Flow injection surface enhanced raman spectroscopy measures the detection means of copper and detection in water body
Method
Technical field
The invention belongs in water body copper detection method field, specifically a kind of scene, quick, sensitive flowing note
Reflective surface strengthens the detection means of copper and detection method in Raman spectroscopy water body.Based on ring paste on nano Au colloid for the absorption
Smart molecule can produce surface-enhanced Raman effects, and the complex that in water, copper is produced with 4- aminothiophenol can reduce absorption in nanometer
Surface enhanced Raman intensity degree produced by cyclodextrin molecular on gold size, the degree that surface enhanced Raman intensity degree reduces simultaneously
With the concentration of copper in water body, there is linear relationship, using Flow Injection Technique, produced by blank solution and detected water sample
The method of copper in the raw difference measurement water of surface enhanced Raman intensity degree.
Background technology
Copper is one kind that underwater gold belongs to element, and excessive copper is very big to the harm of human body.Free state copper ion pair
The harm of human body is more much bigger than cooperation state copper.Excessive copper ion has great negative interaction to many aquatiles, is because
It is combined with the sulfydryl in protein, the activity of interference sulfydryl enzyme, if as there being excessive copper in the ecosystem such as Corallium Japonicum Kishinouye, pasture and water
Ion, will biology get killed quickly.Copper is trace element necessary to animals and plants, and human body lacks copper and can cause the diseases such as anemia, diarrhoea,
But the copper of excess also can work the mischief to people and animals and plants.Therefore in water, the detection of copper seems particularly significant.
At present, the method for copper detection is a lot, has atomic absorption spectrophotometry, spectrophotography, electric heating evaporation-electricity
The technology such as sense coupled plasma optical emission spectrographic method, mass spectrography or graphite oven atomic absorption.These method general character are to need to hold high
Expensive instrument, complex operation, the persistent period is long, needs special technical staff to complete, and reagent consumption is big, and some sides
What method was also different degrees of introduces harmful organic solvent, produces secondary pollution.Many counting methods need price to hold high simultaneously
Your large-scale instrument, in addition method is all using the pattern arriving lab analysis after field investigation and sampling, does not enable scene, surveys in real time
The mode of amount, sample transportation and processing procedure are easily introduced other interfering materials, the accuracy of impact analysis.Therefore this
Process is for trace level elementary analysiss it is impossible to ensureing is not in the secondary probability got dirty, and for complicated and changeable
Water body environment, for example:Element morphology is affected greatly by space-time;Majority is in interrelated, interactional state again;The middle temperature of environment
Degree pressure change is big, and the accuracy of its result and reliability are under suspicion, thus water quality situation and its exception can not definitely be grasped
Change.
Content of the invention
The invention provides a kind of live, quick, sensitive flow injection surface enhanced raman spectroscopy measures copper in water body
Detection means and detection method method.
In order to reach the purpose solving above-mentioned technical problem, the technical scheme is that:
Flow injection surface enhanced raman spectroscopy method measures the detection means of copper in water body, it is characterized in that being drawn by surface enhanced
Graceful spectral detection room (8), Raman spectrum system (12), control device (14), data handling system (13), sample peristaltic pump (3),
Chelating agent peristaltic pump (5) and hydrochloric acid solution peristaltic pump (6) composition, wherein, surface enhanced raman spectroscopy sensing chamber (8) passes through pipe
Road is connected with sample peristaltic pump (3), chelating agent peristaltic pump (5) and hydrochloric acid solution peristaltic pump (6) respectively, and described surface enhanced draws
Graceful spectral detection room (8) is connected with data handling system (13) and control device (14), and described surface enhanced raman spectroscopy is examined
Survey and be provided with attemperating unit outside room (8).
Described surface enhanced raman spectroscopy sensing chamber (8) is U-shaped, the bottom of surface enhanced raman spectroscopy sensing chamber (8)
It is provided with ceramic substrate (9), ceramic substrate (9) attaches porous nano gold thin film (10) above, described porous nano gold thin film
(10) surface is coupled with cyclodextrin compound, and sample passes through from ceramic substrate surface.
Made using polytetrafluoroethylmaterial material in described pipeline.
Flow injection surface enhanced raman spectroscopy measures the detection method of the detection means of method of copper in water body, described side
Method is carried out in the steps below by described detection means:
(1) sample solution is conveyed by pump;
(2) sample solution in the presence of pump successively with hydrochloric acid solution pipeline in hydrochloric acid solution, and chelating agent pipeline
In the mixing of 4- aminothiophenol solution chelating agent, mixed proportion is:Sample solution with hydrochloric acid solution is:1:0.2-1:0.5, sample
Product solution and chelating agent are:1:2-1:5;
(3) by described surface enhanced raman spectroscopy sensing chamber, 4- aminothiophenol is selected mixed solution with copper in water body
Property formed complex pass through U-shaped sensing chamber's bottom internal when couple with porous nano-Au film surface cyclodextrin compound generation
Even nitridation reaction, the surface enhanced raman spectroscopy peak intensity being allowed to produce reduces.Described attemperating unit controls temperature to regulation
Temperature range;
(4) raman spectral signal that the solution that Raman spectrometer convection current is passed through is sent is acquired amplifying, and is converted into
The signal of telecommunication sends into microcomputer data handling system, obtained by data handling system is to the distilled water circulation detection apparatus obtaining
The signal of telecommunication calculated with sample signal, further according to after opto-electronic conversion the signal of telecommunication reduce degree and standard sample signal
The degree corresponding relation reducing, calculates the concentration of copper in water-outlet body, and carry out showing, printout.
In the present invention, also there is following technical characteristic, described sample liquid inventory is 1.0-5.0ml/min.
In the present invention, also there is following technical characteristic, described hydrochloric acid solution flow is 0.5-1.0ml/min, pH model
Enclose for 3.00~4.00.
In the present invention, also there is following technical characteristic, described complexation agent flux is 5.0-10.0ml/min, and concentration is
(1.0-1.5)×10-3mol/L.
In the present invention, also there is following technical characteristic, described U-shape structure designs, and bottom internal is provided with ceramic substrate,
Porous nano gold thin film is attached, described porous nano-Au film surface is coupled with cyclodextrin compound, and top is meeting above it
Poly- lens, sample passes through from ceramic substrate surface with collecting lenses.
In the present invention, also there is following technical characteristic, described ceramic substrate, attach porous nano-Au above it thin
Film, has adhesion layer between gold thin film and ceramic substrate, and this adhesion layer is located between substrate and metal level, main increase metal level
Adhesive force, makes metal level be difficult in use to take off, adhesion layer is mainly made up of Graphene, in order to ensure that obtaining maximum surface increases
The formant of strong Raman substrate, the thickness of adhesion layer is 3-5 nanometer, and the thickness of metal level is 30-40 nanometer.
In the present invention, also there is following technical characteristic, described porous nano-Au film surface is coupled with cyclodextrin
Compound as surface enhanced raman spectroscopy probe, in order to ensure that cyclodextrin is coupled to gold thin film surface-stable, is operated environment
Temperature control is it is ensured that temperature range 10-15 DEG C.
In the present invention, also there is following technical characteristic, with nano Au colloid as substrate, ring paste on nano Au colloid for the absorption
Smart chemical molecules can produce surface-enhanced Raman effects, in 1512cm-1There is a stronger surface-enhanced Raman at Raman shift
Peak.When in 4- aminothiophenol with water body, selective copper forms when complex passes through U-shaped sensing chamber's bottom internal and porous nano
The cyclodextrin compound of gold thin film surface coupling produces even nitridation reaction, leads to 1512cm-1Surface-enhanced Raman at Raman shift
Peak intensity reduces, and increases with complex concentration, system is in 1512cm-1Surface enhanced Raman intensity degree at Raman shift is in line
Sexual intercourse, therefore available 1512cm-1Surface enhanced raman spectroscopy measures copper concentration in water body.
The effect of the present invention is:The present invention is by integrated complexation technology, Flow Injection Technique, surface enhanced raman spectroscopy
Technology, data acquisition, the method measuring to copper in water body for the software processes.By complexation-surface enhanced raman spectroscopy one
Bodyization designs, and enables the efficient complexation collection of copper trace in water body and Flow Injection Technique has and is automatically injected, controlled dispersion and essence
Really quick feature, then adopt sensitive Raman spectrum method for detecting surface reinforcement, increase hence with integrated complexation surface
Surface enhanced Raman spectroscopic signals are reduced what degree difference was set up by detecting formed complex by strong Raman spectrum
The method that flow injection surface enhanced raman spectroscopy method measures copper in water body has scene, quick, easy, sensitive feature, it
The work on the spot that is unable to of prior art presence can be solved, the analysis persistent period is long, and analysis process is numerous and diverse, and condition is harsh, energy consumption
Greatly, especially produce secondary pollution problems, be very effective at present quick analysis means, be preferable environmental analyses detection
Method, belongs to environmental protection method.The technical advantage that the inventive method has can make this method in fields such as environmental analyses
It is developed and promote.
The present invention is described further with reference to the accompanying drawings and examples.
Brief description
Fig. 1 is structure of the detecting device schematic diagram of the present invention;
Fig. 2 is the inventive method operation principle flow chart.
1. blank solution-distilled water;2. sample solution;3. sample peristaltic pump;4. metal chelating agent;5. chelating agent is wriggled
Pump;6. hydrochloric acid solution peristaltic pump;7. hydrochloric acid solution;8. surface enhanced raman spectroscopy sensing chamber;9. ceramic substrate;10. porous is received
Rice gold thin film;11. collecting lenses;12. Raman spectrum systems;13. data handling systems;14. control devices;15. waste collection
Device.
Specific embodiment
In Fig. 1, flow injection surface enhanced raman spectroscopy method measures the detection means of copper in water body, by surface-enhanced Raman
Spectral detection room 8, Raman spectrum system 12, control device 14, data handling system 13, sample peristaltic pump 3, chelating agent peristaltic pump
5 and hydrochloric acid solution peristaltic pump 6 form, wherein, surface enhanced raman spectroscopy sensing chamber 8 pass through pipeline respectively with sample peristaltic pump
3rd, chelating agent peristaltic pump 5 and hydrochloric acid solution peristaltic pump 6 connect, described surface enhanced raman spectroscopy sensing chamber 8 and data processing
System 13 and control device 14 connect, and described surface enhanced raman spectroscopy sensing chamber 8 is provided with attemperating unit.
Described surface enhanced raman spectroscopy sensing chamber 8 is U-shaped, and the bottom of surface enhanced raman spectroscopy sensing chamber 8 is provided with
Ceramic substrate 9, ceramic substrate 9 attaches porous nano gold thin film 10 above, and the surface of described porous nano gold thin film 10 couples
There is cyclodextrin compound, sample passes through from ceramic substrate surface.Described pipeline is made using polytetrafluoroethylmaterial material.
In Fig. 2, following step is included using the detection method of above-described embodiment detection means:
(1) sample solution is conveyed by pump;
(2) sample solution in the presence of pump successively with hydrochloric acid solution pipeline in hydrochloric acid solution, and chelating agent liquid pipe
The molten chelating agent of 4- aminothiophenol in road mixes, and mixed proportion is:Sample solution with hydrochloric acid solution is:1:0.2-1:0.5, sample
Product solution and chelating agent are:1:2-1:5;
(3) by described surface enhanced raman spectroscopy sensing chamber, 4- aminothiophenol is selected mixed solution with copper in water body
Property formed complex pass through U-shaped sensing chamber's bottom internal when couple with porous nano-Au film surface cyclodextrin compound generation
Even nitridation reaction, the surface enhanced raman spectroscopy peak intensity being allowed to produce reduces.Described attemperating unit controls temperature to regulation
Temperature range;
(4) optical signal that the solution that Raman spectrometer convection current is passed through is sent is acquired amplifying, and is converted into the signal of telecommunication
Send into microcomputer data handling system, data processing equipment calculates to the blank signal obtaining and sample signal, then
The degree being reduced according to signal and the degree corresponding relation of the signal reduction of standard sample, calculate the concentration of copper in water-outlet body, and
Carry out showing, printout.
Described water sample flow is 1.0-5.0ml/min.
Described hydrochloric acid solution flow is 0.5-1.0ml/min, and pH scope is 3.00~4.00.
Described complexation agent flux is 5.0-10.0ml/min, and concentration is (1-1.5) × 10-3mol/L.
Described U-shape structure design, bottom internal is provided with ceramic substrate, attaches porous nano gold thin film above it, described
Porous nano-Au film surface be coupled with Cyclodextrin Chemistry thing, top is collecting lenses, and sample is from ceramic substrate surface participant
Pass through in poly- lens.
Described ceramic substrate, attaches porous nano gold thin film above it, has adhesion layer between gold thin film and ceramic substrate,
This adhesion layer is located between substrate and metal level, the main adhesive force increasing metal level, makes metal level be difficult in use to take off, glues
Attached layer is mainly made up of Graphene, in order to ensure to obtain the formant of maximum surface enhanced Raman substrate, the thickness of adhesion layer
For 3-5 nanometer, the thickness of metal level is 30-40 nanometer.
Described porous nano-Au film surface is coupled with cyclodextrin compound as surface enhanced raman spectroscopy probe, is
Ensure that cyclodextrin is coupled to gold thin film surface-stable, be operated ambient temperature control it is ensured that temperature range 10-15 DEG C.
With nano Au colloid as substrate, cyclodextrin chemical molecules on nano Au colloid for the absorption can produce surface-enhanced Raman effect
Should, in 1512cm-1There is a stronger surface-enhanced Raman peak at Raman shift.When in 4- aminothiophenol with water body, copper selects
Property formed complex pass through U-shaped sensing chamber's bottom internal when couple with porous nano-Au film surface cyclodextrin compound generation
Even nitridation reaction, leads to 1512cm-1At Raman shift, surface enhanced Raman intensity degree reduces, and increases with complex concentration, body
Tie up to 1512cm-1Surface enhanced Raman intensity degree at Raman shift is linear, therefore available 1512cm-1Surface enhanced draws
Copper concentration in graceful spectroscopic assay water body.
In the present invention, Raman spectrometer adopts the portable Raman spectrometer of U.S. Inspector.
The operation principle of the present invention is:Flow injection surface enhanced raman spectroscopy measure water body in copper method be by light,
Mechanical, electrical, the integrated flow injection surface enhanced raman spectroscopy detection system of computer composition.It is divided into five by operational module
Point:
Part I is flow injection part, mainly water sample with hydrochloric acid solution and metal chelating agent -4- aminobenzene sulfur
Phenol mixes, and forms metal complex and enter in sensing chamber in the environment of hydrochloric acid provides.
Part II:Surface-enhanced Raman effects part, the surface enhanced raman spectroscopy that mainly described U-shape structure designs
Sensing chamber, bottom internal is provided with ceramic substrate, attaches porous nano gold thin film above it, and porous nano-Au film surface is coupled with
Cyclodextrin compound, top is collecting lenses, and sample passes through from ceramic substrate surface with collecting lenses.With nano Au colloid as base
Bottom, cyclodextrin chemical molecules on nano Au colloid for the absorption can produce surface-enhanced Raman effects, in 1512cm-1At Raman shift
There is a stronger surface-enhanced Raman peak.When in 4- aminothiophenol with water body, selective copper forms complex by U-shaped inspection
Survey the cyclodextrin compound coupling with porous nano-Au film surface during the bottom internal of room and produce even nitridation reaction, lead to
1512cm-1At Raman shift, surface enhanced Raman intensity degree reduces, and increases with complex concentration, system is in 1512cm-1Raman
Surface enhanced Raman intensity degree at displacement is linear, therefore uses 1512cm-1Surface enhanced raman spectroscopy measures copper in water body
Concentration.
Part III:Raman spectroscopy system, using LASER Light Source, optical filter, spectroscope, CCD detection device, generation
Optical signal is transformed into the signal of telecommunication immediately, and is continuously recorded.
Part IV is data acquisition, record part, and this is partially completed the collection of the signal of telecommunication, A/D conversion, transmits and deposit
Storage.
Part V is microcomputer data handling system, mainly is responsible for the blank signal obtaining and sample signal are entered
Row calculates, and reduces degree further according to signal and the signal of standard sample reduces level data corresponding relation, calculate copper in water-outlet body
The concentration of element, and carry out showing, printout.
Have become as the promising approach of present analysis measurement using the high sensitivity of surface enhanced raman spectroscopy.Make simultaneously
With during there is the characteristic not producing secondary pollution it is not necessary to sample pretreatment process, so before there is very big application
Scape.At present, forming " focus " using nanometer gold structure is the Main Means realizing surface enhanced raman spectroscopy Single Molecule Detection, with
When nanometer gold there is Stability Analysis of Structures, good to biomolecule compatibility, the advantages of reusable.But test limit is low, spectrum matter
Amount is poor, is insufficient for the quick detection of trace metal in current water body.Cyclodextrin chemical molecules on nano Au colloid for the absorption
Surface-enhanced Raman effects can be produced, test limit can lift the 2-4 order of magnitude, but but signal to noise ratio is bad.But 4- amino
In phenylmercaptan. and water body selective copper formed complex by with cyclodextrin chemical combination diazo-reaction, ensure that low detection
Limit, and data processing difficulty can be simplified, response speed is very fast, and test limit can reach 10-7Mol/L, signal to noise ratio is very good, simultaneously because
The azo-compound that even nitriding produces has very strong Electron absorption, is well suited for doing surface enhanced raman spectroscopy.4- aminobenzene sulfur
Phenol and selective copper in water body form complex and surface enhanced raman spectroscopy peak intensity angle value can be led to reduce.In condition of the present invention
Under, 1512cm-1The decreasing value Δ I at surface enhanced raman spectroscopy peak at place is in good linear relationship with the concentration of copper in water, according to
This can set up the quantitative analysis method measuring copper in water body.
The above, be only presently preferred embodiments of the present invention, is not the restriction that the present invention is made with other forms, appoints
What those skilled in the art possibly also with the disclosure above technology contents changed or be modified as equivalent variations etc.
Effect embodiment.But every without departing from technical solution of the present invention content, according to the present invention technical spirit to above example institute
Any simple modification, equivalent variations and the remodeling made, still falls within the protection domain of technical solution of the present invention.