CN112033948A - Surface-enhanced Raman test paper and preparation method and application thereof - Google Patents
Surface-enhanced Raman test paper and preparation method and application thereof Download PDFInfo
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- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 81
- 238000012360 testing method Methods 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229940085605 saccharin sodium Drugs 0.000 claims abstract description 46
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 238000001514 detection method Methods 0.000 claims abstract description 24
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000835 fiber Substances 0.000 claims abstract description 11
- 238000007540 photo-reduction reaction Methods 0.000 claims abstract description 7
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004332 silver Substances 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- -1 silver ions Chemical class 0.000 claims abstract description 4
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 235000014214 soft drink Nutrition 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 101710134784 Agnoprotein Proteins 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 18
- BXAVKNRWVKUTLY-UHFFFAOYSA-N 4-sulfanylphenol Chemical compound OC1=CC=C(S)C=C1 BXAVKNRWVKUTLY-UHFFFAOYSA-N 0.000 description 13
- 239000000523 sample Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000001237 Raman spectrum Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002965 ELISA Methods 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008122 artificial sweetener Substances 0.000 description 1
- 235000021311 artificial sweeteners Nutrition 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 235000021096 natural sweeteners Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004557 single molecule detection Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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Abstract
The invention discloses a surface-enhanced Raman test paper and a preparation method and application thereof, wherein the surface-enhanced Raman test paper comprises a paper substrate, a titanium dioxide film and silver nanoparticles, wherein the paper substrate is filter paper with a multi-stage fiber and hole structure; the titanium dioxide film coats the surface of the paper substrate fiber; the silver nanoparticles are separated out through the photoreduction reaction of silver ions and the titanium dioxide film, and are deposited on the surface of the paper substrate and in the hole structure, so that the Raman effect is integrally enhanced. The surface-enhanced Raman test paper can be used for detecting the content of saccharin sodium in an aqueous solution, and has the advantages of simple and quick detection process, high sensitivity of a detection result, good repeatability and good stability.
Description
Technical Field
The invention relates to a saccharin sodium detection method, in particular to surface-enhanced Raman test paper and a preparation method and application thereof.
Background
Saccharin sodium is commonly called "sweet essence" or "saccharin", and is a common artificial sweetener. The saccharinity of the saccharin sodium is 300-600 times sweeter than that of natural sweeteners such as cane sugar, brown sugar and the like, so that the saccharin sodium is widely added into various foods. Relevant researches show that the saccharin sodium has potential carcinogenic effect and influences the health of minors, so that the dosage of the saccharin sodium in dry fruit foods is strictly regulated in many countries, for example, the dosage of the saccharin sodium is 0.5-3.0 g/kg in European Union, and the dosage of the saccharin sodium is 1.0-5.0 g/kg in Chinese national standard. At present, in order to obtain better mouthfeel and consumer acceptance, saccharin sodium is often added in excess to many foods, so that rapid and accurate analysis of the saccharin sodium content in the food is of great significance to product quality monitoring.
At present, the detection method of saccharin sodium mainly comprises a high performance liquid chromatography, a liquid chromatography-mass spectrometry combined method, a thin layer chromatography, an ultraviolet spectrophotometry, a colorimetric method, an electrochemical method, an enzyme-linked immunosorbent assay and the like. Among them, the high performance liquid chromatography is an analysis method adopted by the national standard, but the operation is complex, the analysis takes long time, and the method is not beneficial to the simple and rapid detection of a large amount of samples. The phenolsulfonic titanium colorimetric method and the ultraviolet spectrophotometry method are the national standard method for rapidly screening saccharin sodium, but are finally replaced by the HPLC method because the sample extraction and separation processes are complex and are easily interfered by food matrix components. Therefore, at present, no accurate and effective simple and rapid detection method for saccharin sodium in food exists.
The Surface Enhanced Raman Scattering (SERS) technique can realize single-molecule detection due to its extremely high sensitivity, and is widely used in chemical analysis, biological analysis, and the like. CN103353450A, "a method for rapidly detecting saccharin sodium in wine", discloses a method for rapidly detecting saccharin sodium in wine, which comprises (1) preparing raman detection nanoparticles; (2) preparing saccharin sodium standard solutions with different concentrations; (3) establishing a relation curve of SERS characteristic peak intensity-concentration of saccharin sodium; (4) and detecting the concentration of saccharin sodium in the sample by Raman spectrum. The invention has the advantages of high detection speed, low detection cost, no professional technical requirements on detection personnel, realization of rapid detection and the like. The invention realizes the application of SERS technology in the rapid detection method of saccharin sodium, but the prepared Raman detection nanoparticles are in a sol form, so that the stability problem and the portability problem exist, and the Raman signal enhancement effect and the detection sensitivity need to be improved.
Disclosure of Invention
The invention aims to provide surface-enhanced Raman test paper, a preparation method and application thereof, wherein a paper substrate deposited with silver nanoparticles is used as the surface-enhanced Raman test paper (SERS test paper), and the content of Saccharin Sodium (SS) in soft drinks can be rapidly, simply, conveniently, highly sensitively, stably and repeatedly detected.
The purpose of the invention is realized by the following technical scheme: a surface-enhanced Raman test paper comprises a paper substrate and titanium dioxide (TiO)2) The paper substrate is filter paper with a multi-stage fiber and hole structure; the titanium dioxide film coats the surface of the paper substrate fiber; the Ag NPs are formed by silver ions and TiO2The film is separated out by photoreduction reaction and is deposited on the surface of the paper substrate and in the hole structure.
Preferably, the paper substrate is a paper chip VL 98.
According to the invention, the filter paper with a multi-stage fiber and hole structure is used as a paper substrate, the specific surface area is large, the loading capacity of Ag NPs is increased, the reaction activity is higher, and Raman spectrum signals are greatly enhanced; a large amount of Ag NPs are deposited and uniformly distributed on the surface and in the paper substrate through a photoreduction reaction and are used as SERS test paper to detect hot spots, so that the synergistic enhancement effect of an electromagnetic enhancement and charge transfer mechanism is obtained.
A preparation method of surface enhanced Raman test paper comprises the following steps:
（1）TiO2preparing an aqueous solution;
(2) adding TiO into the mixture2The aqueous solution is coated on the surface of a paper substrate and dried to form TiO2A film-coated paper substrate;
(3) adding TiO into the mixture2Soaking paper substrate coated with film in AgNO3And irradiating the solution under an ultraviolet lamp to obtain the SERS test paper.
Preferably, TiO in the step (1)2The concentration of the aqueous solution is 0.5%; TiO in the step (2)2The dropping amount of the aqueous solution is 20-100 mu L.
Preferably, AgNO in the step (3)3The solvent of the solution was 10% (v/v) aqueous methanol at a concentration of 5X 10- 5mol/L~5×10-3mol/L。
Preferably, the irradiation time of the ultraviolet lamp in the step (3) is 0.5-2 h.
The invention utilizesThe pores between the fibers on the surface of the filter paper are utilized, and the water absorption of the filter paper and the capillary action of the pores between the fibers on the surface of the filter paper are utilized to ensure that the TiO is coated with the water-soluble TiO2Adsorbing to the surface of filter paper; and depositing Ag NPs with nanometer sizes on the paper substrate through a photoreduction reaction.
The application of the surface enhanced Raman test paper comprises the following steps of detecting the SS content in soft drinks:
(1) respectively dripping SS solutions with different concentrations on the surface of SERS test paper, respectively detecting Raman signals by a Raman spectrometer, and establishing a Raman signal-SS concentration standard curve;
(2) heating soft drink samples to remove CO2And adding ethyl acetate to extract SS, taking the upper layer liquid to be dripped on the surface of SERS test paper, detecting a Raman signal, and calculating the SS content according to a standard curve.
The SERS test paper is applied to the detection of SS content in soft drinks, Ag NPs on the SERS test paper can be adsorbed on the surface of a nitro ion coordination site of SS, and the SS content can be obtained according to a Raman signal; matrix interference is eliminated through ethyl acetate extraction and SERS analysis conditions, and finally the simple, convenient and sensitive SERS test paper rapid detection method of SS in soft drinks is realized.
Compared with the prior art, the invention has the following beneficial effects:
1) compared with a hard substrate, the SERS test paper provided by the invention has the advantages that the structure of multilevel fibers and holes is beneficial to depositing a large amount of silver nanoparticles, and the SERS test paper has a better Raman enhancement effect and higher sensitivity; and the paper substrate has low production cost, is light, thin and portable, is convenient to use and can be cut as required.
2) The SERS test paper is applied to the detection of SS content in soft drinks, the detection process is simple and quick, the sensitivity of the detection result is high, and the lowest detection limit can reach 6 multiplied by 10-10mol/L; good repeatability, the Relative Standard Deviation (RSD) is less than 10%; the stability is good, and the integral form and SERS signal intensity of the SERS test paper are not obviously changed after the SERS test paper is stored for 40 days.
Drawings
FIG. 1 shows TiO in the preparation of SERS test paper of examples 1-82Aqueous solutionThe effect of volume on raman signal intensity;
FIG. 2 shows bare paper chip and TiO according to example 42A Raman spectrogram of the paper chip and the SERS test paper coated by the film;
FIG. 3 shows bare paper chips (A) and TiO according to example 42Scanning electron micrographs of the paper chip (B) and the SERS test paper (C) coated by the film;
FIG. 4 shows AgNO in the preparation process of SERS test paper of examples 4 and 9-123The effect of solution concentration on raman signal intensity;
FIG. 5 shows the influence of the irradiation time of an ultraviolet lamp on the Raman signal intensity in the preparation process of SERS test paper of examples 4 and 13-15;
FIG. 6 is a Raman spectrum of the SERS strip treated with different concentrations of the p-ATP probe in example 16;
FIG. 7 is a logarithmic concentration-Raman signal intensity standard curve of the p-ATP probe in example 16;
FIG. 8 is a Raman spectrum of the SERS test paper in the repeatability test of example 17;
FIG. 9 is a graph showing the effect of the reproducibility test of example 17 on the intensity of Raman signal;
FIG. 10 is a graph of the effect of the stability test on the intensity of Raman signals in example 18;
FIG. 11 is a Raman spectrum of the SERS test paper treated with different SS concentrations in example 19;
FIG. 12 is a standard curve graph of the SS concentration versus the Raman signal intensity of example 19.
Detailed Description
Example 1-8 preparation method of surface enhanced Raman test paper (TiO)2Examination of volume of aqueous solution
(1) 0.5g of TiO2The solid is dissolved in 100mL of aqueous solution to prepare 0.5 percent TiO2The aqueous solution is stored in a refrigerator for later use.
(2) The paper chips VL98 were cut into 1.5 cm by 2 cm pieces and different volumes of 0.5% TiO2The aqueous solution was applied to the surface of paper chips VL98 and dried in air to form TiO2A film-coated paper chip.
(3) Adding TiO into the mixture2Soaking the film-coated paper chip in 5 × 10-4 mol/L AgNO3Irradiating the solution (10% (v/v) methanol aqueous solution) for 1h under an ultraviolet lamp of 254 nm to obtain the SERS test paper.
(4) The concentration is 5X 10-5Dripping a p-mercaptophenol (p-ATP) probe of mol/L onto SERS test paper, detecting a Raman signal by using a Raman spectrometer at 1078cm-1The raman signal intensity is characterized for the characteristic peaks.
As shown in FIG. 1, in TiO2The volume of the aqueous solution is within the range of 20 mu L-100 mu L, and the Raman signal intensity is dependent on TiO2Increase and decrease of aqueous solution volume, TiO2The Raman signal is strongest when the dropping amount is 60 uL.
As shown in FIG. 2, the bare paper chip and TiO of example 42The Raman spectrogram of the paper chip coated by the film has no obvious characteristic peak, and the Raman spectrogram of the SERS test paper deposited with the Ag NPs has an obvious Raman signal, so that the Ag NPs deposited by the photoreduction reaction have Raman activity.
As shown in FIG. 3, TiO2After the aqueous solution is coated on a bare paper chip, TiO is formed on the surface of the fiber structure by granular adsorption2A film-coated paper chip; TiO 22Film-coated paper chip immersion in AgNO3After the solution is subjected to photoreduction reaction, a large amount of nano-scale Ag NPs are deposited on the paper chip and are uniformly and densely distributed, a large amount of hot spots are formed, a good enhancement effect can be generated, and the SERS test paper with better performance of the functionalized active substrate is obtained.
Example 9-12 preparation method of surface enhanced Raman test paper (AgNO)3Investigation of solution concentration)
(1) 0.5g of TiO2The solid is dissolved in 100mL of aqueous solution to prepare 0.5 percent TiO2The aqueous solution is stored in a refrigerator for later use.
(2) The paper chips VL98 were cut into 1.5 cm. times.2 cm pieces, and 60. mu.L of 0.5% TiO was added2Application of the aqueous solution toDrying the surface of the paper chip VL98 in air to form TiO2A film-coated paper chip.
(3) Adding TiO into the mixture2Soaking the paper chip coated with the film in AgNO with different concentrations3Irradiating the solution (10% (v/v) methanol aqueous solution) for 1h under an ultraviolet lamp of 254 nm to obtain the SERS test paper.
(4) The concentration is 5X 10-5Dropping a p-ATP probe of mol/L onto the SERS test paper, detecting a Raman signal by a Raman spectrometer at 1078cm-1The raman signal intensity is characterized for the characteristic peaks.
As shown in FIG. 4, in AgNO3The concentration of the solution is 5X 10-5mol/L~5×10-3In the mol/L range, the Raman signal intensity is dependent on AgNO3The decrease of the solution concentration is increased and then decreased when AgNO3The solution is 5X 10-4The Raman signal is strongest when the concentration is mol/L.
Example 13 to 15 preparation of surface-enhanced Raman test paper (UV light irradiation time)
(1) 0.5g of TiO2The solid is dissolved in 100mL of aqueous solution to prepare 0.5 percent TiO2The aqueous solution is stored in a refrigerator for later use.
(2) The paper chips VL98 were cut into 1.5 cm. times.2 cm pieces, and 60. mu.L of 0.5% TiO was added2The aqueous solution was applied to the surface of paper chips VL98 and dried in air to form TiO2A film-coated paper chip.
(3) Adding TiO into the mixture2Soaking the paper chip coated with the film in AgNO with different concentrations3And (3) irradiating the solution (10% (v/v) methanol aqueous solution) for different time under an ultraviolet lamp of 254 nm to obtain the SERS test paper.
(4) The concentration is 5X 10-5Dropping a p-ATP probe of mol/L onto the SERS test paper, detecting a Raman signal by a Raman spectrometer at 1078cm-1The raman signal intensity is characterized for the characteristic peaks.
As shown in fig. 5, in the range of 0.5 h-2 h of the ultraviolet lamp irradiation time, different irradiation times can also affect the generation density, size and shape of the silver particles, and when the irradiation time is 1h, the raman signal of the SERS test paper is strongest.
Example 16 SERS Signal testing
The concentration is 6 x 10-10 、2×10-9、6×10-9、6×10-8、1×10-7mol/L p-ATP is respectively dripped on the surface of the SERS test paper obtained in example 4, and Raman signals are respectively detected by a Raman spectrometer at 1078cm-1The raman signal intensity is characterized for the characteristic peaks.
As shown in FIGS. 6 and 7, the Raman spectra of SERS test paper treated by different concentrations of p-ATP probe are 1004 cm-1、1078 cm-1And 1594 cm-1Characteristic peaks occur, which can be attributed to C — S stretching; at a p-ATP concentration of 6X 10-10 mol/L ~1×10-7In the mol/L range, at 1078cm-1The logarithm of the p-ATP concentration is linear with SERS signal intensity for the characteristic peak, with the linear equation y =4820 log [ C (p-ATP)]+46198, coefficient of correlation R2=0.9900。
Example 17 repeatability test
The concentration is 1 x 10-7Dropwise adding mol/L p-ATP to the surfaces of 20 randomly selected areas of the SERS test paper obtained in example 4, and respectively detecting Raman signals by using a Raman spectrometer at 1078cm-1The raman signal intensity is characterized for the characteristic peaks.
As shown in fig. 8 and 9, the profiles of the raman bands of the 20 p-ATP were very similar, with no change in the main raman band and no significant change in raman intensity. 1078cm-1The Relative Standard Deviation (RSD) of the wave band vibration is less than 10%, and the SERS test paper is proved to have high repeatability and reproducibility.
EXAMPLE 18 stability test
The SERS test paper obtained in example 4 was stored in air at 0, 7,14. After 24 and 40 days, the mixture is dripped into the mixture with the concentration of 1 multiplied by 10-7Detecting Raman signal with Raman spectrometer at 1078cm from mol/L p-ATP-1The raman signal intensity is characterized for the characteristic peaks.
As shown in FIG. 10, the overall morphology of the SERS strip was not significantly changed after 40 days storage, 1078cm-1The Raman signal intensity at the characteristic peak is only slightly changed, which shows that the SERS test paper adopting the light reduction deposition of Ag NPs has good time stability and can meet the requirement of conventional detection.
Example 19 application of SERS test paper in SS detection
(1) Preparing an SS stock solution with an initial concentration of 1g/L by using ultrapure water as a solvent, diluting the SS stock solution to different concentrations (0.5, 10, 20, 50, 80 and 100 mg/L), taking out the SS stock solution by using a liquid transfer gun, dropwise adding the SS stock solution to the surface of SERS test paper, detecting a Raman signal by using a Raman spectrometer, and detecting the Raman signal by 1014cm-1And characterizing the Raman signal intensity for a characteristic peak, and making a Raman signal intensity-SS concentration standard curve.
(2) SS was added to each of the two different soft drinks, Spanish Bill and Cola, at a concentration of 40mg/L, and all samples were heated for 5 minutes to release CO2And adding ethyl acetate for extraction, layering in a short time, and taking the upper liquid to perform Raman signal detection by using SERS test paper.
As shown in FIGS. 11 and 12, the standard curve is at 1014cm-1The SS concentration and the Raman signal intensity are in a linear relation for a characteristic peak, the linear equation is y =458.7x +579.6 (x is the SS concentration and has the unit of mg/L), and the correlation coefficient R2= 0.9909. The SS concentration detected in the soft drink is substituted into a linear equation, and the recovery rate is 90-103 percent, which shows that the method is accurate and reliable.
Claims (7)
1. The surface-enhanced Raman test paper is characterized by comprising a paper substrate, a titanium dioxide film and silver nanoparticles, wherein the paper substrate is filter paper with a multistage fiber and hole structure; the titanium dioxide film coats the surface of the paper substrate fiber; the silver nanoparticles are separated out through the photoreduction reaction of silver ions and the titanium dioxide film and are deposited on the surface of the paper substrate and in the hole structure.
2. The surface-enhanced raman test paper of claim 1, wherein said paper substrate is a paper chip VL 98.
3. A method of preparing the surface-enhanced raman test paper of claim 1, comprising the steps of:
(1) preparing a titanium dioxide aqueous solution;
(2) coating a titanium dioxide aqueous solution on the surface of a paper substrate, and drying to form a titanium dioxide film-coated paper substrate;
(3) soaking the paper substrate coated with the titanium dioxide film in AgNO3And irradiating the solution under an ultraviolet lamp to obtain the SERS test paper.
4. The method for preparing surface-enhanced raman spectroscopy paper according to claim 3, wherein the concentration of the aqueous solution of titanium dioxide in the step (1) is 0.5%; the dropping amount of the titanium dioxide aqueous solution in the step (2) is 20-100 mu L.
5. The method of claim 3, wherein the AgNO test paper prepared in step (3)3The solvent of the solution was 10% (v/v) aqueous methanol at a concentration of 5X 10-5mol/L~ 5×10-3mol/L。
6. The method for preparing the surface-enhanced Raman test paper according to claim 3, wherein the irradiation time of the ultraviolet lamp in the step (3) is 0.5 to 2 hours.
7. Use of a surface enhanced raman test strip according to claim 1 for the detection of sodium saccharin in soft drinks by the steps of:
(1) respectively dripping saccharin sodium solutions with different concentrations onto the surface of the surface enhanced Raman test paper, respectively detecting Raman signals by a Raman spectrometer, and establishing a Raman signal-saccharin sodium concentration standard curve;
(2) heating soft drink samples to remove CO2And adding ethyl acetate to extract the saccharin sodium, taking the upper layer liquid, dropwise adding the upper layer liquid onto the surface of the surface-enhanced Raman test paper, detecting a Raman signal, and calculating the content of the saccharin sodium according to a standard curve.
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