible sensor array, causes the color of sensor to change i.e. visual
Change, by the analysis to this color change, can to sample solution in micro-, trace chemical carry out qualitative and quantitative analysis.
Visualization technique does not need large-scale instrument, easy to operate, expense is low, do not need special operator.Therefore, in recent years, may be used
The wide of domestic and international research worker is subject to depending on changing applied research of the technology in the fields such as food quality, environmental monitoring, medical diagnosiss
General concern.
The content of the invention
In order to overcome existing contents of many kinds of heavy metal ion while many defects of detection technique, the invention provides one kind is based on
Various trace heavy metal ion Simultaneous Detections of visualization technique.
Technical scheme is summarized as follows：A kind of described various trace heavy metal ions based on visualization technique
Simultaneous Detection, including preparation, 3 steps of information gathering and data processing of visible sensor array.
Described visible sensor array is had chemo-responsive dyes, the composite fibre of color response by heavy metal ion
Cellulose ester film, ABS plastic thin plate（Acrylonitrile-butadiene-styrene (ABS)）And prepared by waterproof double faced adhesive tape.
It is porphyrinses and pyridylazo class that described heavy metal ion has the chemo-responsive dyes of color response
Compound, specially：Meso- tetra-（P-hydroxybenzene）Porphyrin, meso- tetra-（P-aminophenyl）Porphyrin, meso- tetraphenyl porphins
Quinoline, meso- tetra-（P-methoxyphenyl）Porphyrin, 1-（2- pyridylazos）- beta naphthal, 4-（2- pyridylazos）Resorcinol etc..
The preparation process of described visible sensor array is：
The first step, the preparation of chemical colour reaction agent solution：By the porphyrin chemo-responsive dyes for being filtered out and pyridylazo class
Chemo-responsive dyes are dissolved in chloroform reagent, are prepared into the chemical colour reaction agent solution that concentration is 1-10mM.
Second step, the preparation of visible sensor array base palte：First ABS plastic thin plate is processed into several uniform
The Rectangular boxes of the aperture of arrangement；Then, cellulose mixture ester film is clipped between 2 ABS thin plates, and makes 2 ABS thin
Apertures align on plate so that middle cellulose mixture ester film can come out；It is finally ABS is thin with waterproof double faced adhesive tape
Plate and cellulose mixture ester film are fixed.
3rd step：The chemical colour reaction agent solution that the first step is obtained takes 0.1-10 μ L by trace sampling apparatus and is fixed on base
On mixed cellulose ester microporous membrane on plate in aperture, an aperture fixes a kind of visualization sensitive material, then by chloroform
Obtain visualizing taste sensor array after drying.
A kind of described various trace heavy metal ion Simultaneous Detections based on visualization technique, mixed cellulose ester
Meagre membrane aperture is 0.15-8 μm；ABS plastic lamella thickness is 0.1-2mm；After processing, on ABS plastic thin plate, hole diameter is 2-
6cm, Rectangular boxes area are 3-5cm2。
The signal of described collection be reaction system in react forward and backward visible sensor array R, the difference of G, B color value
Value.
A kind of described various trace heavy metal ion Simultaneous Detections based on visualization technique, data processing method
For the regression algorithm in Chemical Measurement, including neural net regression, PLS or Support vector regression etc..
Using the visible sensor array data that collects as independent variable, heavy metal is built as dependent variable using concentration of heavy metal ion
The Quantitative Prediction Model of ion.According to regression model performance, filter out for specific sample concentration of heavy metal ion prediction effect
Optimum regression algorithm is used as data processing method.The evaluation index of model performance is as follows：
1. validation-cross root-mean-square error (Root mean square error of cross-validation,
RMSECV)：The index is mainly used in the predictive ability of the feasibility and institute's established model for evaluating certain modeling method, in model training
During by the method for validation-cross calculating.
In formula,For in calibration setiThe measured value of individual sample；For is rejected in training setiAfter individual sample, with remainder
Sample Establishing model, the model is toiIndividual sample predictions value,nFor training set sample number.
2. predicted root mean square error (Root mean squared error of prediction, RMSEP)：That is mould
Predicted root mean square error of the type to forecast set sample, is mainly used in evaluating predictive ability of institute's established model to external samples.Prediction
Root-mean-square error is less, then show that the predictive ability of model to external sample is higher, otherwise predictive ability is lower.RMSEP values are pressed
Following formula is calculated：
In formula,WithRespectively in forecast setiThe actual measurement collection of individual sample and forecast set,nFor forecast set sample number.
3. correlation coefficient (Correlation coefficient,R)：Or claim squared correlation coefficient, for investigating sample
Predictive value and measured value between degree of correlation,R1 is closer to, then illustrates the degree of correlation between predictive value and measured value
Better,R 2 It is calculated as follows：
In formula,WithThe respectively in sample set (include calibration set and forecast set)iThe measured value of individual sample and prediction
Value,For the meansigma methodss of the measured value of all samples in sample set.
The invention has the beneficial effects as follows：（1）As this method adopts porphyrin and pyridylazo class chemo-responsive dyes conduct
Visible sensor sensitive material, sensor heavy metal ion have it is non-specific, therefore can realize various heavy from
Detect while sub-；
（2）Due to using hydrophilic cellulose mixture ester film as baseplate material so that the heavy metal ion in sample liquid
Can fully react with chemo-responsive dyes, therefore, substantially increase the detection sensitivity of this method, can to ppm levels heavy metal from
Sub- accurate quantitative analysis；
（3）Visible sensor array performance is stable, reproducible, reliable results；
（4）Detection time is short, and the response time is 5min；
（5）Low cost.
Description of the drawings：
The neural net regression model result that Fig. 1 visualization techniques are detected simultaneously to trace Pb, Cd, Hg in aqueous solution.
Specific embodiment：
Below in conjunction with the accompanying drawings to a kind of various trace heavy metal ions based on visualization technique of the present invention simultaneously
Detection method is described in more detail：
（1）A kind of various trace heavy metal ion Simultaneous Detections based on visualization technique of the present invention, bag
Include preparation, 3 steps of information gathering and data processing of visible sensor array.
（2）Visible sensor array is had the chemo-responsive dyes of color response, cellulose mixture by heavy metal ion
Ester film, ABS plastic thin plate（Acrylonitrile-butadiene-styrene (ABS)）And prepared by waterproof double faced adhesive tape.Through test of many times, selection
Chemo-responsive dyes are 4 kinds of porphyrinses and 2 kinds of pyridylazo class compounds, specifically, meso- tetra-（P-hydroxybenzene）Porphin
Quinoline, meso- tetra-（P-aminophenyl）Porphyrin, meso- tetraphenylporphyrins, meso- tetra-（P-methoxyphenyl）Porphyrin, 1-（2- pyrroles
Pyridine azo）- beta naphthal, 4-（2- pyridylazos）Resorcinol；Selected mixed cellulose ester membrane pore size is 0.45 μm；It is selected
ABS lamella thickness be 0.5mm.
The making step of visible sensor array is as follows：
The first step, the preparation of chemical colour reaction agent solution：By filter out 4 kinds of porphyrinses and 2 kinds of pyridylazo classes
Compound chemo-responsive dyes are dissolved in chloroform reagent respectively, chemical colour reaction agent solution of the compound concentration for 3mM；
Second step, the preparation of visible sensor array base palte：First ABS plastic thin plate is processed into uniform with 6
The Rectangular boxes of the 4mm apertures of arrangement, the Rectangular boxes specification after processing are 28mm*20mm；Then, by cellulose mixture
It is 28mm*20mm that ester film is processed into specification, the cellulose mixture ester film after processing is clipped between 2 ABS thin plates, and is allowed
Apertures align on 2 ABS thin plates so that middle cellulose mixture ester film can come out；It is finally two-sided with waterproof
ABS thin plates and cellulose mixture ester film are fixed by glue.
3rd step：The chemical colour reaction agent solution that the 5 μ L first steps obtain is taken with 10 μ L microscale samplers and drops in aperture on substrate
On interior mixed cellulose ester microporous membrane, an aperture fixes a kind of visualization sensitive material, after then be dried chloroform
To visible sensor array.
（3）A kind of various trace heavy metal ion Simultaneous Detections based on visualization technique of the present invention, adopt
The signal for integrating as reaction system in react forward and backward visible sensor array R, the difference of G, B color value.
（4）A kind of various trace heavy metal ion Simultaneous Detections based on visualization technique of the present invention, number
According to processing method be Chemical Measurement in regression algorithm, including, neural net regression, PLS or support to
Amount machine recurrence etc..For embodiment, detect while series concentration trace Pb, Cd, Hg in aqueous solution, contrast regression model performance
It was found that, BP- neural net regressions model is optimum.In BP- neural network model building processs, the 2/3 of sample number is randomly selected
Used as training set, remaining 1/3 sample is used as test set.BP- neural network topology structures are set to 3 layers, are input into including 1
Layer, 1 output layer and 1 hidden layer, and the method using leaving-one method validation-cross are optimized to hidden layer number of network node.
Initialization network parameter is as follows, and it is that 0.1, factor of momentum is missed for 0.7, training objective that repetition training number of times is 1000, learning rate
Difference is 1 × 10-8。
Fig. 1 is a kind of various trace heavy metal ion Simultaneous Detections pair based on visualization technique of the present invention
The BP- neural net regression model prediction results that trace Pb, Cd, Hg are detected simultaneously in aqueous solution.It can be seen that this
The neural net regression model that bright described method builds is less to the forecast error of trace Pb, Cd, Hg, model prediction phase relation
Number is higher, shows that a kind of various trace heavy metal ion Simultaneous Detections based on visualization technique of the present invention are that have
Effect.
Claims (6)
1. a kind of various trace heavy metal ion Simultaneous Detections based on visualization technique, including visible sensor array
Preparation, 3 steps of information gathering and data processing, it is characterised in that visible sensor array is had by heavy metal ion
There are the chemo-responsive dyes of color response, cellulose mixture ester film, ABS plastic thin plate（Acrylonitrile-butadiene-styrene (ABS)）And it is anti-
It is prepared by water double faced adhesive tape；The signal of collection is to react the R of forward and backward visible sensor, G, B color difference in reaction system；Adopted
Data processing method is neural net regression algorithm, PLS algorithm or Support vector regression algorithm；Its
There are middle heavy metal ion the chemo-responsive dyes of color response to be：Meso- tetra-（P-hydroxybenzene）Porphyrin, meso- tetra-（To ammonia
Base phenyl）Porphyrin, meso- tetraphenylporphyrins, meso- tetra-（P-methoxyphenyl）Porphyrin, 1-（2- pyridylazos）- beta naphthal and
4-（2- pyridylazos）Resorcinol；
Wherein visible sensor array making step is：
The first step, the preparation of chemical colour reaction agent solution：By the porphyrin chemo-responsive dyes for being filtered out and pyridylazo class chemistry
Developer is dissolved in chloroform reagent, prepares chemical colour reaction agent solution；
Second step, the preparation of visible sensor array base palte：First ABS plastic thin plate is processed into evenly distributed with 6
The Rectangular boxes of aperture；Then, cellulose mixture ester film is clipped between 2 ABS thin plates, and is allowed on 2 ABS thin plates
Apertures align so that middle cellulose mixture ester film can come out；Finally with waterproof double faced adhesive tape is by ABS thin plates and mixes
Condensating fiber cellulose ester film is fixed；
3rd step：The chemical colour reaction agent solution that the first step is obtained takes 0.1-10 μ L by trace sampling apparatus and is fixed on substrate
On cellulose mixture ester film in aperture, an aperture fixes a kind of chemo-responsive dyes, and obtaining after then be dried chloroform can
Depending on changing sensor array.
2. a kind of various trace heavy metal ion Simultaneous Detections based on visualization technique according to claim 1,
Characterized in that, chemo-responsive dyes solution concentration is 1-10mMol.
3. a kind of various trace heavy metal ion Simultaneous Detections based on visualization technique according to claim 1,
Characterized in that, mixed cellulose ester membrane pore size is 0.15-8 μm.
4. a kind of various trace heavy metal ion Simultaneous Detections based on visualization technique according to claim 1,
Characterized in that, ABS plastic lamella thickness is 0.1-2mm.
5. a kind of various trace heavy metal ion Simultaneous Detections based on visualization technique according to claim 1,
Characterized in that, on ABS plastic thin plate, hole diameter is 4mm after processing.
6. a kind of various trace heavy metal ion Simultaneous Detections based on visualization technique according to claim 1,
Characterized in that, the area of the ABS plastic thin plate after processing is 3-5cm2。
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| CN108764589A (en) * | 2018-08-10 | 2018-11-06 | 武汉工程大学 | A kind of ion concentration prediction technique based on support vector machines |
| CN109115704B (en) * | 2018-08-29 | 2020-08-04 | 中南大学 | Spectral differential preprocessing method for trace multi-metal ion detection under high-zinc background |
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| CN102660629A (en) * | 2012-04-19 | 2012-09-12 | 江苏大学 | Method for rapidly identifying dominant spoilage bacteria of livestock meat on basis of olfaction visualization technology |
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