CN106053414A - Water body heavy metal online detection method and device based on fluorescence quenching - Google Patents

Water body heavy metal online detection method and device based on fluorescence quenching Download PDF

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Publication number
CN106053414A
CN106053414A CN201610530549.0A CN201610530549A CN106053414A CN 106053414 A CN106053414 A CN 106053414A CN 201610530549 A CN201610530549 A CN 201610530549A CN 106053414 A CN106053414 A CN 106053414A
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solution
heavy metal
water
quantum dot
cuvette
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张辉
邓超
潘孙强
陈哲敏
陈怡�
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Zhejiang Province Institute of Metrology
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Zhejiang Province Institute of Metrology
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching

Abstract

The invention discloses a method and device utilizing a fluorescence quenching principle to online detect content of heavy metal in water. The method includes that a quantum dot solution and a detected water sample are parallelly connected in a low-pressure gradient mixer, and liquid after mixing is fed into a cuvette through a constant flow pump for detection; the cuvette is provided with a liquid inlet and a liquid outlet, so that continuous feeding and discharging of a mixed solution can be realized; the cuvette is positioned in a detection light path, a laser device emits laser to be ejected into the cuvette, emitted fluorescence intensity is converted into electric signals, and concentration of heavy metal ions in the water by detecting changing of the electric signals. Real-time continuation from sampling and reaction to detection is realized, so that quick continuous online detection of the heavy metal in the water is realized.

Description

A kind of heavy metal in water online test method based on fluorescent quenching and device thereof
Technical field
The present invention relates to a kind of detection method, a kind of simple and efficient to handle, the shortest, low cost, highly sensitive and Heavy metal in water online test method based on fluorescent quenching that selectivity is high and device thereof.
Background technology
Heavy metal has extremely strong enriching, produces degraded in natural environment hardly, and its source is wide, residual time Between long, have cumulative bad, can along food chain transport, pollute after be difficult to be found and be difficult to recovery etc., severely compromise the mankind's Healthy.Therefore in water, the detection of content of beary metal to protection health and is curbed environmental pollution significant.A conventional huge sum of money Belong to detection method and have atomic absorption spectrography (AAS), atomic fluorescence spectrometry, spectrophotography, electrochemical methods etc..These tradition Analytical technology be widely used at present, but still come with some shortcomings, such as instrument and equipment is expensive, detection process more Loaded down with trivial details, sample pretreatment is complicated, and operation requires the shortcomings such as high, the most simply, quickly, heavy metal efficient, with low cost from Sub-detection method is the study hotspot of society.
Quantum dot (quantum dots, QDs) i.e. radius less than or close to the semiconductor nanocrystal of Exciton Bohr Radius (semiconductor nanocrystals), diameter is between 1-10nm, it is possible to accept exciting light or plus producing fluorescence after voltage Semiconductor nanoparticle.Quantum dot was widely used in analyzing in the middle of detection as fluorescent probe in recent years.Organic glimmering with traditional Light probe is compared, and quantum dot has preferable light stability, higher fluorescence quantum yield, is used for detecting heavy metal ion and has High sensitivity, and quantum dot surface modify different groups special metal is had higher selectivity.Quantum dot with not With Action of Metal Ions, this effect shows as fluorescent quenching or Fluorescence Increasing, and concentration of metal ions with cause fluorescent quenching Or the change intensity of Fluorescence Increasing is certain linear relationship.Utilize this linear relationship, thus realize quantum dot to metal ion Quantitative determination.
Chen et al. reports the CdS QDs alternative modified through different modifying agent and measures Zn2+And Cu2+[Chen Y F, Rosenzweig Z.Luminescent CdS Quantum Dots as Selective Ion Probes[J],Anal Chem.2002, 74(19):5132-5138.]。
Cai et al. has synthesized the CdTe QDs that dimercaptosuccinic acid is stable in aqueous phase, and this quantum dot can detect trace in water sample The Ag of level+, and there is higher degree of accuracy, detection is limited to 54nmol L-1。[Cai C,Cheng H,Wang Y,et al. Mercaptosuccinic acid modified CdTe quantum dots as a selective fluorescence sensor for Ag+ determination in aqueous solutions[J].RSC Adv.2014,4(103):59157-59163.]
The CdSe quantum dot that Zheng et al. modifies with Cys is to Hg2+Ion is detected.[(Zheng likes ZHENG Ai-fang Virtue), FANG Dian-jun (Fang Dianjun), CHEN Jin-long (Chen Jinlong) .Preparation of functionalized CdSe Quantum dots and studies on the selective determination of mercury ion be (functionalization CdSe quantum dots Preparation and the research as mercury ion fluorescence probe) [J] .J of Anqing Teach Coll (Nat Sci Edition) (learn by Anqing normal school Institute's journal (natural science edition)), 2008,14 (2): 39-44.]
Bu etc.[16]People is coated with CdSe quantum dot by bionical mode degeneration bovine serum albumin (dBSA), utilizes Cu2+High to it Sensitivity, high selective fluorescence quenching establish detection Cu2+Method, and discuss Fluorescence quenching mechanism.[Bu X H, Zhou Y M,He M,Chen.et al.Bioinspired,direct synthesis of aqueous CdSe quantum dots for high-sensitive copper(ii)ion detection[J].Dalton Trans,2013,42(43):15411-15420.]
In the method for existing quantum dots characterization heavy metal ion, being all intermittent detection, offline inspection, about on-line continuous detection Method and apparatus research has no report.Our research is to build to utilize the side of heavy metal in quantum dot continuous on-line detection water Method and device.
Summary of the invention
The invention discloses and a kind of utilize the apparatus and method of content of beary metal in Fluorescence Quenching Principle on-line checking water.The present invention Method and apparatus, from sample introduction, be reacted to detection, it is achieved real-time continuous, it is achieved thereby that quickly continuously the existing of heavy metal in water Line detects.
To achieve these goals, the present invention is by the following technical solutions:
A kind of heavy metal in water online test method based on fluorescent quenching, said method comprising the steps of:
1) buffer solution configuration；
2) quantum dot solution synthesis；Quantum dot solution is for using 3-mercaptopropionic acid and composite modified dose of ascorbic acid, or Cys is Dressing agent CdSe quantum dot solution；
3) configuration of the detected water sample containing heavy metal ion；
4) quantum dot solution and water sample after buffered solution regulation pH carry out mixing instead by low pressure gradient blender in the ratio of 1:1 Should；
5) mixed solution is detected by inlet injection cuvette through constant flow pump, and the solution after detection is discharged through leakage fluid dram； 6) laser that laser instrument sends is divided into two-way, light path 1 and light path 2 through beam splitter；
7) light path 1 is after cuvette, at the light of vertical direction after optical filter filters out veiling glare, then converges through collecting lens, Detected by detector one；
8) light path 2 is reference light paths, and the laser after light splitting is converged by collecting lens, detector two detect, and is used for observing Laser power has undamped, it is ensured that data do not occur deviation；
9) result that two-way light path detector detects is sent into data processing module and is carried out photoelectric signal transformation, then inputs computer, passes through After software processes, the optical signal of light path 1 changes and obtains corresponding electric signal value, by a series of concentration of heavy metal ion with collect Electrical signal data, determines detection model y=ax+b, and in detection model, x is heavy metal concentration in water, and y is each concentration heavy metal The signal of telecommunication difference that solution and blank solution collect, a, b are coefficient constant, use Linear Regression Model in One Unknown to enter data Row processes, and obtains the heavy metal concentration of solution to be measured.In the technical program, use low pressure gradient blender and accurate constant flow pump Realize in the detection cell that quantum dot, heavy metal solution are mixed into self-service design the most continuously, mixed solution Constantly flowed into by above detection cell, slowly discharge from bottom during detection, be achieved in the continuous detecting of fluorescence intensity change, Thus realize the on-line monitoring of heavy metal concentration in solution to be measured.
As preferably, step 2) CdSe quantum dot that quantum dot solution is prepared by hydrothermal synthesis method, use 3-mercaptopropionic acid Being dressing agent with ascorbic acid mixed solution, synthetic method is addition ultra-pure water in 100ml reaction vessel, protects at noble gas Protect down and be sequentially added into selenium powder and NaBH4, reaction under the conditions of 35-40 DEG C is until black Se powder is wholly absent, and solution is become by muddiness Colourless or pink colour is transparent, prepare NaHSe precursor solution, be cooled to room temperature standby, selenium powder and NaBH4Mol ratio is 1:2-1:4； After another reaction vessel adds ultra-pure water, under inert gas shielding, it is sequentially added into CdCl2·2.5H2O and 3-mercaptopropionic acid With ascorbic acid mixed solution, in mixed solution, the mol ratio of 3-mercaptopropionic acid and ascorbic acid is that 0.3:1-2:1, Se and Cd rub That ratio is 1:3-1:6, CdCl2·2.5H2The mol ratio of O and ascorbic acid is 1:6-1:10, adds buffering molten after being sufficiently stirred for dissolving Liquid regulation pH to 9-11, prepares Cd presoma；NaHSe precursor solution is joined in Cd precursor solution, in 80-100 DEG C Lower backflow 1h, it is thus achieved that orange-yellow CdSe quantum dot solution.
As preferably, step 2) CdSe quantum dot that quantum dot solution is prepared by hydrothermal synthesis method, use Cys For dressing agent, synthetic method is addition ultra-pure water in 100ml reaction vessel, be sequentially added under inert gas shielding selenium powder and NaBH4, reacting under the conditions of 35-40 DEG C to the reaction of black Se powder completely, reaction solution is become clarification by muddiness, prepares NaHSe Precursor solution, is cooled to room temperature standby, selenium powder and NaBH4Mol ratio is 1:2-1:4；Another reaction vessel adds ultra-pure water, Under inert gas shielding, it is sequentially added into CdCl2·2.5H2O and Cys, Se and Cd mol ratio is 1:2.5-1:4.5, CdCl2·2.5H2The mol ratio of O and Cys is 1:1-1:2.5, regulates pH to 9-11, prepare after being sufficiently stirred for dissolving Cd presoma, joins NaHSe precursor solution in Cd precursor solution, and reflux at 50-65 DEG C 1h, it is thus achieved that yellowish The CdSe quantum dot solution of color.
As preferably, step 3) in detected water sample be dimercurion solution or lead ion solution；Lead ion solution preparation side Method is: precision weighs plumbi nitras 0.16g, puts in 100ml volumetric flask, after adding concentrated nitric acid 0.5ml and 5ml water dissolution, dilute with water Release to scale, shake up, as stock solution (concentration is 100mg/L)；Low concentration Pb2+Solution uses the mode of stepwise dilution to obtain； Mercury ion solution uses concentration to be that 1000mg/L mercury standard solution stepwise dilution obtains.
As preferably, it is characterised in that step 1) in buffer solution be pH be the Tris-HCl buffer solution of 8, configuration Method is: weighs 6.057g trishydroxymethylaminomethane and is dissolved in constant volume in 500ml volumetric flask, obtains 0.1mol/L Tris solution, After measure this Tris solution of 50ml and 29.2ml0.1mol/L hydrochloric acid solution and mix and be diluted to 100ml, it is thus achieved that pH is 8 Tris-HCl buffer solution.
As preferably, it is characterised in that step 6) in, the wavelength of laser is 450nm.
As preferably, step 7) in, the filter range of optical filter is 550-590nm.
A kind of heavy metal in water on-line measuring device based on fluorescent quenching, described detection device includes reacting circuit, detection line Road, data processor and computer, detection device is placed in the casing of airtight dark.
As preferably, described reaction circuit is: quantum dot solution and detected water sample parallel connection access low pressure gradient blender, mixed After conjunction, liquid detects through constant flow pump feeding cuvette.
As preferably, described detection circuit is: the laser that laser instrument sends is divided into two-way through beam splitter, and a road is as reference Light path is detected by detector one after collecting lens converges, and another road is irradiated to cuvette, the fluorescence warp that cuvette sends Optical filter and collecting lens are detected by detector two after converging, and the fluorescence signal that two detectors detect is processed mould by data Block changes into the signal of telecommunication after processing and shows through software on computers.
The present invention is simple and efficient to handle, the shortest, low cost, and testing result is obvious, and sensitivity and selectivity are higher, and Completely dispense with the problem worrying to be polluted by test substance, from sample introduction, be reacted to detection, it is achieved real-time continuous, it is achieved thereby that water The quick continuous on-line detection of middle heavy metal.
Accompanying drawing explanation
Fig. 1 is assembly of the invention structural representation.
In figure: 1, quantum dot solution；2, water sample；3, blender；4, pump；5, cuvette；6, laser instrument；7、 Beam splitter；8, collecting lens；9, detector one；10, optical filter；11, collecting lens；12, detector two；13, number According to processing module；14, computer.
Fig. 2 is the linear graph of embodiment 3.
Detailed description of the invention
Below by specific embodiment, technical scheme is described in further detail.Should be appreciated that the present invention Enforcement be not limited to the following examples, any pro forma accommodation being made the present invention and/or change fall within this Invention protection domain.
In the present invention, if not refering in particular to, all of part, percentage ratio are unit of weight, and the equipment used and raw material etc. are equal It is commercially available or commonly used in the art.Method in following embodiment, if no special instructions, is the routine of this area Method.
Reference Fig. 1, a kind of heavy metal in water on-line measuring device based on fluorescent quenching:
Reaction circuit: quantum dot solution and detected water sample parallel connection access low pressure gradient blender, and after hybrid reaction, liquid is sent into through constant flow pump Cuvette detects.
Detection circuit: the laser that laser instrument sends is divided into two-way through beam splitter, a road as reference light paths through collecting lens Being detected by detector after convergence, another road is irradiated to cuvette, and filtered of the fluorescence that cuvette sends and collecting lens converge Detected by detector after Ju, the fluorescence signal that two detectors detect processed by data processing module after on computers through soft Part shows.Detection device needs to be placed in the casing of airtight dark.
Embodiment 1
A kind of heavy metal in water online test method based on fluorescent quenching, said method comprising the steps of:
1) buffer solution configuration；Buffer solution be pH be the Tris-HCl buffer solution of 8, collocation method is: weigh 6.057g tri-hydroxyl Aminomethane is dissolved in constant volume in 500ml volumetric flask, obtains 0.1mol/L Tris solution, after measure this Tris solution of 50ml with 29.2ml 0.1mol/L hydrochloric acid solution mixes and is diluted to 100ml, it is thus achieved that pH is the Tris-HCl buffer solution of 8；
2) quantum dot solution synthesis；The CdSe quantum dot prepared by hydrothermal synthesis method, uses 3-mercaptopropionic acid and ascorbic acid mixing molten Liquid is composite modified dose, and synthetic method is addition ultra-pure water in 100ml reaction vessel, is sequentially added under inert gas shielding Selenium powder and NaBH4, reaction under the conditions of 35 DEG C is until black Se powder is wholly absent, and solution, by muddy bleach, prepares NaHSe Precursor solution, is cooled to room temperature standby, selenium powder and NaBH4Mol ratio is 1:2；After another reaction vessel adds ultra-pure water, Under inert gas shielding, it is sequentially added into CdCl2·2.5H2O and 3-mercaptopropionic acid and ascorbic acid mixed solution, mixed solution The mol ratio of middle 3-mercaptopropionic acid and ascorbic acid be 0.3:1, Se and Cd mol ratio be 1:3, CdCl2·2.5H2O and Vitamin C The mol ratio of acid is 1:6, adds buffer solution regulation pH to 9, prepare Cd presoma after being sufficiently stirred for dissolving；By NaHSe Precursor solution joins in Cd precursor solution, and reflux at 80 DEG C 1h, it is thus achieved that orange-yellow CdSe quantum dot solution, CdSe quantum dot solution concentration is 6.25 × 10-3mol/L；
3) configuration of the detected water sample containing heavy metal ion；Detected water sample is lead ion solution；Lead ion solution compound method is: essence Close weigh plumbi nitras 0.16g, put in 100ml volumetric flask, after adding concentrated nitric acid 0.5ml and 5ml water dissolution, be diluted with water to scale, Shake up, as stock solution (concentration is 100mg/L)；Stock solution is diluted to Pb2+Solution for content 0.01mg/L；
4) quantum dot solution and water sample after buffered solution regulation pH carry out mixing instead by low pressure gradient blender in the ratio of 1:1 Should；
5) mixed solution is detected by inlet injection cuvette with flow velocity 3ml/min through constant flow pump, the solution warp after detection Cross leakage fluid dram to discharge；
6) laser (wavelength is 450nm) that laser instrument sends is divided into two-way, light path 1 and light path 2 through beam splitter；
7) light path 1 is after cuvette, and the light in vertical direction filters out spuious through optical filter (filter range is 550-590nm) After light, then converge through collecting lens, detector detect；
8) light path 2 is reference light paths, and the laser after light splitting is converged by collecting lens, detector detect, sharp for observing Light device power has undamped, it is ensured that data do not occur deviation；
9) result that two-way light path detector detects is sent into data processing module and is carried out photoelectric signal transformation, then inputs computer, passes through After software processes, the optical signal of light path 1 changes and obtains corresponding electric signal value, by a series of concentration of heavy metal ion with collect Electrical signal data, determines detection model y=ax+b, and in detection model, x is heavy metal concentration in water, and y is the electricity collected Signal value, a, b are coefficient constant, Linear Regression Model in One Unknown process data, and obtaining heavy metal concentration is 0.0092 mg/L。
Embodiment 2
A kind of heavy metal in water online test method based on fluorescent quenching, said method comprising the steps of:
1) buffer solution configuration；Buffer solution be pH be the Tris-HCl buffer solution of 8, collocation method is: weigh 6.057g tri-hydroxyl Aminomethane is dissolved in constant volume in 500ml volumetric flask, obtains 0.1mol/L Tris solution, after measure this Tris solution of 50ml with 29.2ml0.1mol/L hydrochloric acid solution mixes and is diluted to 100ml, it is thus achieved that pH is the Tris-HCl buffer solution of 8；
2) quantum dot solution synthesis；The CdSe quantum dot prepared by hydrothermal synthesis method, uses 3-mercaptopropionic acid and ascorbic acid mixing molten Liquid is composite modified dose, and synthetic method is addition ultra-pure water in 100ml reaction vessel, is sequentially added under inert gas shielding Selenium powder and NaBH4, reaction under the conditions of 40 DEG C is until black Se powder is wholly absent, and solution, by muddy bleach, prepares NaHSe Precursor solution, is cooled to room temperature standby, selenium powder and NaBH4Mol ratio is 1:4；After another reaction vessel adds ultra-pure water, Under inert gas shielding, it is sequentially added into CdCl2·2.5H2O, 3-mercaptopropionic acid and ascorbic acid mixed solution, in mixed solution The mol ratio of 3-mercaptopropionic acid and ascorbic acid be 2:1, Se and Cd mol ratio be 1:6, CdCl2·2.5H2O and ascorbic acid Mol ratio is 1:10, adds buffer solution regulation pH to 11, prepare Cd presoma after being sufficiently stirred for dissolving；Before NaHSe Driving liquid solution and join in Cd precursor solution, reflux at 100 DEG C 1h, it is thus achieved that orange-yellow CdSe quantum dot solution, amount The concentration of son point solution is 1.25 × 10-2mol/L；
3) configuration of the detected water sample containing heavy metal ion；Detected water sample is lead ion solution；Lead ion solution compound method is: essence Close weigh plumbi nitras 0.16g, put in 100ml volumetric flask, after adding concentrated nitric acid 0.5ml and 5ml water dissolution, be diluted with water to scale, Shake up, as stock solution (concentration is 100mg/L)；Stock solution dilution obtains Pb2+Content is the solution of 5.0mg/L；
4) quantum dot solution and water sample after buffered solution regulation pH carry out mixing instead by low pressure gradient blender in the ratio of 1:1 Should；
5) mixed solution is detected by inlet injection cuvette with flow velocity 3ml/min through constant flow pump, the solution warp after detection Cross leakage fluid dram to discharge；
6) laser (wavelength is 450nm) that laser instrument sends is divided into two-way, light path 1 and light path 2 through beam splitter；
7) light path 1 is after cuvette, and the light in vertical direction filters out spuious through optical filter (filter range is 550-590nm) After light, then converge through collecting lens, detector detect；
8) light path 2 is reference light paths, and the laser after light splitting is converged by collecting lens, detector detect, sharp for observing Light device power has undamped, it is ensured that data do not occur deviation；
9) result that two-way light path detector detects is sent into data processing module and is carried out photoelectric signal transformation, then inputs computer, passes through After software processes, the optical signal of light path 1 changes and obtains corresponding electric signal value, by a series of concentration of heavy metal ion with collect Electrical signal data, determines detection model y=ax+b, and in detection model, x is heavy metal concentration in water, and y is each concentration heavy metal The signal of telecommunication difference that solution and blank solution collect, a, b are coefficient constant, Linear Regression Model in One Unknown carry out data Processing, obtaining heavy metal concentration is 4.8mg/L.
Embodiment 3
A kind of heavy metal in water online test method based on fluorescent quenching, said method comprising the steps of:
1) buffer solution configuration；Buffer solution be pH be the Tris-HCl buffer solution of 8, collocation method is: weigh 6.057g tri-hydroxyl Aminomethane is dissolved in constant volume in 500ml volumetric flask, obtains 0.1mol/L Tris solution, after measure this Tris solution of 50ml with 29.2ml0.1mol/L hydrochloric acid solution mixes and is diluted to 100ml, it is thus achieved that pH is the Tris-HCl buffer solution of 8；
2) quantum dot solution synthesis；The CdSe quantum dot prepared by hydrothermal synthesis method, employing Cys is dressing agent, synthesis side Method is addition ultra-pure water in 100ml reaction vessel, is sequentially added into selenium powder and NaBH under inert gas shielding4, 35 DEG C of conditions To the reaction of black Se powder completely, reaction solution is become clarification by muddiness, prepares NaHSe precursor solution, is cooled to room in lower reaction Temperature is standby, selenium powder and NaBH4Mol ratio is 1:2；Another reaction vessel adds ultra-pure water, under inert gas shielding, depends on Secondary addition CdCl2·2.5H2O and Cys, Se and Cd mol ratio is 1:2.5, CdCl2·2.5H2O and L-half Guang ammonia The mol ratio of acid is 1:1, regulates pH to 10, prepare Cd presoma, added by NaHSe precursor solution after being sufficiently stirred for dissolving Entering in Cd precursor solution, reflux at 50 DEG C 1h, it is thus achieved that flaxen CdSe quantum dot solution, CdSe quantum dot is molten The concentration of liquid is 1.04 × 10-3mol/L；
3) configuration of the detected water sample containing heavy metal ion；The stock solution dilution of 1000mg/L obtains Hg2+Content is 0.05mg/L's Solution；
4) quantum dot solution and water sample after buffered solution regulation pH carry out mixing instead by low pressure gradient blender in the ratio of 1:1 Should；
5) mixed solution is detected by inlet injection cuvette with flow velocity 3ml/min through constant flow pump, the solution warp after detection Cross leakage fluid dram to discharge；
6) laser (wavelength is 450nm) that laser instrument sends is divided into two-way, light path 1 and light path 2 through beam splitter；
7) light path 1 is after cuvette, and the light in vertical direction filters out spuious through optical filter (filter range is 550-590nm) After light, then converge through collecting lens, detector detect；
8) light path 2 is reference light paths, and the laser after light splitting is converged by collecting lens, detector detect, sharp for observing Light device power has undamped, it is ensured that data do not occur deviation；
9) result that two-way light path detector detects is sent into data processing module and is carried out photoelectric signal transformation, then inputs computer, passes through After software processes, the optical signal of light path 1 changes and obtains corresponding electric signal value, by a series of concentration of heavy metal ion with collect Electrical signal data, determines detection model y=ax+b, and in detection model, x is heavy metal concentration in water, and y is each concentration heavy metal The signal of telecommunication difference that solution and blank solution collect, a, b are coefficient constant, see Fig. 2, by Linear Regression Model in One Unknown Processing data, obtaining heavy metal concentration is 0.052mg/L.
Cys is used to modify the quantum dot of synthesis to Hg2+Solution carries out on-line monitoring, and y-axis is each concentration Hg2+Solution The difference of the value of electrical signals deduction blank solution value of electrical signals gained obtained, x-axis is corresponding Hg2+The concentration of solution. the gained signal of telecommunication Difference and Hg2+Concentration in the range of 0.005-2mg/L in good linear relationship (R2=0.9987).
Embodiment 4
A kind of heavy metal in water online test method based on fluorescent quenching, said method comprising the steps of:
1) buffer solution configuration；Buffer solution be pH be the Tris-HCl buffer solution of 8, collocation method is: weigh 6.057g tri-hydroxyl Aminomethane is dissolved in constant volume in 500ml volumetric flask, obtains 0.1mol/L Tris solution, after measure this Tris solution of 50ml with 29.2ml0.1mol/L hydrochloric acid solution mixes and is diluted to 100ml, it is thus achieved that pH is the Tris-HCl buffer solution of 8；
2) quantum dot solution synthesis；The CdSe quantum dot prepared by hydrothermal synthesis method, employing Cys is dressing agent, synthesis side Method is addition ultra-pure water in 100ml reaction vessel, is sequentially added into selenium powder and NaBH under inert gas shielding4, 40 DEG C of conditions To the reaction of black Se powder completely, reaction solution is become clarification by muddiness, prepares NaHSe precursor solution, is cooled to room in lower reaction Temperature is standby, selenium powder and NaBH4Mol ratio is 1:4；Another reaction vessel adds ultra-pure water, under inert gas shielding, depends on Secondary addition CdCl2·2.5H2O and Cys, Se and Cd mol ratio is 1:4.5, CdCl2·2.5H2O and L-half Guang ammonia The mol ratio of acid is 1:2.5, regulates pH to 11, prepare Cd presoma, by NaHSe precursor solution after being sufficiently stirred for dissolving Joining in Cd precursor solution, reflux at 65 DEG C 1h, it is thus achieved that flaxen CdSe quantum dot solution, CdSe quantum dot The concentration of solution is 1.872 × 10-3mol/L；
3) configuration of the detected water sample containing heavy metal ion；The stock solution dilution of 1000mg/L obtains Hg2+Content is 5.0mg/L's Solution.
4) quantum dot solution and water sample after buffered solution regulation pH are carried out in the ratio of 1:1 by low pressure gradient blender Hybrid reaction；
5) mixed solution is detected by inlet injection cuvette with flow velocity 3ml/min through constant flow pump, the solution warp after detection Cross leakage fluid dram to discharge；
6) laser (wavelength is 450nm) that laser instrument sends is divided into two-way, light path 1 and light path 2 through beam splitter；
7) light path 1 is after cuvette, and the light in vertical direction filters out spuious through optical filter (filter range is 550-590nm) After light, then converge through collecting lens, detector detect；
8) light path 2 is reference light paths, and the laser after light splitting is converged by collecting lens, detector detect, sharp for observing Light device power has undamped, it is ensured that data do not occur deviation；
9) result that two-way light path detector detects is sent into data processing module and is carried out photoelectric signal transformation, then inputs computer, passes through After software processes, the optical signal of light path 1 changes and obtains corresponding electric signal value, by a series of concentration of heavy metal ion with collect Electrical signal data, determines detection model y=ax+b, and in detection model, x is heavy metal concentration in water, and y is each concentration heavy metal The signal of telecommunication difference that solution and blank solution collect, a, b are coefficient constant, Linear Regression Model in One Unknown carry out data Processing, obtaining heavy metal concentration is 4.9mg/L.
Embodiment 5
A kind of heavy metal in water online test method based on fluorescent quenching, said method comprising the steps of:
1) buffer solution configuration；Buffer solution be pH be the Tris-HCl buffer solution of 8, collocation method is: weigh 6.057g tri-hydroxyl Aminomethane is dissolved in constant volume in 500ml volumetric flask, obtains 0.1mol/L Tris solution, after measure this Tris solution of 50ml with 29.2ml0.1mol/L hydrochloric acid solution mixes and is diluted to 100ml, it is thus achieved that pH is the Tris-HCl buffer solution of 8；
2) quantum dot solution synthesis；The CdSe quantum dot prepared by hydrothermal synthesis method, uses 3-mercaptopropionic acid and ascorbic acid mixing molten Liquid is composite modified dose, and synthetic method is addition ultra-pure water in 100ml reaction vessel, is sequentially added under inert gas shielding Selenium powder and NaBH4, reaction under the conditions of 40 DEG C is until black Se powder is wholly absent, and solution, by muddy bleach, prepares NaHSe Precursor solution, is cooled to room temperature standby, selenium powder and NaBH4Mol ratio is 1:3；After another reaction vessel adds ultra-pure water, Under inert gas shielding, it is sequentially added into CdCl2·2.5H2O, 3-mercaptopropionic acid and ascorbic acid mixed solution, in mixed solution The mol ratio of 3-mercaptopropionic acid and ascorbic acid be 0.7:1, Se and Cd mol ratio be 1:5, CdCl2·2.5H2O and ascorbic acid Mol ratio be 1:8, be sufficiently stirred for dissolve after add buffer solution regulation pH to 11, prepare Cd presoma；By NaHSe Precursor solution joins in Cd precursor solution, and reflux at 100 DEG C 1h, it is thus achieved that orange-yellow CdSe quantum dot solution, The concentration of quantum dot solution is 9.8 × 10-3mol/L；
3) configuration of the detected water sample containing heavy metal ion；Detected water sample is lead ion solution；Lead ion solution compound method is: essence Close weigh plumbi nitras 0.16g, put in 100ml volumetric flask, after adding concentrated nitric acid 0.5ml and 5ml water dissolution, be diluted with water to scale, Shake up, as stock solution (concentration is 100mg/L)；Stock solution dilution obtains Pb2+Content is the solution of 1.0mg/L；
4) quantum dot solution and water sample after buffered solution regulation pH carry out mixing instead by low pressure gradient blender in the ratio of 1:1 Should；
5) mixed solution is detected by inlet injection cuvette with flow velocity 3ml/min through constant flow pump, the solution warp after detection Cross leakage fluid dram to discharge；
6) laser (wavelength is 450nm) that laser instrument sends is divided into two-way, light path 1 and light path 2 through beam splitter；
7) light path 1 is after cuvette, and the light in vertical direction filters out spuious through optical filter (filter range is 550-590nm) After light, then converge through collecting lens, detector detect；
8) light path 2 is reference light paths, and the laser after light splitting is converged by collecting lens, detector detect, sharp for observing Light device power has undamped, it is ensured that data do not occur deviation；
9) result that two-way light path detector detects is sent into data processing module and is carried out photoelectric signal transformation, then inputs computer, passes through After software processes, the optical signal of light path 1 changes and obtains corresponding electric signal value, by a series of concentration of heavy metal ion with collect Electrical signal data, determines detection model y=ax+b, and in detection model, x is heavy metal concentration in water, and y is each concentration heavy metal The signal of telecommunication difference that solution and blank solution collect, a, b are coefficient constant, Linear Regression Model in One Unknown carry out data Processing, obtaining heavy metal concentration is 1.05mg/L.

Claims (10)

1. a heavy metal in water online test method based on fluorescent quenching, it is characterised in that said method comprising the steps of:
1) buffer solution configuration；
2) quantum dot solution synthesis；Quantum dot solution is for using 3-mercaptopropionic acid and composite modified dose of ascorbic acid, or Cys is The CdSe quantum dot solution of dressing agent；
3) configuration of the detected water sample containing heavy metal ion；
4) quantum dot solution and water sample after buffered solution regulation pH carry out mixing instead by low pressure gradient blender in the ratio of 1:1 Should；
5) mixed solution is detected by inlet injection cuvette through constant flow pump, and the solution after detection is discharged through leakage fluid dram；
6) laser that laser instrument sends is divided into two-way, light path 1 and light path 2 through beam splitter；
7) light path 1 is after cuvette, at the light of vertical direction after optical filter filters out veiling glare, then converges through collecting lens, Detected by detector；
8) light path 2 is reference light paths, and the laser after light splitting is converged by collecting lens, detector detect, sharp for observing Light device power has undamped, it is ensured that data do not occur deviation；
9) result that two-way light path detector detects is sent into data processing module and is carried out photoelectric signal transformation, then inputs computer, passes through After software processes, the optical signal of light path 1 changes and obtains corresponding electric signal value, by a series of concentration of heavy metal ion with collect Electrical signal data, determines detection model y=ax+b, and in detection model, x is heavy metal concentration in water, and y is each concentration heavy metal The signal of telecommunication difference that solution and blank solution collect, a, b are coefficient constant, use Linear Regression Model in One Unknown to enter data Row processes, and obtains the heavy metal concentration of solution to be measured.
A kind of heavy metal in water online test method based on fluorescent quenching the most according to claim 1, it is characterised in that step 2) CdSe quantum dot that quantum dot solution is prepared by hydrothermal synthesis method, it is multiple for using 3-mercaptopropionic acid and ascorbic acid mixed solution Close dressing agent, synthetic method be in 100ml reaction vessel addition ultra-pure water, be sequentially added under inert gas shielding selenium powder with NaBH4, reaction under the conditions of 35-40 DEG C is until black Se powder is wholly absent, and solution is transparent by muddy bleach or pink colour, system Obtain NaHSe precursor solution, be cooled to room temperature standby, selenium powder and NaBH4Mol ratio is 1:2-1:4；In another reaction vessel After adding ultra-pure water, under inert gas shielding, it is sequentially added into CdCl2·2.5H2O and 3-mercaptopropionic acid and ascorbic acid mixing Solution, in mixed solution the mol ratio of 3-mercaptopropionic acid and ascorbic acid be 0.3:1-2:1, Se and Cd mol ratio be 1:3-1:6, CdCl2·2.5H2The mol ratio of O and ascorbic acid is 1:6-1:10, adds buffer solution regulation pH extremely after being sufficiently stirred for dissolving 9-11, prepares Cd presoma；NaHSe precursor solution is joined in Cd precursor solution, reflux at 80-100 DEG C 1h, it is thus achieved that orange-yellow CdSe quantum dot solution.
A kind of heavy metal in water online test method based on fluorescent quenching the most according to claim 1, it is characterised in that step 2) CdSe quantum dot that quantum dot solution is prepared by hydrothermal synthesis method, employing Cys is dressing agent, and synthetic method is 100ml reaction vessel adds ultra-pure water, under inert gas shielding, is sequentially added into selenium powder and NaBH4, under the conditions of 35-40 DEG C Reacting to the reaction of black Se powder completely, reaction solution is become clarification by muddiness, prepares NaHSe precursor solution, is cooled to room temperature Standby, selenium powder and NaBH4Mol ratio is 1:2-1:4；Another reaction vessel adds ultra-pure water, under inert gas shielding, depends on Secondary addition CdCl2·2.5H2O and Cys, Se and Cd mol ratio is 1:2.5-1:4.5, CdCl2·2.5H2O and L- The mol ratio of cysteine is 1:1-1:2.5, regulates pH to 9-11, prepare Cd presoma, by NaHSe after being sufficiently stirred for dissolving Precursor solution joins in Cd precursor solution, and reflux at 50-65 DEG C 1h, it is thus achieved that flaxen CdSe quantum dot solution.
4., according to a kind of based on fluorescent quenching the heavy metal in water online test method described in claim 1 or 2 or 3, its feature exists In, step 3) in detected water sample be dimercurion solution or lead ion solution；Lead ion solution compound method is: accurate title Take plumbi nitras 0.16g, put in 100ml volumetric flask, after adding concentrated nitric acid 0.5ml and 5ml water dissolution, be diluted with water to scale, shake Even, as stock solution (concentration is 100mg/L)；Low concentration Pb2+Solution uses the mode of stepwise dilution to obtain；Mercury ion solution Using concentration is that 1000mg/L mercury standard solution stepwise dilution obtains.
5., according to a kind of based on fluorescent quenching the heavy metal in water online test method described in claim 1 or 2 or 3, its feature exists In, step 1) in buffer solution be pH be the Tris-HCl buffer solution of 8, collocation method is: weigh 6.057g tri-hydroxyl first Base aminomethane is dissolved in constant volume in 500ml volumetric flask, obtains 0.1mol/L Tris solution, after measure this Tris solution of 50ml with 29.2ml0.1mol/L hydrochloric acid solution mixes and is diluted to 100ml, it is thus achieved that pH is the Tris-HCl buffer solution of 8.
6., according to a kind of based on fluorescent quenching the heavy metal in water online test method described in claim 1 or 2 or 3, its feature exists In, step 6) in, the wavelength of laser is 450nm.
7. according to a kind of based on fluorescent quenching the heavy metal in water online test method described in claim 1 or 2 or 3, step 7) In, the filter range of optical filter is 550-590nm.
8. a heavy metal in water on-line measuring device based on fluorescent quenching, it is characterised in that described detection device include react circuit, Detection circuit, data processor and computer, detection device is placed in the casing of airtight dark.
A kind of heavy metal in water on-line measuring device based on fluorescent quenching the most according to claim 8, it is characterised in that described Reaction circuit is: quantum dot solution (1) and detected water sample (2) access in parallel low pressure gradient blender (3), liquid after mixing Send into cuvette (5) through constant flow pump (4) to detect.
A kind of heavy metal in water on-line measuring device based on fluorescent quenching the most according to claim 8, it is characterised in that institute Stating detection circuit is: the laser that laser instrument (6) sends is divided into two-way through beam splitter (7), and a road is passed through as reference light paths Collecting lens (8) is detected by detector one (9) after converging, and another road is irradiated to cuvette (5), and cuvette (5) is sent out The fluorescence gone out filtered (10) and collecting lens (11) are detected by detector two (12) after converging, two detectors The fluorescence signal detected changes into the signal of telecommunication after being processed by data processing module (13) and shows through software on computer (14) Show.
CN201610530549.0A 2016-06-30 2016-06-30 Water body heavy metal online detection method and device based on fluorescence quenching Pending CN106053414A (en)

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