CN108398418A - A kind of interior reference surfaces enhancing Raman test paper, preparation method and application - Google Patents

A kind of interior reference surfaces enhancing Raman test paper, preparation method and application Download PDF

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Publication number
CN108398418A
CN108398418A CN201810218647.XA CN201810218647A CN108398418A CN 108398418 A CN108398418 A CN 108398418A CN 201810218647 A CN201810218647 A CN 201810218647A CN 108398418 A CN108398418 A CN 108398418A
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test paper
reference surfaces
interior reference
raman
solution
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CN108398418B (en
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张磊
罗勇泉
关博鑫
于博昊
张凌怡
张维冰
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East China University of Science and Technology
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East China University of Science and Technology
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • G01N21/658Raman scattering enhancement Raman, e.g. surface plasmons

Abstract

It further includes modifying in the silver nano-grain on the hydroxyapatite overlong nanowire to enhance Raman test paper using hydroxyapatite overlong nanowire as medium the invention discloses a kind of interior reference surfaces.The invention also discloses the interior reference surfaces to enhance the preparation method of Raman test paper, and discloses application of the interior reference surfaces enhancing Raman test paper in the quick detection kit of environmental sample pollutant.The interior reference surfaces enhancing Raman test paper of the present invention has higher stability, it is applied in kit, 4 nitro thiophenol of multiple compounds, 4 aminothiophenols, benzidine etc. are responded with SERS, it is used as interior reference by the distinctive Raman peaks of test paper, the Characteristic Raman peak of sample compound is test signal, and the quantitative analysis to sample compound may be implemented.

Description

A kind of interior reference surfaces enhancing Raman test paper, preparation method and application
Technical field
The invention belongs to chemical analysis detection technique fields, specifically, being related to a kind of interior reference surfaces enhancing Raman survey It has a try paper, preparation method and application.
Background technology
Surface enhanced Raman scattering (SERS) refers to when some molecules or functional group are adsorbed to certain metals or partly lead When on the special surface (such as surface of nano particle, nano wire and the surface with nanoscale rough degree) of body, in lasing region A kind of Spectral Phenomenon that its Raman scattering signal intensity can be significantly increased in domain.SERS is highly sensitive, quick, rich due to having Rich spectral information is widely used in studying surface, absorption interface surface state, the interface orientation of biological sized molecules and configuration Conformation, structural analysis etc., can effectively analysis of compounds in the gas absorption quantity at interface, the variation of ADSORPTION STATE, interface information etc.. It is utilizing and is developing in the detections of SERS to environmental pollutants, currently, mainly by enhancing base material SERS effects, improving base The means such as bottom material selectivity, optimization base material practicability are realized.The roughness of substrate surface be generate SERS phenomenons must Condition, the physicochemical property of substrate is wanted to determine the power of SERS effects.Therefore, it is established using Surface Enhanced Raman Scattering Spectrum During analysis method, it is always the weight of SERS detection methods that preparing, which has high stable, high duplication, highly selective substrate, Point research direction.
Hydroxyapatite is the main inorganic composition of a kind of group of adult body and animal skeleton, it has excellent bio-compatible Property and bioactivity, are a kind of widely applied biomedical materials.Structural modification can be carried out using hydroxyapatite to obtain The hydroxyapatite of silver nano-grain load, forms filter paper or test paper.
Kit is the box for holding the chemical reagent such as detection chemical composition, medicament residue, viral species.With tradition Laboratory operation is compared, and is carried out sample pre-treatments using kit or is analyzed, and entire detection process is simple, quick, square Just, it is suitble to execute-in-place, it is low to analysis operation skill set requirements, in a short period of time, it can be detected result.
Invention content
The object of the present invention is to provide a kind of interior reference surfaces to enhance Raman test paper.
It is a further object to provide the preparation methods that a kind of interior reference surfaces enhance Raman test paper.
It is also another object of the present invention to provide a kind of interior reference surfaces to enhance Raman test paper in environmental sample Application in the quick detection kit of pollutant.
To achieve the goals above, the technical solution adopted by the present invention is as follows:
One aspect of the present invention provides a kind of interior reference surfaces enhancing Raman test paper, with hydroxyapatite overlength Nano wire is medium, further includes modifying in the silver nano-grain on the hydroxyapatite overlong nanowire.
The length of the hydroxyapatite overlong nanowire be 100~300 μm, preferably 200 μm, a diameter of 10~ 30nm, preferably 20nm.
The thickness of the interior reference surfaces enhancing Raman test paper is 0.1-0.5mm, preferably 0.2mm.
The modification is 5.0~10% in the content of the silver nano-grain on the hydroxyapatite overlong nanowire, excellent It is selected as 7.8%.
Another aspect of the present invention provides a kind of preparation method of the interior reference surfaces enhancing Raman test paper, Include the following steps:
Oleic acid is scattered in the mixed solution of deionized water and methanol by the first step, and mechanical agitation is uniformly mixed, and obtains oil The homogeneous mixture solotion of acid;
Mixed solution and a concentration of 8~10% sodium hydrate aqueous solution that the first step obtains are stirred by second step Uniformly, the liquid being uniformly mixed;
Third walks, and a concentration of 1~3% calcium chloride water and a concentration of is added in the mixed solution obtained to second step 2~7% biphosphate sodium water solution, is uniformly mixed, the liquid being uniformly mixed;
The mixed solution that third step obtains is heated reaction, obtains suspension particle solution, product is centrifuged, use by the 4th step Deionized water and methanol cleaning, preserve in water;
Solution and a concentration of 40~60% silver nitrate solution that 4th step obtains are uniformly mixed, obtain by the 5th step To suspension liquid, vacuum filtration obtains the interior reference surfaces enhancing Raman test paper.
The mass ratio of the oleic acid, methanol and deionized water is (8~12):(2~6):(5~15), preferably (8~ 10):(3~5):(10~15).
The mass ratio of mixed solution and sodium hydrate aqueous solution that the first step obtains is (26~28):(14~18).
The mass ratio of the mixed solution that the second step obtains and calcium chloride water, biphosphate sodium water solution is (40 ~50):(10~14):(15~20).
The temperature that reaction is heated in 4th step is 100~250 DEG C, and the reaction time is 12~36h.
The mass ratio of the 4th step obtains in 5th step solution and silver nitrate solution is (30~50):(90~110).
The size of the interior reference surfaces enhancing Raman test paper is (2~20mm) × (2~20mm).
Another aspect of the invention, which provides a kind of interior reference surfaces, enhances Raman test paper in environment sample Application in the quick detection kit of product pollutant.
An additional aspect of the present invention provides a kind of kit answering in the quick detection of organic pollution With.
The organic pollution is 4- nitro thiophenols, 4- aminothiophenols, benzidine.
The application includes the following steps:40~60 μ L are taken to be added in kit in environmental testing sample, in interior reference table Face enhances 2~5min of soaking at room temperature in Raman test paper, and interior reference surfaces enhancing Raman test paper is taken out with tweezers, in Above glass slide, it is detected using Raman spectrometer.
Due to the adoption of the above technical scheme, the present invention has the following advantages and beneficial effect:
The interior reference surfaces of the present invention enhance Raman test paper, using oleic acid, calcium chloride and sodium dihydrogen phosphate as raw material Hydroxyapatite overlong nanowire is prepared by hot melt, using the combination of silver ion and phosphate radical, Yin Na is prepared The hydroxyapatite overlong nanowire of rice grain load, further obtaining interior reference surfaces enhances Raman test paper, the present invention Interior reference surfaces enhancing Raman test paper have higher stability, be applied in kit, to multiple compounds 4- nitro thiophenols, 4- aminothiophenols, benzidine etc. are responded with SERS, are used as internal reference by the distinctive Raman peaks of test paper Characteristic Raman peak than, sample compound is test signal, and the quantitative analysis to sample compound may be implemented, can quickly into Row detection.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the interior reference surfaces enhancing Raman test paper of the present invention.
Fig. 2 is the transmission electron microscope picture of the interior reference surfaces enhancing Raman test paper of the present invention.
Fig. 3 is the X-ray diffractogram of the interior reference surfaces enhancing Raman test paper of the present invention.
Fig. 4 is tested using the Raman of the interior reference surfaces enhancing Raman test paper detection 4- nitro thiophenols of the present invention As a result;A is the Raman spectrogram of direct analysis 4- nitro thiophenol solids, and b is a concentration of 1.0mmol L-14- nitro thiophenols Surface enhanced Raman spectroscopy figure, c is the saturation ethanol solution Raman spectrogram of 4- nitro thiophenols.
Fig. 5 is tested using the Raman of the interior reference surfaces enhancing Raman test paper detection 4- aminothiophenols of the present invention As a result;A is the Raman spectrogram of direct analysis 4- aminothiophenol solids, and b is a concentration of 1.0 μm of ol L-14- aminothiophenols Surface enhanced Raman spectroscopy figure, c be in blank reference surfaces enhancing Raman test paper Raman spectrogram.
Fig. 6 is to enhance Raman test paper using the interior reference surfaces of the present invention to test the steady of 4- aminothiophenols as substrate Qualitative comparison diagram, a are test signal figure of the same day to 4- aminothiophenols, and b is the test signal figure after placing 14 days.
Fig. 7 is the Raman test result using the interior reference surfaces enhancing Raman test paper detection benzidine of the present invention;a It is the Raman spectrogram of direct analysis benzidine solid, b is a concentration of 1.0 μm of ol L-1The Surface enhanced Raman spectroscopy of benzidine Figure, c are the Raman spectrograms of reference surfaces enhancing Raman test paper in blank.
Fig. 8 is to compare the linear relationship chart that benzidine is detected using internal reference.
Fig. 9 is the analysis to benzidine in environmental water sample using the interior reference surfaces enhancing Raman test paper of the present invention Figure;A is the SERS spectra figure for enhancing Raman test paper to blank water using the interior reference surfaces of the present invention, and b is to utilize this hair For bright interior reference surfaces enhancing Raman test paper to the SERS spectra figure of environmental wastewater, c is the interior reference table using the present invention Face enhances Raman test paper and 1.0 μm of ol L is added to environmental wastewater-1The SERS spectra figure of benzidine, d are to utilize the present invention's 2.0 μm of ol L are added to environmental wastewater in interior reference surfaces enhancing Raman test paper-1The SERS spectra figure of benzidine, wherein draw Graceful peak 1451.63cm-1As the characteristic signal peak of benzidine, Raman peaks 911.43cm-1As interior reference peak.
Specific implementation mode
In order to illustrate more clearly of the present invention, with reference to preferred embodiment, the present invention is described further.Ability Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this The protection domain of invention.
The reagents and materials used in the present invention are commercially available or can be prepared by literature method.Unless otherwise stated, otherwise hundred Divide than being calculated by weight with number.
Reagent and material used in the embodiment of the present invention is as follows:
96 hole kits are purchased from silent winged scientific and technological (China) Co., Ltd of generation that of match, 96 hole MicrotiterTM microwell plates, rule Lattice:Vinyl 400μL.
Embodiment 1
(1) 9.36g oleic acid and 4.75g methanol and the mixed solution of 13.5g deionized waters are slowly stirred, pass through machine Tool stirs, and obtains the homogeneous mixture solotion of oleic acid.
(2) sodium hydrate aqueous solution of 16g a concentration of 8% will be added in oleic acid mixed solution, carry out mechanical agitation 30min gets a uniform mixture.
(3) calcium chloride water and 19g concentration of 12g a concentration of 2% will be added in the sodium hydroxide mixed solution of oleic acid It is uniformly mixed for 5% biphosphate sodium water solution, obtains homogeneous solution.
(4) mixed solution is transferred in the tetrafluoroethene reaction kettle of 250mL and is heated to 180 DEG C of reactions for 24 hours to get suspension Particle solution centrifuges product, is cleaned for several times, is preserved in water, for use with deionized water and methanol.
(5) the 40g suspension liquids obtained by step (4) is taken to be mixed with the silver nitrate aqueous solution of 100g a concentration of 60%, Mechanical agitation 4h is carried out under illumination, obtains uniformly mixed grey suspension liquid, is filtered by vacuum, and is obtained interior reference surfaces enhancing and is drawn Graceful test paper.As shown in Figures 1 to 3 to test paper progress test result, Fig. 1 is the interior reference surfaces enhancing Raman test of the present invention The scanning electron microscope (SEM) photograph of test paper.As can be seen from the figure the test paper is silver nanoparticles loaded overlong nanowire structure;Fig. 2 is this hair The transmission electron microscope picture of bright interior reference surfaces enhancing Raman test paper.As can be seen from the figure the test paper is load silver nanoparticle Grain overlong nanowire structure;Fig. 3 is the X-ray diffractogram of the interior reference surfaces enhancing Raman test paper of the present invention.From figure It can be seen that the test paper is silver-colored silver orthophosphate structure.
The length of hydroxyapatite overlong nanowire manufactured in the present embodiment is 200 μm, a diameter of 20nm, interior reference surfaces The thickness for enhancing Raman test paper is 0.2mm, is modified in the silver nano-grain on the hydroxyapatite overlong nanowire Content is 7.8%.
(6) test paper obtained by step (5) is cut, obtains the test paper of 4mm × 4mm, stored in 96 hole kits, Obtain interior reference surfaces enhancing Raman detection kit.
Embodiment 2
By a concentration of 1.0mmol L-14- nitro thiophenol ethanol solutions take 50 μ L that kit prepared by embodiment 1 is added In wherein correspond in test paper, soaking at room temperature 2min takes out test paper with tweezers, above glass slide, using Raman spectrometer into Row detection.The results are shown in Figure 4, and Fig. 4 is the interior reference surfaces enhancing Raman test paper detection 4- nitrobenzenes using the present invention The Raman test result of thiophenol;A is the Raman spectrogram of direct analysis 4- nitro thiophenol solids, and b is a concentration of 1.0mmol L-1The Surface enhanced Raman spectroscopy figure of 4- nitro thiophenols, c are the saturation ethanol solution Raman spectrograms of 4- nitro thiophenols.By Figure can be seen that the test of interior reference surfaces enhancing Raman test paper through the invention, can obviously detect low concentration The raman spectral signal of 4- nitro thiophenols.
Embodiment 3
By a concentration of 1.0 μm of ol L-14- aminothiophenol ethanol solutions take 50 μ L that kit prepared by embodiment 1 is added In wherein correspond in test paper, soaking at room temperature 2min takes out test paper with tweezers, above glass slide, using Raman spectrometer into Row detection.The results are shown in Figure 5, and Fig. 5 is the interior reference surfaces enhancing Raman test paper detection 4- aminobenzenes using the present invention The Raman test result of thiophenol;A is the Raman spectrogram of direct analysis 4- aminothiophenol solids, and b is a concentration of 1.0 μm of ol L-1The Surface enhanced Raman spectroscopy figure of 4- aminothiophenols, c are the Raman lights of reference surfaces enhancing Raman test paper in blank Spectrogram.As can be seen from Figure, the test for enhancing Raman test paper by using the interior reference surfaces of the present invention, can be apparent Detect the raman spectral signal of the 4- aminothiophenols of low concentration, blank internal reference specific surface enhancing Raman test paper in c Two Raman peaks 911cm-1And 963cm-1For the interior reference Raman peaks of quantitative analysis.
Fig. 6 is to enhance Raman test paper using the interior reference surfaces of the present invention to test the steady of 4- aminothiophenols as substrate Qualitative comparison diagram, a are test signal figure of the same day to 4- aminothiophenols, and b is the test signal figure after placing 14 days.By figure pair Than it is found that the interior reference surfaces of the present invention enhance Raman test paper as substrate, stability is good.
Embodiment 4
By a concentration of 1.0 μm of ol L-1It is wherein right in kit prepared by embodiment 1 that benzidine ethanol solution takes 50 μ L to be added It answers in test paper, soaking at room temperature 2min, test paper is taken out with tweezers, above glass slide, is detected using Raman spectrometer, tie Fruit is as shown in fig. 7, Fig. 7 is the Raman test knot using the interior reference surfaces enhancing Raman test paper detection benzidine of the present invention Fruit;A is the Raman spectrogram of direct analysis benzidine solid, and b is a concentration of 1.0 μm of ol L-1The surface-enhanced Raman of benzidine Spectrogram, c are the Raman spectrograms of reference surfaces enhancing Raman test paper in blank.As seen from the figure, increased by surface The test of graceful test paper is haled, can obviously detect the raman spectral signal of the benzidine of low concentration, blank internal reference ratio in c Two Raman peaks 911cm of surface-enhanced Raman test paper-1And 963cm-1For the interior reference Raman peaks of quantitative analysis.
Fig. 8 is to compare the linear relationship chart that benzidine is detected using internal reference.Increased using the interior reference surfaces of the present invention Graceful test paper is haled to a concentration of 0.4,0.8,1.0,2.0,4.0,6.0 μm of ol L-1Benzidine tested, will be different dense Characteristic Raman peak 1451.63cm in the SERS signal of the benzidine of degree-1With interior reference Raman peaks 911.43cm-1Ratio is carried out, Linear relationship chart is done with ratio and concentration.By the linear relationship of ratio and concentration, it is R=to obtain linear relationship curve 0.0416C+1.766, linearly dependent coefficient 0.9919.
Embodiment 5
Sample in environmental wastewater is added in water blanks, environmental wastewater and benzidine, takes 50 μ L to be added respectively and implements It wherein being corresponded in test paper in kit prepared by example 1, soaking at room temperature 2min takes out test paper with tweezers, above glass slide, profit It is detected with Raman spectrometer, test results are shown in figure 9 for Raman, and Fig. 9 is drawn using the interior reference surfaces enhancing of the present invention Analysis chart of the graceful test paper to benzidine in environmental water sample;A is the interior reference surfaces enhancing Raman test examination using the present invention For paper to the SERS spectra figure of blank water, b is to enhance Raman test paper to environmental wastewater using the interior reference surfaces of the present invention SERS spectra figure, c are that 1.0 μm of ol L are added to environmental wastewater using the interior reference surfaces enhancing Raman test paper of the present invention-1 The SERS spectra figure of benzidine, d are to be added 2.0 to environmental wastewater using the interior reference surfaces enhancing Raman test paper of the present invention μmol L-1The SERS spectra figure of benzidine, wherein Raman peaks 1451.63cm-1As the characteristic signal peak of benzidine, Raman peaks 911.43cm-1As interior reference peak.By using standard curve, it is 3.3 μm of ol L to measure the biphenyl amine content in environmental wastewater-1, recovery of standard addition is respectively 117% and 140%.
Embodiment 6
(1) 8g oleic acid and 2g methanol and the mixed solution of 15g deionized waters are slowly stirred, by mechanical agitation, Obtain the homogeneous mixture solotion of oleic acid.
(2) sodium hydrate aqueous solution of 14g a concentration of 9% will be added in oleic acid mixed solution, carry out mechanical agitation 30min gets a uniform mixture.
(3) calcium chloride water and 15g concentration of 10g a concentration of 3% will be added in the sodium hydroxide mixed solution of oleic acid It is uniformly mixed for 7% biphosphate sodium water solution, obtains homogeneous solution.
(4) mixed solution is transferred in the tetrafluoroethene reaction kettle of 250mL and is heated to 180 DEG C of reactions for 24 hours to get suspension Particle solution centrifuges product, is cleaned for several times, is preserved in water, for use with deionized water and methanol.
(5) the 30g suspension liquids obtained by step (4) are taken to be mixed with the silver nitrate aqueous solution of 90g a concentration of 50%, light According to lower progress mechanical agitation 4h, uniformly mixed grey suspension liquid is obtained, is filtered by vacuum, interior reference surfaces enhancing Raman is obtained Test paper.
The length of hydroxyapatite overlong nanowire manufactured in the present embodiment is 200 μm, a diameter of 20nm, interior reference surfaces The thickness for enhancing Raman test paper is 0.2mm, is modified in the silver nano-grain on the hydroxyapatite overlong nanowire Content is 7.8%.
(6) test paper obtained by step (5) is cut, obtains the test paper of 4mm × 4mm, stored in 96 hole kits, Obtain interior reference surfaces enhancing Raman detection kit.
Embodiment 7
(1) 12g oleic acid and 6g methanol and the mixed solution of 10g deionized waters are slowly stirred, by mechanical agitation, Obtain the homogeneous mixture solotion of oleic acid.
(2) sodium hydrate aqueous solution of 18g a concentration of 10% will be added in oleic acid mixed solution, carry out mechanical agitation 30min gets a uniform mixture.
(3) calcium chloride water and 20g concentration of 14g a concentration of 1% will be added in the sodium hydroxide mixed solution of oleic acid It is uniformly mixed for 2% biphosphate sodium water solution, obtains homogeneous solution.
(4) mixed solution is transferred in the tetrafluoroethene reaction kettle of 250mL and is heated to 180 DEG C of reactions for 24 hours to get suspension Particle solution centrifuges product, is cleaned for several times, is preserved in water, for use with deionized water and methanol.
(5) the 50g suspension liquids obtained by step (4) is taken to be mixed with the silver nitrate aqueous solution of 110g a concentration of 40%, Mechanical agitation 4h is carried out under illumination, obtains uniformly mixed grey suspension liquid, is filtered by vacuum, and is obtained interior reference surfaces enhancing and is drawn Graceful test paper.
The length of hydroxyapatite overlong nanowire manufactured in the present embodiment is 200 μm, a diameter of 20nm, interior reference surfaces The thickness for enhancing Raman test paper is 0.2mm, is modified in the silver nano-grain on the hydroxyapatite overlong nanowire Content is 7.8%.
(6) test paper obtained by step (5) is cut, obtains the test paper of 4mm × 4mm, stored in 96 hole kits, Obtain interior reference surfaces enhancing Raman detection kit.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this The principle of invention, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these changes Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its Equivalent defines.

Claims (10)

1. a kind of interior reference surfaces enhance Raman test paper, it is characterised in that:Using hydroxyapatite overlong nanowire as medium, Further include modifying in the silver nano-grain on the hydroxyapatite overlong nanowire.
2. interior reference surfaces according to claim 1 enhance Raman test paper, it is characterised in that:The hydroxyapatite The length of overlong nanowire be 100~300 μm, preferably 200 μm, a diameter of 10~30nm, preferably 20nm.
3. interior reference surfaces according to claim 1 enhance Raman test paper, it is characterised in that:The interior reference surfaces The thickness for enhancing Raman test paper is 0.1-0.5mm, preferably 0.2mm.
4. interior reference surfaces according to claim 1 enhance Raman test paper, it is characterised in that:The modification is in described The content of silver nano-grain on hydroxyapatite overlong nanowire is 5.0~10%, preferably 7.8%.
5. the preparation method of reference surfaces enhancing Raman test paper, feature in a kind of Claims 1-4 any one of them It is:Include the following steps:
Oleic acid is scattered in the mixed solution of deionized water and methanol by the first step, and mechanical agitation is uniformly mixed, and obtains oleic acid Homogeneous mixture solotion;
Mixed solution and a concentration of 8~10% sodium hydrate aqueous solution that the first step obtains are uniformly mixed by second step, The liquid being uniformly mixed;
Third walks, be added in the mixed solution obtained to second step a concentration of 1~3% calcium chloride water and it is a concentration of 2~ 7% biphosphate sodium water solution, is uniformly mixed, the liquid being uniformly mixed;
4th step, by third step obtain mixed solution heat reaction, obtain suspension particle solution, product is centrifuged, spend from Sub- water and methanol cleaning, preserve in water;
Solution and a concentration of 40~60% silver nitrate solution that 4th step obtains are uniformly mixed, are hanged by the 5th step Supernatant liquid body, vacuum filtration obtain the interior reference surfaces enhancing Raman test paper.
6. the preparation method of interior reference surfaces enhancing Raman test paper according to claim 5, it is characterised in that:It is described The mass ratio of oleic acid, methanol and deionized water is (8~12):(2~6):(5~15), preferably (8~10):(3~5):(10 ~15);
The mass ratio of mixed solution and sodium hydrate aqueous solution that the first step obtains is (26~28):(14~18);
The mass ratio of the mixed solution that the second step obtains and calcium chloride water, biphosphate sodium water solution be (40~ 50):(10~14):(15~20).
7. the preparation method of interior reference surfaces enhancing Raman test paper according to claim 5, it is characterised in that:It is described The temperature that reaction is heated in 4th step is 100~250 DEG C, and the reaction time is 12~36h;
The mass ratio of the 4th step obtains in 5th step solution and silver nitrate solution is (30~50):(90~110);
The size of the interior reference surfaces enhancing Raman test paper is (2~20mm) × (2~20mm).
8. reference surfaces enhancing Raman test paper is polluted in environmental sample in a kind of such as Claims 1-4 any one of them Application in the quick detection kit of object.
9. a kind of application of kit as claimed in claim 8 in the quick detection of organic pollution.
10. application of the kit according to claim 9 in the quick detection of organic pollution, it is characterised in that:Institute It is 4- nitro thiophenols, 4- aminothiophenols, benzidine to state organic pollution.
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CN112014373A (en) * 2020-08-28 2020-12-01 陕西理工大学 SERS Raman substrate, preparation method thereof and method for analyzing and detecting pesticide residues
CN112014373B (en) * 2020-08-28 2023-01-13 陕西理工大学 SERS Raman substrate, preparation method thereof and method for analyzing and detecting pesticide residues
CN112525887A (en) * 2020-12-10 2021-03-19 福建师范大学 Body fluid Raman spectrum detection method of HAP/Ag composite SERS enhanced substrate

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