CN103575728A - Trace heavy metal ion detection method taking filter paper as basic colorimetric sensor array - Google Patents

Trace heavy metal ion detection method taking filter paper as basic colorimetric sensor array Download PDF

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CN103575728A
CN103575728A CN201210272015.4A CN201210272015A CN103575728A CN 103575728 A CN103575728 A CN 103575728A CN 201210272015 A CN201210272015 A CN 201210272015A CN 103575728 A CN103575728 A CN 103575728A
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heavy metal
metal ion
indicator
filter paper
color
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CN201210272015.4A
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CN103575728B (en
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冯亮
关亚风
李笑
李慧
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中国科学院大连化学物理研究所
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Abstract

The invention discloses a method for detecting multiple trace heavy metal ions through a colorimetric sensor array. The method comprises the steps of drawing specific hydrophilic channels on quantitative filter paper through a wax spray type printer, respectively fixing several heavy metal ion indicators in the respective hydrophilic channels to form an indicator array, and connecting a water absorption unit fixed with a macromolecular water absorption material to the rear end of each channel, wherein a heavy metal ion solution generates reaction with the indicators through the hydrophilic channels; furthermore, under the water absorption action of the macromolecular materials at the rear ends, the heavy metal ion solution can continuously flow through the indicators and generate enrichment reaction, so that the aim of half-quantitative measurement on contents of eight trace heavy metal ions in water can be achieved. Color imaging equipment is used for collecting color changes of the indicators in front of and behind different heavy metal ions and constructing a fingerprint of each heavy metal ion. In a test process, a mathematical statistics method is adopted; a sample atlas is compared with the fingerprints, so that unknown heavy metal ions can be qualitatively and half-quantitatively analyzed.

Description

Filter paper is that basic colorimetric sensor array is for trace heavy metal ion detection method
Technical field
The present invention relates to sensor, specifically a kind ofly take the method that filter paper detects for the multiple trace heavy metal ion of water as basic colorimetric sensor array.
Background technology
In recent years, the fast development of global industrial economy and the series of environmental problems that brings has caused serious harm to ecosystem balance and human health, has caused everybody common concern.Water is the mankind's Source of life, and it and nature and the mankind's harmony development is closely bound up, thereby the pollution problem of water resource becomes one of hot issue of environmental area.In numerous water pollutes, heavy metal pollution has accounted for sizable proportion, in view of having easily, it is bioaccumulation, has the feature such as biological amplification, toxicity be large, therefore the timely early warning of heavy metal pollution in water, express-analysis detects and effectively administers effective utilization of human health and water resource is become to particularly important.
Some heavy metals pass through mining, smelting and processing of metals, the discharge of wastewater from chemical industry, the abuse of agriculture chemical, the natural source forms such as artificial pollution and geologic erosion, weathering such as throw aside of house refuse enter in water, and final major part is converted into the cationic salts of solubility and is extensively present in occurring in nature.The World Health Organization (WHO) and EPA (EPA) have all given the attention of height to heavy-metal pollution thing in water.China also in new < < drinking water sanitary standard > > to daily potable water in the content of heavy metal ion carried out clearly regulation, and formulated < < integrated wastewater discharge standard > >, strictly limit the discharge of heavy metal ions in sewage.
At present increasingly mature for the research of Heavy Metal Pollution Control in water, the heavy metal ion qualitative and quantitative detection technology extensively adopting in the world comprises Atomic absorption (AAS), inductively coupled plasma atomic emission (ICP-AES), inductivity coupled plasma mass spectrometry (ICP-MS), anodic stripping voltammetry, x ray fluorescence spectrometry, plasma induction spectrum etc.These methods can successfully detect underwater trace heavy-metal pollution thing, and the various detection of heavy metal ion instrument based on these methods are the Safe Guard of commercialization ,Ru U.S. Trace Detect company also, the series of products such as Yield Guard.Yet the general cost of above-mentioned all multi-methods is higher, need large-scale instrument and skilled operating personnel, and generally sampling at the scene, then delivers to laboratory and carries out off-line analysis, exists consuming time, analytical procedure is complicated, and analytical instrument is expensive, and the low and sample of sample frequency is difficult for the shortcomings such as preservation.In some cases, need to know in time environmental pollution situation, to formulate rapidly corresponding treatment Countermeasures; And the variform heavy metal ion of tool, between its each chemical form, often in mobile equilibrium, loaded down with trivial details sample pre-treatments (pre-separation, enrichment, derivative etc.) also can cause redistributing of different chemical form, thereby greatly affects measurement result.
In the face of these difficult problems, optimal solution is exactly that original position detects in real time.Have on the market at present some commercial detection of heavy metal ion test paper, some is taked to infiltrate to contain the organic solution of indicator and dry and makes, and does not take into full account the fixing of indicator, causes test paper easily to decolour; Other adopt in manufacturing test paper process indicator are mixed and is prepared with paper pulp, and manufacturing process is loaded down with trivial details, and detection sensitivity is not satisfactory.Remove outside simple visual colorimetric determination, the spectrum color comparator of the at present existing import in market, can only assess a kind of indicator but these colorimetric equipment are many, the phase mutual interference in the time of can not eliminating several samples same indicator is responded simultaneously.This wherein, photochemistry colorimetric method is easy and simple to handle because of it, with low cost and be subject to the extensive favor of scientists, array analysis becomes and solves different heavy-metal pollution things to one of best mode of the mutual intersection interference problem of indicator.
Summary of the invention
The object of the present invention is to provide a kind of method that filter paper detects for the multiple trace heavy metal ion of water as basic colorimetric sensor array of take.
For achieving the above object, the technical solution used in the present invention is:
1) preparation of sensor array: use solid ink jet printer to draw passage on quantitative filter paper, after solid wax chine baking oven high-temperature heating, melt, from test paper surface, infiltrate into the back side, by the hydrophobic effect of wax, isolate the hydrophilic channel of corresponding therefrom mind-set external diffusion.Indicator is fixed on the centre of hydrophilic channel by polymkeric substance, hydrophilic channel end is macromolecule water absorbent material fixedly;
2) foundation of finger-print: by heavy metal ion standard solution (5x10 to be detected -5mol/L mercury, lead, cadmium, silver, cobalt, nickel, copper or zinc) join the center sample application zone of the sensor array that fixes indicator, solution evenly spreads apart rapidly from center along different hydrophilic channels, passes through indicator thereupon; By means of the water sorption of passage rear end macromolecule water absorbent material, solution can be along hydrophilic channel continuously from the center sample application zone indicator of flowing through, constantly enrichment reaction;
Sensor array filter paper bottom is provided with color-image forming apparatus, by indicator on acquisition testing test paper, be exposed to the change color before and after various different heavy metal ion, 2 kinds or red, green, blue (RGB) look spectral value corresponding to two or more indicator change color built to " finger-print " of every heavy metal species ion;
3) mathematical statistics: the change color digitizing under 5x10-5mol/L concentration also builds after corresponding " finger-print " to different heavy metal ion by sensor array, for reducing sample bias, every heavy metal species ion is repeated to 5 corresponding experiments, by the Δ R of every group of experiment corresponding under all heavy metal ion 5x10-5mol/L normal concentrations to be measured, Δ G, Δ B value builds matrix, adopt multidimensional variable statistical package (Matlab, MVSP(Multi-Variate Statistic Package) or SPSS(Statistical Package for the Social Sciences) etc. statistical software, matrix is imported after software, in software, adopt the mathematical statistics methods such as cluster analysis or principal component analysis (PCA) to sort out result, for unknown sample, the result in conjunction with after existing fingerprint databases and cluster analysis, is normalized, and by its heavy metal species ion why of the kind judging of unknown sample normalizing, by finger-print aberration power, determines whether the normal concentration that exceeds 5x10-5mol/L.Also can carry out semiquantitative concentration analysis to unknown sample under certain condition.
Be specially:
The method that filter paper detects for multiple trace heavy metal ion as basic colorimetric sensor array, described sensor comprises the priming reservoir that circular ring distributes that is being mutually independent, hydrophilic channel, and heavy metal ion chelating agent,
Use solid ink jet printer on quantitative filter paper, to draw out hydrophilic channel, respectively different heavy metal ion indicator is fixed in the same position of respective channel; The heavy metal ion indicator being fixed on quantitative filter paper of take is sensing material, builds sensor array; After each hydrophilic channel, termination is to be fixed with the suction unit of macromolecule water absorbent material, heavy metal ion solution is via hydrophilic channel and indicator reaction, while is by means of the water sorption of rear end macromolecular material, heavy metal ion solution is continued to flow through indicator, there is enrichment, promote indicator detection sensitivity; Change color gathers relatively by color-image forming apparatus.
1) preparation of sensor array: use solid ink jet printer to draw out live width 0.25-1.25 pound on quantitative filter paper, some of the hydrophobic isolation strip of line length 0.4-1.5cm, are placed in heating 20-60min in 80-150 ℃ of baking oven; Solid wax seal on test paper is melted after being heated, and from test paper surface, infiltrates into the back side, thereby forms many hydrophilic passages.By polyvinyl butyral: trioctyl phosphate: PEG-4000 mixes and is dissolved in 3-10mL absolute ethyl alcohol with 30-75mg:200-280mg:75-200mg mass ratio, under normal temperature, concussion mixes 1-1.5 hour, obtains polymer solution; With 2-6mg/L ratio, various heavy metal ion indicator are joined in above-mentioned synthetic polymkeric substance, stirring and dissolving, adopts kapillary (0.2uL) point sample mode, the polymer solution that is dissolved with heavy metal ion indicator is evenly fixed on the passage of Test paper ( between 20-25 μ m), drying at room temperature under nitrogen protection; Must be for the Test paper of detection of heavy metal ion; Hydrophilic channel end is macromolecule water absorbent material fixedly;
2) foundation of finger-print: by heavy metal ion standard solution (5x10 to be detected -5mol/L mercury, lead, cadmium, silver, cobalt, nickel, copper or zinc) join the center sample application zone of the sensor array that fixes indicator, solution evenly spreads apart rapidly from center along different hydrophilic channels, passes through indicator thereupon; By means of the water sorption of passage rear end macromolecule water absorbent material, solution can be along hydrophilic channel continuously from the center dropping liquid indicator of flowing through, constantly enrichment reaction;
Sensor array filter paper bottom is provided with color-image forming apparatus, by indicator on acquisition testing test paper, be exposed to the change color before and after various different heavy metal ion, 2 kinds or red, green, blue (RGB) look spectral value corresponding to two or more indicator change color built to " finger-print " of every heavy metal species ion;
3) unknown heavy metal ion aqueous sample test process:
According to step 1)-2) operate, difference is, step 2) heavy metal ion aqueous solution is unknown heavy metal ion aqueous sample;
By corresponding red of its change color, green, blue (RGB) look spectral value builds the collection of illustrative plates of sample: adopt scanner color-image forming apparatus to extract the color of each indicator reaction front and back, the color producing on film before and after by Photoshop software, indicator being reacted with heavy metal ion is carried out digitized processing, obtain rgb value corresponding to indicator reaction front and back image, the rgb value of image after reaction is deducted to the rgb value of the front image of reaction, extract the Δ R of " the poor image that subtracts ", Δ G, with Δ B value, then press Δ R, Δ G, the color image that the reduction of Δ B value is corresponding, for unknown heavy metal ion aqueous solution is set up " finger-print " of its correspondence,
After sample test process, adopt mathematical statistics method, use Matlab, MVSP(Multi-Variate Statistic Package) or SPSS(Statistical Package for the Social Sciences) statistical analysis software, the spectrum data of sample and the database in " finger-print " storehouse are contrasted, thereby unknown heavy metal ion is carried out to qualitative or semiquantitative analysis.
Described sensor array host material is hydrophilic quantitative filter paper.
Described hydrophilic channel is printed by wax spray printer, and hot melt is penetrated in filter paper and forms.
Described color-image forming apparatus is CCD, digital camera or scanner.
Described mathematical statistics be by after image digitazation to data cluster analysis or principal component analytical method.
After sample test process, the image of extraction indicator before and after reacting with heavy metal ion, the specific region of selected homogeneous, tries to achieve its corresponding color average RGB value, by image digitazation intuitively, and differs from and subtracts;
The change color producing after indicator reacts with heavy metal ion can reflect by digitized form, for quantitative and semi-quantitative analysis provide foundation, the Mathematical Statistics Analysis that is simultaneously conducive to database, for every heavy metal species ion builds corresponding with it " finger-print ".
By color of image, change the database building and carry out Mathematical Statistics Analysis, adopt a kind of cluster analysis or principal component analysis (PCA) for the method for data normalization, classify.
Described heavy metal ion indicator is 2-(3,5-bis-Bromo-2-pyridylazos)-5-diethylamino phenol, 1,3-diamido-4-(5-Bromo-2-pyridylazo) benzene, 2-(5-Bromo-2-pyridylazo)-5-(diethylin) phenol, 4-(5-Chloro-2-pyridylazo)-1,3-diamino-benzene, 4-(3,5-bis-Bromo-2-pyridylazos)-1,3-diamino-benzene, 2-(5-Bromo-2-pyridylazo)-5-[N, N-dimethyl] phenol, 1-pyridylazo-beta naphthal, 4-(2-pyridylazo) resorcinol;
Quantitative filter paper is ashless level filter paper, aperture between 20-25 μ m.
In described sensor array, have contents of many kinds of heavy metal ion indicator, every heavy metal species ion may also have response on other non-specific indicator, therefore can form corresponding fingerprint response spectra, and be not only a kind of indicator response; Increase the response dimension of sensor, effectively got rid of the phase mutual interference of different heavy metal ion to same indicator response;
The image of extraction indicator before and after reacting with heavy metal ion, the specific region of selected homogeneous, tries to achieve its corresponding color average RGB value, by image digitazation intuitively, and differs from and subtracts.
Described macromolecule water absorbent material can allow sample solution flow through to be continuously fixed with the Test paper passage of indicator.Heavy metal ion, can be by enrichment in the indicator of flowing through, and with the abundant contact reaction of indicator, accelerate its reaction kinetics process.
The reasonable classification that described Mathematical Statistics Analysis is unknown sample provides theoretical and supports.
Tool of the present invention has the following advantages:
1. solid ink jet printer is drawn out hydrophobic isolation strip on hydrophilic quantitative filter paper, and wax infiltrates the filter paper back side after melted by heat, and isolation solution, forms hydrophilic channel.
Macromolecule water absorbent material by sample solution constantly by being fixed with the hydrophilic channel of indicator.Heavy metal ion can constantly by indicator process by effectively enrichment, and fully contact with indicator, accelerated the reaction kinetics process of indicator and heavy metal ion.
3. contents of many kinds of heavy metal ion indicator forms sensor array, and each heavy metal ion has its corresponding dactylogram, and is not only an indicator response.
4. the change color that indicator produces after reacting with heavy metal ion can reflect by digitized form, for quantitative and semi-quantitative analysis provide basis, the Mathematical Statistics Analysis that is simultaneously conducive to database, for every heavy metal species ion builds corresponding with it finger-print.
Accompanying drawing explanation
Fig. 1 is the design of sensor array, sample solution is evenly spread apart rapidly along eight different hydrophilic channels (301) by quantitative filter paper (101) center sample application zone (201), the indicator (401) of flowing through, until by rear end suction unit (501) inner macromolecule absorbent material (601) Heavy metal constantly.Water absorption device bottom is transparent class visual window, and imaging system sees through the direction capture of Test paper via solution.
Fig. 2 be colorimetric sensor array to 8 heavy metal species ions at 5x10 -5the response of mol/L concentration (for ease of observing, color gamut expands to 0-255 from 4-35).
The change color producing is via Photoshop tMsoftware shows in the drawings after strengthening with equal proportion.This software is only processed as showing the power of change color, does not affect the numerical value of " finger-print " after each heavy metal ion digitizing.From figure, can obviously find out, 8 heavy metal species ions have shown respectively " finger-print " that it is exclusive, for it is effectively distinguished and lay a good foundation.
Fig. 3 be colorimetric sensor array to 8 heavy metal species ions at 5x10 -5the cluster analysis of mol/L concentration-response.Every heavy metal species ion carries out 5 parallel experiments, and the good reappearance of sensor has guaranteed that 5 groups of parallel experiments of same heavy metal ion are classified as a class well; , be based upon in the Basis of Database of " finger-print " after each heavy metal ion digitizing, the response of various dimensions makes 8 heavy metal species ions be able to each other effective differentiation meanwhile.
Embodiment
The method that filter paper detects for multiple trace heavy metal ion as basic colorimetric sensor array, described sensor comprises the priming reservoir that is circular ring distribution being mutually independent, hydrophilic channel, and heavy metal ion chelating agent.
Use solid ink jet printer on quantitative filter paper, to draw out hydrophilic channel, respectively different heavy metal ion indicator is fixed in the same position of respective channel; The heavy metal ion indicator being fixed on quantitative filter paper of take is sensing material, builds sensor array; After each hydrophilic channel, termination is to be fixed with the suction unit of macromolecule water absorbent material, heavy metal ion solution is via hydrophilic channel and indicator reaction, while is by means of the water sorption of rear end macromolecular material, heavy metal ion solution is continued to flow through indicator, there is enrichment, promote indicator detection sensitivity; Change color gathers relatively by color-image forming apparatus.
The foundation in standard " finger-print " storehouse:
1) the sensor array test paper for detection of heavy metal ion of immobilizing indicator, concrete preparation process is as follows:
Use solid ink jet printer on quantitative filter paper, to draw out 1 pound of live width, 16 of the hydrophobic isolation strip of line length 0.6cm, are placed in heating 30min in 120 ℃ of baking ovens; Solid wax seal on test paper is melted after being heated, and from test paper surface, infiltrates into the back side, thereby forms many hydrophilic passages.
By polyvinyl butyral: trioctyl phosphate: PEG-4000 mixes and is dissolved in 5mL absolute ethyl alcohol with 30mg:200mg:75mg mass ratio, under normal temperature, concussion mixes 1 hour, obtains polymer solution, by different quality heavy metal ion indicator [2-(3, 5-bis-Bromo-2-pyridylazos)-5-diethylamino phenol (4mg), 1, 3-diamido-4-(5-Bromo-2-pyridylazo) benzene (2mg), 2-(5-Bromo-2-pyridylazo)-5-(diethylin) phenol (2mg), 4-(5-Chloro-2-pyridylazo)-1, 3-diamino-benzene (4mg), 4-(3, 5-bis-Bromo-2-pyridylazos)-1, 3-diamino-benzene (4mg), 2-(5-Bromo-2-pyridylazo)-5-[N, N-dimethyl] phenol (4mg), 1-pyridylazo-beta naphthal (4mg), 4-(2-pyridylazo) resorcinol (4mg)] join respectively in the above-mentioned synthetic polymer solution of 1mL, stirring and dissolving, adopt kapillary (0.2uL) point sample mode, the polymer solution that is dissolved with heavy metal ion indicator is evenly fixed on eight passages of Test paper ( between 20-25 μ m), drying at room temperature under nitrogen protection, must be for the Test paper of detection of heavy metal ion,
2) colorimetric reads: in priming reservoir, fill in macromolecule water absorbent material, and with glue, macromolecule water absorbent material and Test paper can be fitted tightly; In the accumulation of dropping liquid place, Test paper center, adding 800uL concentration is respectively 5x10 -5mol/L mercury, lead, cadmium, silver, cobalt, nickel, copper, zinc eight heavy metal species ion standard solution, solution is evenly spread apart rapidly along eight different " hydrophilic " passages by Test paper center, the indicator of flowing through, by the continuous Heavy metal of priming reservoir, rear end inner macromolecule absorbent material, after the different indicator of each passage react with heavy metal ion enrichment, produce respectively different colours and change, by scanner, read.
3) by the rgb value before and after each indicator change color of Photoshop software analysis, reacted indicator rgb value is deducted to the rgb value before reaction, obtain the Δ R of error image, Δ G, Δ B value.Then press Δ R, Δ G, the color image that the reduction of Δ B value is corresponding, for each heavy metal ion is at 5x10 -5under mol/L concentration, set up " finger-print " of its correspondence.Every heavy metal species ion is repeated to 5 corresponding experiments, by all metals to be measured at 5x10 -5the Δ R of every group of corresponding experiment under mol/L concentration, Δ G, Δ B value builds matrix, adopt multidimensional variable statistical package MVSP(Multi-Variate Statistic Package) statistical software, matrix is imported after software, in software, adopt cluster analysis mathematical statistics method to sort out result, obtain heavy metal ion at 5x10 -5cluster analysis database under mol/L concentration.
The mensuration of unknown sample:
Get wherein a kind of heavy metal ion as testing sample, by it at 5x10 -5mol/L concentration left and right configuration unknown sample solution.
1) the sensor array test paper for detection of heavy metal ion of immobilizing indicator, concrete preparation process is as follows:
Use solid ink jet printer on quantitative filter paper, to draw out 1 pound of live width, 16 of the hydrophobic isolation strip of line length 0.6cm, are placed in heating 30min in 120 ℃ of baking ovens; Solid wax seal on test paper is melted after being heated, and from test paper surface, infiltrates into the back side, thereby forms many hydrophilic passages.
By polyvinyl butyral: trioctyl phosphate: PEG-4000 mixes and is dissolved in 5mL absolute ethyl alcohol with 30mg:200mg:75mg mass ratio, under normal temperature, concussion mixes 1 hour, obtains polymer solution, by different quality heavy metal ion indicator [2-(3, 5-bis-Bromo-2-pyridylazos)-5-diethylamino phenol (4mg), 1, 3-diamido-4-(5-Bromo-2-pyridylazo) benzene (2mg), 2-(5-Bromo-2-pyridylazo)-5-(diethylin) phenol (2mg), 4-(5-Chloro-2-pyridylazo)-1, 3-diamino-benzene (4mg), 4-(3, 5-bis-Bromo-2-pyridylazos)-1, 3-diamino-benzene (4mg), 2-(5-Bromo-2-pyridylazo)-5-[N, N-dimethyl] phenol (4mg), 1-pyridylazo-beta naphthal (4mg), 4-(2-pyridylazo) resorcinol (4mg)] join respectively in the above-mentioned synthetic polymer solution of 1mL, stirring and dissolving, adopt kapillary (0.2uL) point sample mode, the polymer solution that is dissolved with heavy metal ion indicator is evenly fixed on eight passages of Test paper ( between 20-25 μ m), drying at room temperature under nitrogen protection, must be for the Test paper of detection of heavy metal ion,
2) colorimetric reads: in priming reservoir, fill in macromolecule water absorbent material, and with glue, macromolecule water absorbent material and Test paper can be fitted tightly; The accumulation of dropping liquid place, Test paper center adds the solution of the unknown concentration of heavy metal ion of 800uL, solution is evenly spread apart rapidly along eight different " hydrophilic " passages by Test paper center, the indicator of flowing through, by the continuous Heavy metal of priming reservoir, rear end inner macromolecule absorbent material, after the different indicator of each passage react with heavy metal ion enrichment, produce respectively different colours and change, by scanner, read.
3) by the rgb value before and after each indicator change color of Photoshop software analysis, reacted indicator rgb value is deducted to the rgb value before reaction, obtain the Δ R of error image, Δ G, Δ B value.Then press Δ R, Δ G, the color image that Δ B value reduction is corresponding, for unknown sample is set up " finger-print " of its correspondence.By the Δ R of this finger-print, Δ G, Δ B value substitution matrix, adopt multidimensional variable statistical package MVSP(Multi-Variate Statistic Package) statistical software, in software, adopt cluster analysis mathematical statistics method to sort out result, obtain the qualitative of this heavy metal ion and sxemiquantitative information.
The present invention draws out hydrophilic channel by colored solid ink jet printer on quantitative filter paper, several heavy metal ion indicator are fixed wherein and forming array respectively, and after passage termination to be plugged with the water absorption device of macromolecule water absorbent material, thereby reach in 10 minutes can be to water in the multiple trace heavy metal ion content such as mercury, lead, cadmium, silver, cobalt, nickel, copper, zinc by constantly accumulating, carry out the mensuration of rapid semi-quantitative.This sensor array gathers with color-image forming apparatus the change color that indicator is exposed to various different heavy metal ion front and back, red, green, blue corresponding to its change color (RGB) look spectral value is built to " finger-print " of every heavy metal species ion.In sample test process, adopt the mathematical statistics methods such as cluster analysis and principal component analysis (PCA), the collection of illustrative plates of sample is contrasted with " finger-print " storehouse, thereby unknown heavy metal ion is carried out to qualitative or semiquantitative analysis.This method comprises the drafting of hydrophilic channel, the extraction of the design of water absorption device, aberration and the mathematical statistics of data three steps.Colored solid ink jet printer is drawn out the selectivity hydrophilic channel of heavy metal ion solution on Test paper; The water absorber of unique design can allow heavy metal sample solution constantly when being fixed with " water delivery " passage of indicator by effectively enrichment, improved the probability that indicator reacts with heavy metal ion; Many separate hydrophobic channel arrays have been avoided interference to each other; Heavy metal ion by enrichment after, with indicator generation chromogenic reaction, its change color is through imaging device collection, and digitizing, for quantitative or semiquantitative determination provide foundation, and the tiny aberration that can cannot observe naked eyes distinguishes, further promotes the detection sensitivity of sensor.

Claims (8)

  1. Filter paper be basic colorimetric sensor array for trace heavy metal ion detection method, it is characterized in that:
    Use solid ink jet printer on quantitative filter paper, to draw out hydrophilic channel, respectively more than 2 kinds or 3 kinds different heavy metal ion indicator are fixed on the position of respective channel Yu center sample application zone equidistance; The heavy metal ion indicator being fixed on quantitative filter paper of take is sensing material, builds sensor array; At each hydrophilic channel end, be connected with the suction unit of pbz polymer absorbent material, heavy metal ion solution is via hydrophilic channel and indicator reaction, while is by means of the water sorption of end macromolecular material, heavy metal ion solution is continued to flow through indicator, there is enrichment, promote indicator detection sensitivity; Change color gathers relatively by color-image forming apparatus;
    1) preparation of sensor array:
    Use solid ink jet printer on quantitative filter paper, to draw passage, after solid wax chine baking oven high-temperature heating, melt, from test paper surface, infiltrate into the back side, by the hydrophobic effect of wax, isolate the hydrophilic channel of corresponding therefrom mind-set external diffusion; Indicator is fixed on the middle part of hydrophilic channel by polymkeric substance, hydrophilic channel is fixed with macromolecule water absorbent material away from the end of center sample application zone;
    Described sensor array is arranged on filter paper, comprises center sample application zone and hydrophilic channel, and center sample application zone is the closed circle that wax is printed, and does not wax in the hydrophilic channel place of being attached thereto, and sample solution Ke You center sample application zone is directly diffused into each hydrophilic channel; Hydrophilic channel is more than 2 or 2, and length is identical;
    2) foundation of finger-print: heavy metal ion standard solution to be detected is joined to the sensor array center sample application zone that fixes indicator, solution evenly spreads apart rapidly from center along different hydrophilic channels, passes through indicator thereupon; By means of the water sorption of passage rear end macromolecule water absorbent material, solution can be along hydrophilic channel continuously from the center sample application zone indicator of flowing through, constantly enrichment reaction;
    Sensor array filter paper bottom is provided with color-image forming apparatus, as scanner, digital camera etc., by indicator on acquisition testing test paper, be exposed to the change color before and after various different heavy metal ion, 2 kinds or red, green, blue (RGB) look spectral value corresponding to two or more indicator change color built to " finger-print " of every heavy metal species ion;
    Heavy metal ion standard solution is 5x10 -5the aqueous solution of mol/L mercury, lead, cadmium, silver, cobalt, nickel, copper or zinc;
    3) unknown heavy metal ion aqueous sample test process:
    According to step 1)-2) operate, difference is, step 2) heavy metal ion aqueous solution is unknown heavy metal ion aqueous sample;
    By corresponding red of its change color, green, blue (RGB) look spectral value builds the collection of illustrative plates of sample: adopt color-image forming apparatus to extract the color of each indicator reaction front and back, the color producing on film before and after by Photoshop software, indicator being reacted with heavy metal ion is carried out digitized processing, obtain rgb value corresponding to indicator reaction front and back image, the rgb value of image after reaction is deducted to the rgb value of the front image of reaction, extract the Δ R of " the poor image that subtracts ", Δ G, with Δ B value, then press Δ R, Δ G, the color image that the reduction of Δ B value is corresponding, for unknown heavy metal ion aqueous solution is set up " finger-print " of its correspondence,
    After sample test process, adopt mathematical statistics method, use Matlab, MVSP(Multi-Variate Statistic Package) or SPSS(Statistical Package for the Social Sciences) statistical analysis software, the spectrum data of sample and the database in " finger-print " storehouse are contrasted, thereby unknown heavy metal ion is carried out to qualitative or semiquantitative analysis.
  2. 2. method according to claim 1, is characterized in that: described sensor array host material filter paper is hydrophilic quantitative filter paper.
  3. 3. method according to claim 1, is characterized in that: described hydrophilic channel is printed by wax spray printer, and hot melt is penetrated in filter paper and forms.
  4. 4. method according to claim 1, is characterized in that: described color-image forming apparatus is CCD, digital camera or scanner.
  5. 5. method according to claim 1, is characterized in that: described mathematical statistics be by after image digitazation to data cluster analysis or principal component analytical method.
  6. 6. method according to claim 1, is characterized in that: after sample test process, extraction indicator reacts the image of front and back with heavy metal ion, the specific region of selected homogeneous, try to achieve its corresponding color average RGB value, by image digitazation intuitively, and differ from and subtract;
    The change color producing after indicator reacts with heavy metal ion can reflect by digitized form, for quantitative and semi-quantitative analysis provide foundation, the Mathematical Statistics Analysis that is simultaneously conducive to database, for every heavy metal species ion builds corresponding with it " finger-print ";
    To changing by color of image the database building, carry out Mathematical Statistics Analysis, adopt a kind of cluster analysis or principal component analysis (PCA) for the method for data normalization, classify.
  7. 7. method according to claim 1, it is characterized in that: described heavy metal ion indicator is 2-(3, 5-bis-Bromo-2-pyridylazos)-5-diethylamino phenol, 1, 3-diamido-4-(5-Bromo-2-pyridylazo) benzene, 2-(5-Bromo-2-pyridylazo)-5-(diethylin) phenol, 4-(5-Chloro-2-pyridylazo)-1, 3-diamino-benzene, 4-(3, 5-bis-Bromo-2-pyridylazos)-1, 3-diamino-benzene, 2-(5-Bromo-2-pyridylazo)-5-[N, N-dimethyl] phenol, 1-pyridylazo-beta naphthal, 4-(2-pyridylazo) in resorcinol more than 2 kinds or 3 kinds,
    Quantitative filter paper is ashless level filter paper, aperture between 20-25 μ m.
  8. 8. method according to claim 1, is characterized in that:
    Described sensor array is arranged on filter paper, center sample application zone is circular, away from the hydrophilic channel end of center sample application zone, be connected with the circular priming reservoir of pbz polymer absorbent material, hydrophilic channel is uniformly distributed in center sample application zone surrounding, makes priming reservoir be mutually independent, be circular ring and is distributed in center sample application zone surrounding;
    In priming reservoir, be filled with macromolecule water absorbent material, form suction unit.
CN201210272015.4A 2012-08-01 2012-08-01 Based on filter paper, colorimetric sensor array is used for trace heavy metal ion detection method CN103575728B (en)

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