CN104237217A - Method for simultaneously detecting various trace heavy metal ions based on visualization technology - Google Patents
Method for simultaneously detecting various trace heavy metal ions based on visualization technology Download PDFInfo
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Abstract
The invention provides a method for simultaneously detecting various trace heavy metal ions based on a visualization technology, belonging to the technical field of detection of the trace heavy metal ions. According to the simultaneous detection method, a porphyrin and pyridine azos chemical developing agent is used as a visualized sensor sensitive material; a visualized sensor array base plate is prepared from a hydrophilic mixed fiber ester thin film, an ABS (acrylonitrile-butadiene-styrene) plastic thin plate and a waterproof double-faced adhesive tape; the chemical developing agent is applied to the base plate in a manner of applying a sample through a capillary tube array to prepare a visualized sensor array; a collected signal is a difference value of R, G and B color values of the visualized sensor array before and after a reaction in a reaction system; and a multiple regression algorithm in chemometrics is used for carrying out data processing. The method can be used for realizing simultaneous detection of trace Ph, Cd and Hg heavy metal ions, and has the advantages of low detection cost, short detection time, simplicity in operation, high sensitivity, good repeatability and the like. The test can obtain a practical result.
Description
Technical field
The invention belongs to trace heavy metal ion detection technique field, what be specifically related to is a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique, comprises the preparation of visible sensor array, information acquisition and data processing.
Background technology
Heavy metal contaminants is difficult to degraded in the environment, can at animal and plant body accumulation, and by the continuous enrichment of food chain, concentration can the increase of thousands of times, causes huge potential hazard to health.Therefore, heavy metal is the important Testing index in the fields such as food quality control, environmental monitoring always.The research of strong toxic heavy metal (Pb, Cd, Hg etc.) Simultaneous Detection is study hotspot problem both domestic and external always.At present, the detection method of heavy metal mainly contains, spectroscopic methodology (comprises, atomic absorption spectrography (AAS), Inductive coupling plasma-atomic emission spectrometry, atomic fluorescence spectrometry, spectrophotometric method etc.), mass spectroscopy (inductively coupled plasma mass spectrometry method etc.) and electrochemical methods (voltammetry, potential method, conductance method etc.) etc.Spectroscopic methodology, mass spectroscopy generally need large-scale instrument, and need special operating personnel; The defect that electrochemical process exists is that test fluid preparation process is loaded down with trivial details, electrode costly and reuse comparatively difficulty etc.Therefore, detect while needing the new detection method of exploitation to realize multiple trace heavy metal.
Visual sensing technology is micro-in a kind of novel sample, trace chemistry composition detection technology, its ultimate principle is that chemical substance in sample solution and visible sensor array react, the color of sensor is caused to change namely visual, by the analysis changed this color, qualitative and quantitative analysis can be carried out to micro-, the trace chemical in sample solution.Visualization technique does not need large-scale instrument, easy to operate, expense is low, do not need special operating personnel.Therefore, in recent years, the applied research of visualization technique in the fields such as food quality, environmental monitoring, medical diagnosis is subject to the extensive concern of domestic and international researchist.
Summary of the invention
In order to overcome many defects of existing contents of many kinds of heavy metal ion simultaneously detection technique, the invention provides a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique.
Technical scheme of the present invention is summarized as follows: described a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique, comprises the preparation of visible sensor array, information acquisition and data processing 3 steps.
Described visible sensor array has the chemo-responsive dyes of color response, cellulose mixture ester film, ABS plastic thin plate (acrylonitrile-butadiene-styrene (ABS)) and waterproof double faced adhesive tape by heavy metal ion to be prepared.
The chemo-responsive dyes that described heavy metal ion has color response is porphyrins and pyridylazo compounds, is specially: meso-tetra-(p-hydroxybenzene) porphyrin, meso-tetra-(p-aminophenyl) porphyrin, meso-tetraphenylporphyrin, meso-tetra-(p-methoxyphenyl) porphyrin, 1-(2-pyridylazo)-2-naphthol, 4-(2-pyridylazo) resorcinol etc.
The preparation process of described visible sensor array is:
The first step, the preparation of chemical colour reaction agent solution: filtered out porphyrin chemo-responsive dyes and pyridylazo class chemo-responsive dyes are dissolved in chloroform reagent, is 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 the Rectangular boxes with several evenly distributed aperture; Then, by mixed cellulose ester film-clamp between 2 ABS thin plates, and allow the apertures align on 2 ABS thin plates, middle cellulose mixture ester film can be come out; Finally with waterproof double faced adhesive tape, ABS thin plate and cellulose mixture ester film are fixed.
3rd step: the chemical colour reaction agent solution first step obtained is got on the mixed cellulose ester microporous membrane that 0.1-10 μ L is fixed on substrate in aperture by trace sampling apparatus, an aperture fixes a kind of visual sensitive material, then obtains visual taste sensor array by after chloroform drying.
Described a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique, mixed cellulose ester mems thin film aperture is 0.15-8 μm; ABS plastic sheet gauge is 0.1-2mm; After processing, on ABS plastic thin plate, hole diameter is 2-6cm, and Rectangular boxes area is 3-5cm
2.
The signal of described collection is react forward and backward visible sensor array R in reaction system, the difference of G, B color value.
Described a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique, data processing method is the regression algorithm in Chemical Measurement, comprises, neural net regression, partial least squares regression or Support vector regression etc.Using the visible sensor array data collected as independent variable, build the Quantitative Prediction Model of heavy metal ion using concentration of heavy metal ion as dependent variable.According to regression model performance, filter out regression algorithm for specific sample concentration of heavy metal ion prediction effect optimum 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): this index is mainly used in evaluating the feasibility of certain modeling method and the predictive ability of institute's established model, is calculated in model training process by the method for validation-cross.
In formula,
for in calibration set
ithe measured value of individual sample;
for rejecting the in training set
iafter individual sample, with the model of the Sample Establishing of remainder, this model is to
iindividual sample predictions value,
nfor training set sample number.
2. predicted root mean square error (Root mean squared error of prediction, RMSEP): namely model is to the predicted root mean square error of forecast set sample, is mainly used in evaluating institute's established model to the predictive ability of external samples.Predicted 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 value is calculated as follows:
In formula,
with
to be respectively in forecast set
ithe actual measurement collection of individual sample and forecast set,
nfor forecast set sample number.
3. related coefficient (Correlation coefficient,
r): or claim squared correlation coefficient, for investigating the degree of correlation between the predicted value of sample and measured value,
rmore close to 1, then illustrate that the degree of correlation between predicted value and measured value is better,
r 2 be calculated as follows:
In formula,
with
to be respectively in sample set (comprising calibration set and forecast set)
ithe measured value of individual sample and predicted value,
for the mean value of the measured value of samples all in sample set.
The invention has the beneficial effects as follows: (1) is because this method employing porphyrin and pyridylazo class chemo-responsive dyes are as visible sensor sensitive material, sensor heavy metal ion has non-specific, detects while therefore can realizing contents of many kinds of heavy metal ion;
(2) owing to adopting water wettability cellulose mixture ester film as baseplate material, the heavy metal ion in sample liquid fully can be reacted with chemo-responsive dyes, therefore, substantially increase the detection sensitivity of this method, can to ppm level heavy metal ion accurate quantitative analysis;
(3) visible sensor array performance is stablized, reproducible, reliable results;
(4) detection time is short, and the reaction time is 5min;
(5) cost is low.
Accompanying drawing illustrates:
The neural net regression model result that Fig. 1 visualization technique detects trace Pb, Cd, Hg in aqueous solution simultaneously.
Embodiment:
Below in conjunction with accompanying drawing, a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique of the present invention is described in more detail:
(1) a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique of the present invention, comprises the preparation of visible sensor array, information acquisition and data processing 3 steps.
(2) visible sensor array has the chemo-responsive dyes of color response, cellulose mixture ester film, ABS plastic thin plate (acrylonitrile-butadiene-styrene (ABS)) and waterproof double faced adhesive tape by heavy metal ion and prepares.Through test of many times, the chemo-responsive dyes selected is 4 kinds of porphyrinses and 2 kinds of pyridylazo compounds, be specially, meso-tetra-(p-hydroxybenzene) porphyrin, meso-tetra-(p-aminophenyl) porphyrin, meso-tetraphenylporphyrin, meso-tetra-(p-methoxyphenyl) porphyrin, 1-(2-pyridylazo)-2-naphthol, 4-(2-pyridylazo) resorcinol; Selected mixed cellulose ester membrane pore size is 0.45 μm; Selected ABS sheet gauge is 0.5mm.
The making step of visible sensor array is as follows:
The first step, the preparation of chemical colour reaction agent solution: be dissolved in chloroform reagent respectively by filter out 4 kinds of porphyrinses and 2 kinds of pyridylazo compounds chemo-responsive dyes, compound concentration is the chemical colour reaction agent solution of 3mM;
Second step, the preparation of visible sensor array base palte: first ABS plastic thin plate is processed into the Rectangular boxes with 6 evenly distributed 4mm apertures, the Rectangular boxes specification after processing is 28mm*20mm; Then, mixed cellulose ester processing film become specification to be 28mm*20mm, the mixed cellulose ester film-clamp after processing between 2 ABS thin plates, and allow the apertures align on 2 ABS thin plates, middle cellulose mixture ester film can be come out; Finally with waterproof double faced adhesive tape, ABS thin plate and cellulose mixture ester film are fixed.
3rd step: get with 10 μ L microscale samplers the chemical colour reaction agent solution that the 5 μ L first steps obtain and drop on the mixed cellulose ester microporous membrane on substrate in aperture, an aperture fixes a kind of visual sensitive material, then obtains visible sensor array by after chloroform drying.
(3) a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique of the present invention, the signal of collection is react forward and backward visible sensor array R in reaction system, the difference of G, B color value.
(4) a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique of the present invention, data processing method is the regression algorithm in Chemical Measurement, comprise, neural net regression, partial least squares regression or Support vector regression etc.For embodiment, detect in aqueous solution while series concentration trace Pb, Cd, Hg, contrast regression model performance finds, BP-neural net regression model is optimum.In BP-neural network model building process, random selecting sample number 2/3 as training set, all the other samples of 1/3 are as test set.BP-neural network topology structure is set to 3 layers, comprises 1 input layer, 1 output layer and 1 hidden layer, and adopts the method for leaving-one method validation-cross to be optimized hidden layer number of network node.Initialization network parameter is as follows, and repetition training number of times is 1000, learning rate is 0.1, factor of momentum is 0.7, training objective error is 1 × 10
-8.
Fig. 1 is a kind of BP-neural net regression model prediction result simultaneously detected trace Pb, Cd, Hg in aqueous solution based on the multiple trace heavy metal ion Simultaneous Detection of visualization technique of the present invention.As can be seen from the figure, the predicated error of neural net regression model to trace Pb, Cd, Hg that method of the present invention builds is less, model prediction related coefficient is higher, shows that a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique of the present invention is effective.
Claims (10)
1. the multiple trace heavy metal ion Simultaneous Detection based on visualization technique, comprise the preparation of visible sensor array, information acquisition and data processing 3 steps, it is characterized in that, visible sensor array has the chemo-responsive dyes of color response, cellulose mixture ester film, ABS plastic thin plate (acrylonitrile-butadiene-styrene (ABS)) and waterproof double faced adhesive tape by heavy metal ion to be prepared; The signal gathered is the color change of reacting forward and backward visible sensor array in reaction system; The data processing method adopted is the multivariate regression algorithm in Chemical Measurement.
2. a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique according to claim 1, is characterized in that, the chemo-responsive dyes that heavy metal ion has color response is porphin series and pyridylazo class developer.
3. a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique according to claim 1, it is characterized in that, visible sensor array making step is:
The first step, the preparation of chemical colour reaction agent solution: filtered out porphyrin chemo-responsive dyes and pyridylazo class chemo-responsive dyes are dissolved in chloroform reagent, preparative chemistry chromogenic reagent solution;
Second step, the preparation of visible sensor array base palte: first ABS plastic thin plate is processed into the Rectangular boxes with several evenly distributed aperture; Then, by mixed cellulose ester film-clamp between 2 ABS thin plates, and allow the apertures align on 2 ABS thin plates, middle cellulose mixture ester film can be come out; Finally with waterproof double faced adhesive tape, ABS thin plate and cellulose mixture ester film are fixed;
3rd step: the chemical colour reaction agent solution first step obtained is got on the cellulose mixture ester film that 0.1-10 μ L is fixed on substrate in aperture by trace sampling apparatus, an aperture fixes a kind of visual sensitive material, then obtains visible sensor array by after chloroform drying.
4. a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique according to claim 3, it is characterized in that, chemo-responsive dyes solution concentration is 1-10mM.
5. a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique according to claim 3, it is characterized in that, mixed cellulose ester membrane pore size is 0.15-8 μm.
6. a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique according to claim 3, it is characterized in that, ABS plastic sheet gauge is 0.1-2mm.
7. a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique according to claim 3, is characterized in that, after processing, on ABS plastic thin plate, hole diameter is 2-6cm.
8. a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique according to claim 3, is characterized in that, the ABS plastic thin plate 3-5cm after processing
2.
9. a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique according to claim 1, it is characterized in that, the signal of collection is the R reacting forward and backward visible sensor in reaction system, G, B color difference.
10. a kind of multiple trace heavy metal ion Simultaneous Detection based on visualization technique according to claim 1, it is characterized in that, data processing method is the multivariate regression algorithm in Chemical Measurement, comprise, neural net regression, partial least squares regression or Support vector regression etc.
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| CN104911905A (en) * | 2015-03-25 | 2015-09-16 | 天津大学 | Coloration and recognition functions fiber used for mercury ion and preparation method thereof |
| CN108444991A (en) * | 2018-02-09 | 2018-08-24 | 江苏大学 | A kind of production method of visible sensor suitable for polymorphic detection object |
| 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 |
| CN109115704A (en) * | 2018-08-29 | 2019-01-01 | 中南大学 | The more metal ion detection Spectroscopy differential preprocess methods of trace under a kind of high zinc background |
| CN113267464A (en) * | 2021-06-17 | 2021-08-17 | 江苏大学 | Method and device for detecting multi-component heavy metal in edible oil based on near infrared combined colorimetric sensor array |
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| US20030143112A1 (en) * | 2000-03-21 | 2003-07-31 | Board Of Trustees Of The University Of Illinois | Colorimetric artificial nose having an array of dyes and method for artificial olfaction |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104911905A (en) * | 2015-03-25 | 2015-09-16 | 天津大学 | Coloration and recognition functions fiber used for mercury ion and preparation method thereof |
| CN104911905B (en) * | 2015-03-25 | 2017-06-23 | 天津大学 | Special colour developing identification function fiber of mercury ion and preparation method thereof |
| CN108444991A (en) * | 2018-02-09 | 2018-08-24 | 江苏大学 | A kind of production method of visible sensor suitable for polymorphic detection object |
| 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 |
| CN109115704A (en) * | 2018-08-29 | 2019-01-01 | 中南大学 | The more metal ion detection Spectroscopy differential preprocess methods of trace under a kind of high zinc background |
| CN113267464A (en) * | 2021-06-17 | 2021-08-17 | 江苏大学 | Method and device for detecting multi-component heavy metal in edible oil based on near infrared combined colorimetric sensor array |
| CN113267464B (en) * | 2021-06-17 | 2024-06-07 | 江苏大学 | Method and device for detecting multi-component heavy metals in edible oil based on near infrared combined colorimetric sensor array |
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