CN105067575A - Method for detecting mercury in water based on quantum dot fluorescence probe, and apparatus thereof - Google Patents

Method for detecting mercury in water based on quantum dot fluorescence probe, and apparatus thereof Download PDF

Info

Publication number
CN105067575A
CN105067575A CN201510389181.6A CN201510389181A CN105067575A CN 105067575 A CN105067575 A CN 105067575A CN 201510389181 A CN201510389181 A CN 201510389181A CN 105067575 A CN105067575 A CN 105067575A
Authority
CN
China
Prior art keywords
mercury
solution
quantum dot
emitting diode
unit
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510389181.6A
Other languages
Chinese (zh)
Inventor
孙明
邹玲
陈炳太
李道亮
位耀光
刘春红
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Agricultural University
Original Assignee
China Agricultural University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Agricultural University filed Critical China Agricultural University
Priority to CN201510389181.6A priority Critical patent/CN105067575A/en
Publication of CN105067575A publication Critical patent/CN105067575A/en
Pending legal-status Critical Current

Links

Landscapes

  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The invention provides a method for detecting mercury in water based on a quantum dot fluorescence probe. The method comprises the following steps: 1, preparing different concentration gradients of a mercury-containing solution; 2, adding an L-cysteine modified CdTe quantum dot solution and a buffer solution into the mercury-containing solution to prepare a solution to be detected; 3, acquiring the spectrum data of the solution to be detected through using a fluorospectrophotometer, screening the characteristic waveband of the mercury element, that is the peak value range of a light-emitting diode, and establishing a detection model; and 4, collecting a water sample, mixing the water sample with the quantum dot solution and the buffer solution, carrying out fluorescence detection, and substituting into the detection model to obtain the mercury content of the water sample. The fluorescence light intensity value of the solution irradiated by a light source is detected through luminescence of the light-emitting diode with specific waveband. Relationship between the mercury content of water and the change of the CdTe quantum dot fluorescence intensity can be obtained from the determined model through the detection method, so the content of heavy metal mercury in water can be obtained through directly measuring the fluorescence intensity of the quantum dot solution.

Description

Based on detection method and the device of the Mercury in Water Body of quantum dot fluorescence probe
Technical field
The invention belongs to field tests, be specifically related to a kind of fluorescence spectrum and detect the method for content of beary metal and the device of detection.
Background technology
Water is lifespring, and be that life exists the necessary condition with economic development, poisonous and hazardous heavy metal causes the water quality in river, lake etc. to go from bad to worse after entering water body, causes heavy metal pollution serious all the more, becomes the focus of world attention.In heavy metal pollution, mercury pollution is poisoned large, and mercury can not be decomposed in water, and people drinks rear toxicity and amplifies, and other toxin are combined and generate the larger organism of toxicity in water.After mercury metal in blood enters brain tissue, accumulate gradually in brain tissue, will cause damage to brain tissue when reaching certain amount, a part of mercury ion transfers to kidney in addition.The inorganic mercury ion entering water body can change the larger organic mercury of toxicity into, enters human body, cause systemic toxicity profiles effect by food chain; Vulnerable crowd has women, especially ready-to-be mother, hobby seafood personage; Seldom mercurous in natural water, be generally no more than 0.1 μ g/L.Mercury in normal human blood is less than 5-10 μ g/L, and the mercury concentration in urine is less than 20 μ g/L.If acute mercury poisoning, hepatitis and blood urine can be brought out.In recent years, the detection method of heavy metal is developed rapidly.There is a lot of method detecting heavy metal ion at present, as spectroscopic methodology, electrochemical methods, high performance liquid chromatography and inhibiting AChE method etc.
When spectroscopic methodology is based on material and radiation energy effect, measures and by material inside, the transition between quantized energy level occurs and the transmitting, the wavelength of absorption or scattered radiation and the intensity that produce carry out the method analyzed.Spectroscopic methodology effectively can be analyzed the heavy metal ion content in various sample with higher sensitivity, but these methods have the following disadvantages, and 1) need expensive large-scale instrument and equipment; 2) testing process is comparatively loaded down with trivial details; 3) sample needs through strict complicated pre-service; 4) detection sensitivity is low, poor selectivity; 5) personnel through specialized training are needed to operate.Thus be difficult to the demand meeting on-the-spot real-time, quick, highly sensitive detection.
Electrochemical methods is the instrument analytical method that can carry out quantitative and qualitative analysis detection to component.Have that sensitivity is higher, accuracy is high, measurement range is wide, instrument and equipment is simpler, the debugging of cheap, instrument and operation all comparatively simple, easily realize the advantages such as robotization, but the problem such as electrochemical analysis also exists selectivity and reappearance is poor.
High performance liquid chromatography have high pressure, at a high speed, efficiently, the feature such as high sensitivity, but because there be " extra column effect ", can cause widening of chromatographic peak, column efficiency reduces.
It is exactly that the heavy metal ion entered in biosome has affinity strong especially with the activated centre of body some enzyme interior that inhibiting AChE measures the ultimate principle of heavy metal, the structure and properties of enzyme active center is changed after the deactivated heavy metal ion of enzyme is combined with the sulfydryl or first sulfydryl that form enzyme active center, enzyme activity is caused to decline, thus make substrate-enzyme system produce a series of change, such as make the color of developer, pH, conductivity and absorbance etc. change, these phenomenons can directly with the naked eye be distinguished or be passed through electric signal, light signal is detected, so just can heavy metal whether be had to exist in judgement sample.The method is quick, easy, even has the advantages such as the Site Detection that can be used for environmental sample (especially water sample), but the stability in enzyme source and susceptibility poor, antijamming capability and repeatability poor.
Except inhibiting AChE, said method all needs instrument costly, there is test period long, the shortcoming such as analytical procedure is complicated.Therefore, set up a kind of simple, fast, the analytical approach of the detection heavy metal of efficient, low cost is significant.
Quantum dot (QuantumDots, QDs) be radius be less than or a based semiconductor close to exciton Bohr radius nanocrystalline.Due to its there is excitation spectrum bandwidth, emission band is narrow, emission wavelength is adjustable, fluorescence quantum yield is high and the photochemical stability excellent optical characteristics such as good, to become in biological fluorescent labelling and Chemical Luminescent Probes very one of fluorescent material having development potentiality.Functional modification is carried out to quantum dot surface, not only can be used for and biomolecule action, also can be applicable to the detection analysis of the environmental contaminants such as heavy metal ion.
The high sensitivity of quantum dot fluorescence probe and high selectivity cause the concern of numerous experts and scholars, and quantum dot is applied on heavy metal sensor becomes possibility gradually.Based on heavy metal ion to the quencher of quantum dot fluorescence or humidification, the relation of concentration of heavy metal ion and quantum dot fluorescence light intensity can be set up, thus realize the mensuration of quantum dot heavy metal content.Based on this principle, current quantum dot is applied to Hg 2+, Cu 2+, Ag +, Cd 2+, Pb 2+etc. the detection of heavy metal ion.The fluorescence of trim to quantum dot of quantum dot surface has a great impact simultaneously, and modifying quantum dot heavy metal ion with different modifying thing has specific identification, and based on this principle, the CdSe quantum dot that Cys is modified is for detecting Cu 2+, the CdTe quantum that mercaptoacetic acid and paddy light ammonia peptide are modified may be used for detecting Hg 2+, the CdS quantum dot that rhodanine is modified may be used for detecting Ag +, the CdTe quantum that levo-carnitine is modified may be used for detecting Cd 2+.Therefore the quantum dot after modifying is applied to the advantage that heavy metal analysis has the good and high specificity of sensitivity, and the sensor of based semiconductor quantum dot has excellent performance, detects the features such as quick.But it is as an emerging technical field, still have many problem demanding prompt solutions and need to be opened up the space with development, such as, although based on quantum dot fluorescent quenching and strengthen phenomenon developed multiple fluorescence probe for analyzing detection, there is the problems such as selectivity is not high toward contact in these methods.How to develop quantum dot surface method of modifying, make quantum dot functionalization by finishing, the high selection analysis realizing heavy metal measures and is still problem to be solved.
In conjunction with current heavy metal analysis present situation, in the urgent need to finding a kind of method of quick, sensitive, efficient detection heavy metal.Portable heavy metal detecting sensor on the market has based on electrochemical, also have based on colourimetry and ultraviolet spectral analysis modeling, the fast development of analytical chemistry make hypersensitive technology to poisonous ion and trace materials quantitatively and detect the study hotspot become from now on fast.The ultra-sensitivity of quantum dot meets the development trend of analytical chemistry, and for exploitation is more microminiaturized and sensor that is robotization provides new thinking.Following quantum dot sensor to be expected to develop into as pH test paper microsensor fast and easily.
Summary of the invention
For the weak point of this area, the object of this invention is to provide a kind of detection method of the Mercury in Water Body based on quantum dot fluorescence probe.
Another object of the present invention is the portable device for fast detecting proposing a kind of Mercury in Water Body based on quantum dot fluorescence probe.
The technical scheme realizing above-mentioned purpose of the present invention is:
Based on a detection method for the Mercury in Water Body of quantum dot fluorescence probe, comprise step:
Step 1: what configure variable concentrations gradient contains mercury solution;
Step 2:L-cysteine modified CdTe quantum solution and buffer solution mixing, what add step 1 configuration contains mercury solution, obtained solution to be measured;
Step 3: adopt fluorospectrophotometer to gather the spectroscopic data of solution to be measured, filter out the feature-sensitive wave band of mercury element, be the crest value scope of light emitting diode, and the detection model setting up that Mercury in Water Body content associates with crest value;
Step 4: gather the water sample polluted by heavy metal Hg, the Cys identical with step 2 modifies CdTe quantum solution, buffer solution mixing, the crest value scope of the light emitting diode determined with step 3 carries out fluoroscopic examination, spectroscopic data will be collected and substitute into detection model, obtain the mercury content in water sample.
Wherein, in described step 1, prepare containing mercury solution mercuric salt, Hg 2+concentration range be 1 × 10 -4to 1 × 10 -2mol/L.Described mercuric salt can be conventional solvable mercuric salt, as HgCl 2, mercuric nitrate, mercuric sulfate.
Cys modifies CdTe quantum solution can adopt the existing method preparation in this area.Cys solution can adopt 0.05 ~ 0.1mol/L concentration.
Wherein, in described step 2, the concentration of Cys solution, CdTe quantum solution is 5 × 10 -8the quantum dot solution of mol/L, described buffer solution to be PH be 7.4 citric acid-Na 2hP0 4buffer solution.
Wherein, in step 3, the spectroscopic data of described collection solution to be measured, that the solution to be measured step 2 obtained is positioned in cuvette, light source irradiation is to the solution to be measured in cuvette, by the light of cuvette mating plate after filtration again, and be incident upon in photo-detector diode, gather spectroscopic data by photo-detector diode; By mercury content and the spectroscopic data collected, determine detection model y=Ax+B, in detection model, x is the spectroscopic data collected, and A, B are coefficient constant, and y is the mercury content in water body.
Wherein, in described step 3, spectra collection scope is all band 400-900nm, sampling interval 1-5nm, collection is counted 100-500, by data processing software, spectroscopic data is processed, the feature-sensitive wave band of mercury element is filtered out by correlation coefficient process, thus determine the crest scope of light emitting diode, again by spectroscopic data that light-emitting diodes is in control, adopt the preprocess method process spectroscopic data of data smoothing process and baseline correction, remove noise, within the scope of characteristic wave bands, adopt one-variable linear regression respectively, multiple linear regression, partial least square method, the modeling method of principal component regression processes data, set up detection model.
Inventor is after Integrated comparative, and the optimization model-Linear Regression Model in One Unknown finally chosen wherein is the quick detection model of Heavy Metals in Waters mercury.
Through the process of above-mentioned steps 3, filtered out the feature-sensitive wave band 550-560nm of mercury element by correlation coefficient process, determine that light emitting diode wavelength coverage is 530-550nm, the filter range of optical filter selects 545-565nm.
According to the detection model that step 3 is set up, can measure the water sample polluted by heavy metal Hg in step 4.Detection model, by downloading in the microcontroller FLASH internal memory of the portable device for fast detecting that the present invention proposes after compiling, debugging, draws mercury content when offline operation detects immediately.
Based on a portable device for fast detecting for the Mercury in Water Body of quantum dot fluorescence probe, described pick-up unit is by integrated apparatus integrated to black box, liquid crystal display, microcontroller, keyboard unit, serial communication unit, driver element, light emitting diode, detection chip, signal amplification unit;
The upper surface of described pick-up unit is provided with liquid crystal display, keyboard unit and black box groove, and described black box is placed in black box groove; In described black box, light emitting diode, cuvette are set in turn; Optical filter, condenser, opto-electronic conversion diode;
Microcontroller, serial communication unit, driver element, detection chip is provided with in described pick-up unit; Described microcontroller connects described driver element, driver element connecting luminous diode; The light path receiving position launched at light emitting diode arranges described opto-electronic conversion diode, and described opto-electronic conversion diode connects described signal amplification unit, and signal amplification unit connects microcontroller; Described microcontroller is also connected with liquid crystal display keyboard unit and serial communication unit.
In order to reduce the interference of external light source, the Environment Design of irradiating cuvette being become the environment of airtight dark, being called black box.
Further, reagent bottle groove and serial ports is also provided with at the upper surface of described pick-up unit.
Further, described light source is the light emitting diode of fixed character wave band 530-550nm.
Wherein, the bandwidth of described optical filter is 20nm.
The method that the present invention proposes, achieves a kind of quick detection of the Heavy Metals in Waters mercury pollution based on quantum dot fluorescence probe, and proposition is used for the mancarried device that mercury metal detects fast, and its beneficial effect comprises:
1 the present invention is by the lumination of light emitting diode of specific band, and detection light source irradiates the fluorescent intensity value of solution.Because the change of the content of Mercury in Water Body and CdTe quantum fluorescence intensity can obtain according to institute's Confirming model in detection method in the relation of specific band, therefore by the direct measurement to quantum dot solution fluorescence intensity, obtain the content of Heavy Metals in Waters mercury.
2 the present invention not only quick and precisely can measure the content of Heavy Metals in Waters mercury simultaneously, provide abundant foundation for water body environment detects; Can also parameter downloads and data upload be carried out, be conducive to late time data analytical applications.
Accompanying drawing explanation
Fig. 1 is the structural representation of the black box in pick-up unit.
Fig. 2 is the structural representation of the filter holder of pick-up unit.
Fig. 3 is the vertical view of pick-up unit.
Fig. 4 is the annexation schematic diagram of each module of pick-up unit.
Fig. 5 is the circuit structure diagram of the driver element of pick-up unit.
Fig. 6 be the serial communication unit of pick-up unit electrical block diagram.
Fig. 7 is the electrical block diagram of the photodiode of pick-up unit.
Fig. 8 be pick-up unit the electrical block diagram of operating unit (keyboard unit).
Fig. 9 is the power unit circuit structural representation of device for fast detecting.9V cell voltage is dropped to 5V by the low pressure difference linear voltage regulator U201 that Fig. 9 (a) is SPX1117M3-5.0 by model; 5V voltage is dropped to 3.3V by the low pressure difference linear voltage regulator U202 of model SPX1117M3-3.3 by Fig. 9 (b).
Figure 10 is the interface circuit structure schematic diagram of the liquid crystal display of device for fast detecting.
Figure 11 is the overhaul flow chart of method for quick.
Wherein: 1-light emitting diode; 2-cuvette; 3-optical filter; 4-condenser; 5-opto-electronic conversion diode; 6-fixes black box groove; 7-filter holder; 8-fiber arm; 9-liquid crystal display; 10-keyboard; 11-serial ports; 12-reagent bottle groove.
Embodiment
Now with following examples, the present invention is described, but is not used for limiting the scope of the invention.
The means used in instructions, if no special instructions, are the technological means of this area routine.
Embodiment 1: based on the detection of quantum dot fluorescence probe
Step 1: with mercuric sulfate configuration variable concentrations gradient containing mercury solution: first prepare 9 × 10 -3mol/L is containing Hg 2+solution, then dilutes, and obtaining 10 concentration is 0,9 × 10 -4, 1.8 × 10 -3, 2.7 × 10 -3... .Hg 2+(concentration gradient is 9 × 10 to solution -4); The quantum dot solution of preparation debita spissitudo; Citric acid-the Na of preparation PH=7.4 2hP0 4buffer solution (PBS);
Step 2:L-cysteine solution (the Cys solution modifying CdTe quantum is 0.08mol/L) modifies CdTe quantum solution and buffer solution mixing, and what add step 1 configuration contains mercury solution, obtained solution to be measured; Electro transfer is there is between mercury ion and CdTe quantum in PBS system, thus the fluorescence of quencher CdTe quantum.That gets many group variable concentrations contains mercury solution 100 μ L, and add the 100 μ L quantum dot solutions prepared respectively, and arrange blank group, its empty group adds the quantum dot solution of 100 μ L and the citric acid-Na of 100 μ L 2hP0 4buffer solution, and fully mixing makes sufficient reacting carry out, and then leaves standstill 15min, namely obtains solution to be measured.
Step 3: adopt fluorospectrophotometer to gather the spectroscopic data of solution to be measured, filter out the feature-sensitive wave band of mercury element, be the crest value scope of light emitting diode, and the detection model setting up that Mercury in Water Body content associates with crest value.Be specially: the fluorescence radiation value measuring quantum dot solution in the rear cuvette of reaction, repeat step 1,2,3, until 10 groups of Hg 2+solution has all reacted with quantum dot, and records their fluorescence curve.Observation analysis curve moves towards to process experimental data.Adopt the preprocess method process spectroscopic data of data smoothing process and baseline correction, remove noise, within the scope of characteristic wave bands, data are processed, after Integrated comparative, the optimization model Linear Regression Model in One Unknown chosen wherein is the quick detection model of Heavy Metals in Waters mercury.
Detection model is y=A.+Bx
In step 3, spectra collection scope is all band 400-900nm, sampling interval 1nm, collection counts-500, by data processing software, spectroscopic data is processed, filtered out the feature-sensitive wave band 550-560nm of mercury element by correlation coefficient process, determine that light emitting diode wavelength coverage is 530-550nm, the filter range of optical filter selects 545-565nm.Based on this, devise the portable device for fast detecting of the Mercury in Water Body based on quantum dot fluorescence probe of the present invention.
The portable device for fast detecting of embodiment 2 Mercury in Water Body
Based on a portable device for fast detecting for the Mercury in Water Body of quantum dot fluorescence probe, pick-up unit described in it is by integrated apparatus integrated to black box, liquid crystal display, microcontroller, keyboard unit, serial communication unit, driver element, light emitting diode, detection chip, signal amplification unit;
See Fig. 3, Fig. 1 and Fig. 2, the upper surface of described pick-up unit is provided with liquid crystal display, keyboard unit and black box groove, and described black box is placed in black box groove; In described black box, light emitting diode 1, cuvette 2, optical filter 3, condenser 4 are set in turn, opto-electronic conversion diode 5.Optical filter 3 is circular, fixes with filter holder 7.The upper surface of pick-up unit is also provided with reagent bottle groove 12 and serial ports 11.
Plant bulk is that the wide x of long x is high: 20x10x4 (cm).
See Fig. 4, in described pick-up unit, be provided with microcontroller, serial communication unit, driver element, detection chip; Described microcontroller connects described driver element, driver element connecting luminous diode; The light path receiving position launched at light emitting diode arranges described opto-electronic conversion diode 5, and described opto-electronic conversion diode 5 connects described signal amplification unit, and signal amplification unit connects microcontroller; Described microcontroller is also connected with liquid crystal display keyboard unit and serial communication unit.Wherein, driver element input connects microcontroller, exports and connects LED source 1; Operating unit is keyboard 10, exports and connects microcontroller; Signal amplifies the input of conciliation unit and connects photo-detector diode 5, exports and connects microcontroller; The input of serial communication unit connects microcontroller, exports and connects bit machine by serial ports 11.Display module is liquid crystal display 9, is connected with the microcontroller in computer module.
In the portable device for fast detecting of the present embodiment, light source is the light emitting diode 1 of fixed character wave band 530-550nm.The bandwidth 20nm of optical filter 3.The each module integration of circuit is circuit board, and circuit board is positioned at pick-up unit inside.
Particularly:
Fig. 5 is the circuit structure diagram of the driver element of computer module of the present invention; I.e. LED constant current driving circuit, it is corresponding P4.0, P4.1, P4.2, P4.3 pin of the single-chip microcomputer (not shown) of MSP430 that Darlington transistor array integrated chip ULN2003 input connects microcontroller model, to improve microcontroller pin current driving ability.The light on and off of light emitting diode 1 are controlled by the pin of microcontroller MSP430 single-chip microcomputer, when exporting high, light emitting diode 1 conducting, light emitting diode 1 is bright; When exporting low, light emitting diode 1 ends.In the present embodiment, No. four driving circuits altogether, and the driving process on each road is all identical or corresponding with annexation, therefore is described for a kind of driving circuit in the present embodiment.Model LM324 operational amplifier U1 and triode composition feedback circuit reach constant current effect, and the adjustable resistance in Fig. 6 is for regulating constant current source size of current; In addition, it can be seen that reference voltage U3 that model is LM336 provides 2.5V reference voltage for operational amplifier U1.
Fig. 6 be the serial communication unit of microcomputer of the present invention electrical block diagram; I.e. serial communication element circuit figure; 2, the 3 pin direct type number of serial ports are 16,17 pins of SP3223 serial port level conversion chip U401.13,15 pins of U401 connect P3.4, P3.5 pin that microcontroller model is the single-chip microcomputer U101 of MSP430.And described serial port level conversion chip U401 is that intelligent serial port chip can have automatic power down and arousal function, realizes the level conversion of tri-state/field effect transistor, namely can complete the level conversion of TTL/COMS to RS232.Link for the light emitting diode showing state is connected to 11 pins of U401, for showing the current state display whether carrying out communication.
Fig. 7 is the electrical block diagram of the opto-electronic conversion diode 5 that the device for fast detecting of the present embodiment uses; Utilize transreactance amplifier, achieve the conversion of faint light electric current to voltage of PIN photodiode output.High-impedance amplifier uses operational amplifier MAX4488. when noise signal is larger, needs circuit restraint speckle to greatest extent, to obtain maximum noise ratio, so design of feedback circuit R in circuit.
Fig. 8 is the electrical block diagram (or being keyboard circuit figure) of the operating unit of the present embodiment.Five button composition 2 × 3 matrixes, be connected to 6,7,9,10,11 pins of I2C interface chip U301,13,14,15 pins of U301 are connected to P1.4, P3.1, P3.3 pin of single-chip microcomputer U101.When there being button to press, PCF8574 will produce look-at-me, and microcontroller response is simultaneously interrupted, and calls interruption subroutine, keyboard scan, and returns key assignments.
Fig. 9 is the power unit circuit structural representation that device for fast detecting of the present invention uses; 9V cell voltage is dropped to 5V by the low pressure difference linear voltage regulator U201 that Fig. 9 (a) is SPX1117M3-5.0 by model, and 5V voltage is dropped to 3.3V by the low pressure difference linear voltage regulator U202 of model SPX1117M3-3.3 by Fig. 9 (b).By 5V and 3.3V for the analyzer in the present embodiment provides voltage.Voltage stabilizer by voltage step-down respectively, be stabilized in 5V and 3.3V, for related circuit is powered.
Figure 10 is the interface circuit structure schematic diagram of the display unit that device for fast detecting uses; Model is P1.0, P5.7, P5.6, P5.3, P5.1 pin that 3,5,8,17,18 pin of the LCD Controlling unit J101 of CSME-12864 meet single-chip microcomputer U101 respectively.3 pin are that liquid crystal reset controls, and 5 pin are liquid crystal chip selection signals, and 8 pin are that control bit selected by order and storer, and 17,18 pin are clock and data line.
Embodiment 3
Adopt the pick-up unit that embodiment 2 proposes, detect, testing process is as Figure 11.
Step 4: gather the water sample polluted by heavy metal Hg, the Cys solution identical with embodiment 1 step 2, CdTe quantum solution, buffer solution mix, the crest value scope of the light emitting diode determined with step 3 carries out fluoroscopic examination, substituting into the detection model y=A+Bx that tries to achieve of embodiment 1 by collecting spectroscopic data, obtaining the mercury content in water sample.
Time 15 ~ the 20min detected.
Above embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various modification that the common engineering technical personnel in this area make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.

Claims (10)

1. based on a detection method for the Mercury in Water Body of quantum dot fluorescence probe, it is characterized in that, comprise step:
Step 1: what configure variable concentrations gradient contains mercury solution;
Step 2:L-cysteine modified CdTe quantum solution and buffer solution add that step 1 configures containing mercury solution, three kinds of solution equal-volumes mixing, obtained solution to be measured;
Step 3: adopt fluorospectrophotometer to gather the spectroscopic data of solution to be measured, filter out the feature-sensitive wave band of mercury element, be the crest value scope of light emitting diode, and the detection model setting up that Mercury in Water Body content associates with crest value;
Step 4: gather the water sample polluted by heavy metal Hg, the Cys identical with step 2 modifies CdTe quantum solution, buffer solution mixing, the crest value scope of the light emitting diode determined with step 3 carries out fluoroscopic examination, spectroscopic data will be collected and substitute into detection model, obtain the mercury content in water sample.
2. detection method according to claim 1, is characterized in that, in described step 1, prepares, Hg containing mercury solution mercuric salt 2+concentration range be 1 × 10 -4to 1 × 10 -2mol/L.
3. detection method according to claim 1, is characterized in that, in described step 2, the concentration that Cys modifies CdTe quantum solution is 5 × 10 -8mol/L, described buffer solution to be PH be 7.4 citric acid-Na 2hP0 4buffer solution.
4. detection method according to claim 1, it is characterized in that, in step 3, the spectroscopic data of described collection solution to be measured, that the solution to be measured step 2 obtained is positioned in cuvette, light source irradiation to the solution to be measured in cuvette, by the light of cuvette mating plate after filtration again, and be incident upon in photo-detector diode, gather spectroscopic data by photo-detector diode; By mercury content and the spectroscopic data collected, determine detection model y=Ax+B, in detection model, x is the spectroscopic data collected, and A, B are coefficient constant, and y is the mercury content in water body.
5. detection method according to claim 1, it is characterized in that, in described step 3, spectra collection scope is all band 400-900nm, sampling interval 1-5nm, collection is counted 100-500, by data processing software, spectroscopic data is processed, the feature-sensitive wave band of mercury element is filtered out by correlation coefficient process, thus determine the crest scope of light emitting diode, again by spectroscopic data that light-emitting diodes is in control, adopt the preprocess method process spectroscopic data of data smoothing process and baseline correction, remove noise, within the scope of characteristic wave bands, adopt one-variable linear regression respectively, multiple linear regression, partial least square method, the modeling method of principal component regression processes data, set up detection model.
6. detection method according to claim 5, it is characterized in that, in described step 3, filtered out the feature-sensitive wave band 550-560nm of mercury element by correlation coefficient process, determine that light emitting diode wavelength coverage is 530-550nm, the filter range of optical filter selects 545-565nm.
7. the portable device for fast detecting of the Mercury in Water Body based on quantum dot fluorescence probe, it is characterized in that, described pick-up unit is by integrated apparatus integrated to black box, liquid crystal display, microcontroller, keyboard unit, serial communication unit, driver element, light emitting diode, detection chip, signal amplification unit;
The upper surface of described pick-up unit is provided with liquid crystal display, keyboard unit and black box groove, and described black box is placed in black box groove; In described black box, light emitting diode (1), cuvette (2) are set in turn; Optical filter (3), condenser (4), opto-electronic conversion diode (5);
Microcontroller, serial communication unit, driver element, detection chip is provided with in described pick-up unit; Described microcontroller connects described driver element, driver element connecting luminous diode; The light path receiving position launched at light emitting diode arranges described opto-electronic conversion diode (5), and described opto-electronic conversion diode (5) connects described signal amplification unit, and signal amplification unit connects microcontroller; Described microcontroller is also connected with liquid crystal display keyboard unit and serial communication unit.
8. portable device for fast detecting according to claim 7, is characterized in that, is also provided with reagent bottle groove and serial ports at the upper surface of described pick-up unit.
9. the portable device for fast detecting of a kind of Heavy Metals in Waters mercury pollution based on fluorescent quenching according to claim 3, is characterized in that described light source is the light emitting diode (1) of fixed character wave band 530-550nm.
10. the portable device for fast detecting of a kind of Heavy Metals in Waters mercury pollution based on fluorescent quenching according to claim 3, is characterized in that, the bandwidth of described optical filter (3) is 20nm.
CN201510389181.6A 2015-07-03 2015-07-03 Method for detecting mercury in water based on quantum dot fluorescence probe, and apparatus thereof Pending CN105067575A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510389181.6A CN105067575A (en) 2015-07-03 2015-07-03 Method for detecting mercury in water based on quantum dot fluorescence probe, and apparatus thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510389181.6A CN105067575A (en) 2015-07-03 2015-07-03 Method for detecting mercury in water based on quantum dot fluorescence probe, and apparatus thereof

Publications (1)

Publication Number Publication Date
CN105067575A true CN105067575A (en) 2015-11-18

Family

ID=54496999

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510389181.6A Pending CN105067575A (en) 2015-07-03 2015-07-03 Method for detecting mercury in water based on quantum dot fluorescence probe, and apparatus thereof

Country Status (1)

Country Link
CN (1) CN105067575A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111781182A (en) * 2020-07-23 2020-10-16 浙江富昇科技有限公司 Portable fluorescence detection device for detecting heavy metal ions in water
CN112126435A (en) * 2020-09-01 2020-12-25 浙江工业大学上虞研究院有限公司 Preparation method and application of same-material dual-emission-ratio fluorescent probe

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103983589A (en) * 2014-05-27 2014-08-13 中国农业大学 Device and method for rapidly detecting heavy metal lead pollution in soil or water

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103983589A (en) * 2014-05-27 2014-08-13 中国农业大学 Device and method for rapidly detecting heavy metal lead pollution in soil or water

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
侯明 等: ""CdTe/CdS量子点荧光探针测定痕量汞(Ⅱ)"", 《广西科学院学报》 *
周华萌: ""L-半胱氨酸修饰的CdTe量子点作为荧光探针的应用研究"", 《中国优秀硕士学位论文全文数据库 医药卫生科技辑》 *
李梦莹 等: ""半胱氨酸包覆的CdTe量子点作为荧光离子探针测定痕量汞(Ⅱ)"", 《冶金分析》 *
那佳,侯明: "CdTe量子点的合成及作为离子荧光探针的应用", 《桂林理工大学学报》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111781182A (en) * 2020-07-23 2020-10-16 浙江富昇科技有限公司 Portable fluorescence detection device for detecting heavy metal ions in water
CN112126435A (en) * 2020-09-01 2020-12-25 浙江工业大学上虞研究院有限公司 Preparation method and application of same-material dual-emission-ratio fluorescent probe

Similar Documents

Publication Publication Date Title
CN103983589A (en) Device and method for rapidly detecting heavy metal lead pollution in soil or water
CN104730054B (en) A kind of integrated probe formula photoelectricity multi-parameter water-quality on-line measurement system
CN101183071B (en) Novel water quality analysis meter
Duffy et al. Recent developments in sensing methods for eutrophying nutrients with a focus on automation for environmental applications
CN204536203U (en) A kind of integrated probe formula photoelectricity multi-parameter water-quality on-line measurement system
CN107064084A (en) Microminiature laser fluorescence spectrum instrument and spectral method of detection
CN104777108A (en) Detection apparatus and method for content of chlorophyll
CN102928390A (en) On-line detection method and device for chlorophyll concentration in water body based on two detectors
CN202916200U (en) Medical fluorescent quantitation analysis meter
CN202393706U (en) Optical fiber multi-parameter water quality analyzer based on fluorescent probes
CN204241366U (en) A kind of device detecting heavy metal in soil
CN201773104U (en) Detecting card for detecting various heavy metals
CN105067575A (en) Method for detecting mercury in water based on quantum dot fluorescence probe, and apparatus thereof
CN104155247A (en) In-situ measurement method and device for chlorophylls and turbidity of water body
CN101261218A (en) Textile optical performance parameter measuring equipment based on double-integrating-sphere
CN1295494C (en) Integrated minisize optical analyser
Kim et al. Recent advances in illicit drug detection sensor technology in water
CN109520967A (en) The detection system and its detection method of trace heavy metal in a kind of food
Zhu et al. Determination of thiamine in pharmaceutical preparations by sequential injection renewable surface solid-phase spectrofluorometry
CN104614421A (en) Electrochemical method for detecting 2,4,6-trichlorophenol
CN103837591A (en) Electrochemical method for detecting polyaromatic hydrocarbon [k] benzofluoranthrene
CN110411963A (en) A kind of portable spectrophotometer of Heavy Metals in Waters ion detection
CN104568799A (en) Monochromatic light composited light scanning type luminosity absorption detection system
CN1458529A (en) Colorimetric component analysis method and its device based on image technology
CN205538649U (en) Embedded spectrum appearance of quantum dot

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20151118