CN108398418B - Internal reference surface enhanced Raman test paper, preparation method and application - Google Patents
Internal reference surface enhanced Raman test paper, preparation method and application Download PDFInfo
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- CN108398418B CN108398418B CN201810218647.XA CN201810218647A CN108398418B CN 108398418 B CN108398418 B CN 108398418B CN 201810218647 A CN201810218647 A CN 201810218647A CN 108398418 B CN108398418 B CN 108398418B
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
Abstract
The invention discloses an internal reference surface enhanced Raman test paper, which takes a hydroxyapatite ultralong nanowire as a medium and also comprises silver nanoparticles modified on the hydroxyapatite ultralong nanowire. The invention also discloses a preparation method of the internal reference surface enhanced Raman test paper, and discloses application of the internal reference surface enhanced Raman test paper in a rapid detection kit for environmental sample pollutants. The internal reference surface enhanced Raman test paper has higher stability, has SERS response to various compounds such as 4-nitrothiophenol, 4-aminothiophenol, benzidine and the like when being applied to a kit, and can realize quantitative analysis of a sample compound by taking a specific Raman peak of the test paper as an internal reference and a characteristic Raman peak of the sample compound as a test signal.
Description
Technical Field
The invention belongs to the technical field of chemical analysis and detection, and particularly relates to internal reference surface enhanced Raman test paper, a preparation method and application.
Background
Surface Enhanced Raman Scattering (SERS) refers to a spectroscopic phenomenon in which the intensity of its raman scattering signal in an excitation region is greatly increased when molecules or functional groups are adsorbed onto specific surfaces of certain metals or semiconductors, such as nanoparticles, surfaces of nanowires, and surfaces with nano-scale roughness. Because the SERS has high sensitivity, rapidness and rich spectral information, the SERS is widely used for researching the surface state of a surface and an adsorption interface, the interface orientation and configuration conformation of biological large and small molecules, structural analysis and the like, and can effectively analyze the adsorption orientation, the change of the adsorption state, the interface information and the like of a compound on the interface. In the detection of environmental pollutants by utilizing and developing SERS, the method is mainly realized by means of enhancing the SERS effect of the substrate material, improving the selectivity of the substrate material, optimizing the practicability of the substrate material and the like. The roughness of the substrate surface is a necessary condition for generating the SERS phenomenon, and the physicochemical property of the substrate determines the strength of the SERS effect. Therefore, in the process of establishing an analysis method by using the surface enhanced raman scattering spectrum, preparing a substrate with high stability, high repeatability and high selectivity is always the key research direction of the SERS detection method.
Hydroxyapatite is a main inorganic component constituting bones of human and animals, has excellent biocompatibility and bioactivity, and is a widely used biomedical material. The hydroxyapatite can be used for structural modification to obtain the hydroxyapatite loaded with silver nanoparticles, and filter paper or test paper is formed.
The kit is a box for containing chemical reagents for detecting chemical components, drug residues, virus species and the like. Compared with the traditional laboratory operation, the kit is adopted for sample pretreatment or analysis, the whole detection process is simple, rapid and convenient, the kit is suitable for field operation, the requirement on analysis operation skills is low, and the detection result can be obtained in a short time.
Disclosure of Invention
The invention aims to provide an internal reference surface enhanced Raman test paper.
The invention also aims to provide a preparation method of the internal reference surface enhanced Raman test paper.
The invention further aims to provide application of the internal reference surface enhanced Raman test paper in a kit for rapidly detecting environmental sample pollutants.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
one aspect of the invention provides an internal reference surface enhanced Raman test paper, which takes a hydroxyapatite ultralong nanowire as a medium and also comprises silver nanoparticles modified on the hydroxyapatite ultralong nanowire.
The length of the hydroxyapatite ultralong nanowire is 100-300 microns, preferably 200 microns, and the diameter of the hydroxyapatite ultralong nanowire is 10-30 nm, preferably 20 nm.
The thickness of the internal reference surface-enhanced Raman test paper is 0.1-0.5mm, and preferably 0.2 mm.
The content of the silver nanoparticles modified on the hydroxyapatite ultralong nanowire is 5.0-10%, and the preferable content is 7.8%.
Another aspect of the present invention provides a method for preparing the internal reference surface enhanced raman test strip, comprising the following steps:
dispersing oleic acid in a mixed solution of deionized water and methanol, and mechanically stirring and uniformly mixing to obtain a uniformly mixed solution of oleic acid;
step two, uniformly stirring and mixing the mixed solution obtained in the step one with a sodium hydroxide aqueous solution with the concentration of 8-10% to obtain uniformly mixed liquid;
thirdly, adding a calcium chloride aqueous solution with the concentration of 1-3% and a sodium dihydrogen phosphate aqueous solution with the concentration of 2-7% into the mixed solution obtained in the second step, and stirring and mixing uniformly to obtain a uniformly mixed liquid;
step four, heating the mixed solution obtained in the step three for reaction to obtain a suspended particle solution, centrifuging a product, washing the product with deionized water and methanol, and storing the product in water;
and fifthly, uniformly stirring and mixing the solution obtained in the fourth step with a silver nitrate solution with the concentration of 40-60% to obtain a suspension, and performing vacuum filtration to obtain the internal reference surface enhanced Raman test paper.
The mass ratio of the oleic acid, the methanol and the deionized water is (8-12): 2-6): 5-15, preferably (8-10): 3-5): 10-15.
The mass ratio of the mixed solution obtained in the first step to the sodium hydroxide aqueous solution is (26-28) to (14-18).
The mass ratio of the mixed solution obtained in the second step to the calcium chloride aqueous solution and the sodium dihydrogen phosphate aqueous solution is (40-50): (10-14): 15-20).
And in the fourth step, the heating reaction temperature is 100-250 ℃, and the reaction time is 12-36 h.
The mass ratio of the solution obtained in the fourth step to the silver nitrate solution in the fifth step is (30-50): 90-110.
The size of the internal reference surface-enhanced Raman test paper is (2-20 mm) × (2-20 mm).
In another aspect, the invention provides an application of the internal reference surface enhanced Raman test paper in a rapid detection kit for environmental sample pollutants.
In yet another aspect, the invention provides the use of the kit in the rapid detection of organic contaminants.
The organic pollutants are 4-nitrothiophenol, 4-aminothiophenol and benzidine.
The application comprises the following steps: and adding 40-60 mu L of an environmental test sample into the kit, soaking the internal reference surface enhanced Raman test paper in the kit at room temperature for 2-5 min, taking out the internal reference surface enhanced Raman test paper by using a pair of tweezers, and detecting the internal reference surface enhanced Raman test paper above the glass slide by using a Raman spectrometer.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the internal reference surface enhanced Raman test paper has high stability, is applied to a kit, has SERS response to various compounds such as 4-nitrothiophenol, 4-aminothiophenol, benzidine and the like, takes a specific Raman peak of the test paper as an internal reference, and takes a characteristic Raman peak of a sample compound as a test signal, thereby realizing quantitative analysis of the sample compound and being capable of rapidly detecting the sample compound.
Drawings
FIG. 1 is a scanning electron micrograph of an internal reference surface enhanced Raman test strip of the present invention.
FIG. 2 is a transmission electron micrograph of the internal reference surface enhanced Raman test strip of the present invention.
FIG. 3 is an X-ray diffraction pattern of the internal reference surface enhanced Raman test strip of the present invention.
FIG. 4 is an enhanced Raman Scan measurement using an internal reference surface of the present inventionDetecting a Raman test result of the 4-nitrothiophenol by using test paper; a is a Raman spectrum of a 4-nitrothiophenol solid directly analyzed, and b is a concentration of 1.0mmol L-1The surface enhanced Raman spectrum of 4-nitrothiophenol, and the Raman spectrum of saturated ethanol solution of 4-nitrothiophenol.
FIG. 5 is a Raman test result of 4-aminothiophenol using the internal reference surface enhanced Raman test paper of the present invention; a is a Raman spectrum of a 4-aminothiophenol solid directly analyzed, and b is a concentration of 1.0. mu. mol L-1The surface enhanced Raman spectrum of the 4-aminothiophenol is shown in the figure, and c is the Raman spectrum of the blank internal reference surface enhanced Raman test paper.
FIG. 6 is a graph showing the stability of 4-aminothiophenol using the internal reference surface-enhanced Raman test paper of the present invention as a substrate, wherein a is a graph showing the signal measured on 4-aminothiophenol on the same day, and b is a graph showing the signal measured after the test paper is left for 14 days.
FIG. 7 is a Raman test result of benzidine detection using the internal reference surface enhanced Raman test strip of the present invention; a is a Raman spectrum of a benzidine solid directly analyzed, and b is a concentration of 1.0. mu. mol L-1And c is a Raman spectrum of the blank internal reference surface enhanced Raman test paper.
FIG. 8 is a graph showing the linear relationship of detection of benzidine using an internal reference.
FIG. 9 is an analysis of benzidine in an environmental water sample using the internal reference surface enhanced Raman test strip of the invention; a is an SERS spectrogram of the internal reference surface enhanced Raman test paper of the invention on empty water, b is an SERS spectrogram of the internal reference surface enhanced Raman test paper of the invention on environmental sewage, and c is an SERS spectrogram of the internal reference surface enhanced Raman test paper of the invention on environmental sewage added with 1.0 mu mol L-1D is adding 2.0 mu mol L of the internal reference surface enhanced Raman test paper into the environmental sewage-1SERS spectrogram of benzidine, wherein Raman peak is 1451.63cm-1Raman peak 911.43cm as characteristic signal peak of benzidine-1As an internal reference peak.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The reagents and starting materials used in the present invention are commercially available or can be prepared according to literature procedures. Unless otherwise indicated, percentages and parts are by weight.
The reagents and materials used in the examples of the invention were as follows:
the 96-well kit was purchased from the saimer feishell science and technology (china) ltd, 96-well MicrotiterTM microplates, specification: vinyl 400. mu.L.
Example 1
(1) A mixed solution of 9.36g of oleic acid and 4.75g of methanol with 13.5g of deionized water was slowly stirred, and a uniform mixed solution of oleic acid was obtained by mechanical stirring.
(2) And adding 16g of 8% sodium hydroxide aqueous solution into the oleic acid mixed solution, and mechanically stirring for 30min to obtain a uniform mixed solution.
(3) Adding 12g of 2% calcium chloride aqueous solution and 19g of 5% sodium dihydrogen phosphate aqueous solution into the oleic acid sodium hydroxide mixed solution, and stirring and mixing uniformly to obtain a uniform solution.
(4) Transferring the mixed solution to a 250mL tetrafluoroethylene reaction kettle, heating to 180 ℃ for reaction for 24h to obtain a suspended particle solution, centrifuging the product, washing the product with deionized water and methanol for several times, and storing the product in water for later use.
(5) And (3) mixing 40g of the suspension liquid obtained in the step (4) with 100g of a 60% silver nitrate aqueous solution, mechanically stirring for 4 hours under illumination to obtain a uniformly mixed gray suspension liquid, and performing vacuum filtration to obtain the internal reference surface enhanced Raman test paper. The test results of the test paper are shown in fig. 1-3, and fig. 1 is a scanning electron microscope image of the internal reference surface enhanced raman test paper of the present invention. The test paper can be seen from the figure as an ultra-long nanowire structure loaded with silver nanoparticles; FIG. 2 is a transmission electron micrograph of the internal reference surface enhanced Raman test strip of the present invention. The test paper can be seen from the figure as an ultra-long nanowire structure loaded with silver nanoparticles; FIG. 3 is an X-ray diffraction pattern of the internal reference surface enhanced Raman test strip of the present invention. The test paper is of a silver phosphate structure.
The length of the hydroxyapatite ultralong nanowire prepared in the embodiment is 200 μm, the diameter of the hydroxyapatite ultralong nanowire is 20nm, the thickness of the internal reference surface enhanced raman test paper is 0.2mm, and the content of silver nanoparticles modified on the hydroxyapatite ultralong nanowire is 7.8%.
(6) And (4) cutting the test paper obtained in the step (5) to obtain test paper of 4mm multiplied by 4mm, and storing the test paper into a 96-hole kit to obtain the internal reference surface enhanced Raman detection kit.
Example 2
The concentration is 1.0mmol L -150 mu L of 4-nitrothiophenol ethanol solution is added into the corresponding test paper in the kit prepared in example 1, the test paper is soaked for 2min at room temperature, the test paper is taken out by using tweezers, and the test paper is placed on a glass slide and detected by using a Raman spectrometer. The results are shown in fig. 4, fig. 4 is a raman test result of detecting 4-nitrothiophenol by using the internal reference surface enhanced raman test paper of the present invention; a is a Raman spectrum of a 4-nitrothiophenol solid directly analyzed, and b is a concentration of 1.0mmol L-1The surface enhanced Raman spectrum of 4-nitrothiophenol, and the Raman spectrum of saturated ethanol solution of 4-nitrothiophenol. It can be seen from the figure that the Raman spectrum signal of the 4-nitrothiophenol with low concentration can be obviously detected through the test of the internal reference surface enhanced Raman test paper.
Example 3
The concentration is 1.0 mu mol L -150 mu L of 4-aminothiophenol ethanol solution is added into the corresponding test paper in the kit prepared in example 1, the test paper is soaked for 2min at room temperature, the test paper is taken out by using tweezers, and the test paper is placed on a glass slide and detected by using a Raman spectrometer. The results are shown in fig. 5, fig. 5 is a raman test result of detecting 4-aminothiophenol using the internal reference surface enhanced raman test paper of the present invention; a is direct analysis of 4-aminothiophenol solidsRaman spectrum, b is concentration of 1.0. mu. mol L-1The surface enhanced Raman spectrum of the 4-aminothiophenol is shown in the figure, and c is the Raman spectrum of the blank internal reference surface enhanced Raman test paper. As can be seen from the figure, through the test of the internal reference surface enhanced Raman test paper, the Raman spectrum signal of the 4-aminothiophenol with low concentration can be obviously detected, and the two Raman peaks of the c hollow white internal reference surface enhanced Raman test paper are 911cm-1And 963cm-1Is an internal reference Raman peak for quantitative analysis.
FIG. 6 is a graph showing the stability of 4-aminothiophenol using the internal reference surface-enhanced Raman test paper of the present invention as a substrate, wherein a is a graph showing the signal measured on 4-aminothiophenol on the same day, and b is a graph showing the signal measured after the test paper is left for 14 days. As can be seen from the comparison of the graphs, the internal reference surface enhanced Raman test paper provided by the invention is good in stability as a substrate.
Example 4
The concentration is 1.0 mu mol L-1Adding 50 mu L of benzidine ethanol solution into the corresponding test paper in the kit prepared in the embodiment 1, soaking at room temperature for 2min, taking out the test paper with forceps, placing the test paper on a glass slide, and detecting by using a Raman spectrometer, wherein the result is shown in FIG. 7, and FIG. 7 is the Raman test result of detecting benzidine by using the internal reference surface enhanced Raman test paper of the invention; a is a Raman spectrum of a benzidine solid directly analyzed, and b is a concentration of 1.0. mu. mol L-1And c is a Raman spectrum of the blank internal reference surface enhanced Raman test paper. As can be seen from the figure, through the test of the surface enhanced Raman test paper, the Raman spectrum signal of the benzidine with low concentration can be obviously detected, and the two Raman peaks of the hollow white internal reference surface enhanced Raman test paper are 911cm-1And 963cm-1Is an internal reference Raman peak for quantitative analysis.
FIG. 8 is a graph showing the linear relationship of detection of benzidine using an internal reference. The internal reference surface enhanced Raman test paper of the invention has the concentration of 0.4, 0.8, 1.0, 2.0, 4.0 and 6.0 mu mol L-1Testing the benzidine, and measuring SERS signals of the benzidine with different concentrationsCharacteristic Raman peak in (2) 1451.63cm-1Raman peak 911.43cm compared with internal reference-1Ratios were performed and a linear plot was made of ratio and concentration. Through the linear relation between the ratio and the concentration, a linear relation curve is obtained, wherein R is 0.0416C +1.766, and a linear correlation coefficient is 0.9919.
Example 5
Adding a blank aqueous solution, environmental sewage and benzidine into a sample in the environmental sewage, respectively taking 50 mu L of the sample, adding the sample into corresponding test paper in the kit prepared in the embodiment 1, soaking the test paper for 2min at room temperature, taking the test paper out by using tweezers, detecting the test paper above a glass slide by using a Raman spectrometer, wherein the Raman test result is shown in figure 9, and figure 9 is an analysis graph of benzidine in an environmental water sample by using the internal reference surface enhanced Raman test paper of the invention; a is an SERS spectrogram of the internal reference surface enhanced Raman test paper of the invention on empty water, b is an SERS spectrogram of the internal reference surface enhanced Raman test paper of the invention on environmental sewage, and c is an SERS spectrogram of the internal reference surface enhanced Raman test paper of the invention on environmental sewage added with 1.0 mu mol L-1D is adding 2.0 mu mol L of the internal reference surface enhanced Raman test paper into the environmental sewage-1SERS spectrogram of benzidine, wherein Raman peak is 1451.63cm-1Raman peak 911.43cm as characteristic signal peak of benzidine-1As an internal reference peak. The benzidine content in the environmental wastewater was determined to be 3.3. mu. mol L by using a standard curve-1The recovery rates of the normalized product are 117% and 140%, respectively.
Example 6
(1) The mixed solution of 8g of oleic acid, 2g of methanol and 15g of deionized water was slowly stirred, and a uniform mixed solution of oleic acid was obtained by mechanical stirring.
(2) And adding 14g of 9% sodium hydroxide aqueous solution into the oleic acid mixed solution, and mechanically stirring for 30min to obtain a uniform mixed solution.
(3) Adding 10g of 3% calcium chloride aqueous solution and 15g of 7% sodium dihydrogen phosphate aqueous solution into the oleic acid sodium hydroxide mixed solution, and stirring and mixing uniformly to obtain a uniform solution.
(4) Transferring the mixed solution to a 250mL tetrafluoroethylene reaction kettle, heating to 180 ℃ for reaction for 24h to obtain a suspended particle solution, centrifuging the product, washing the product with deionized water and methanol for several times, and storing the product in water for later use.
(5) And (3) mixing 30g of the suspension liquid obtained in the step (4) with 90g of 50% silver nitrate aqueous solution, mechanically stirring for 4 hours under illumination to obtain uniformly mixed gray suspension liquid, and performing vacuum filtration to obtain the internal reference surface enhanced Raman test paper.
The length of the hydroxyapatite ultralong nanowire prepared in the embodiment is 200 μm, the diameter of the hydroxyapatite ultralong nanowire is 20nm, the thickness of the internal reference surface enhanced raman test paper is 0.2mm, and the content of silver nanoparticles modified on the hydroxyapatite ultralong nanowire is 7.8%.
(6) And (4) cutting the test paper obtained in the step (5) to obtain test paper of 4mm multiplied by 4mm, and storing the test paper into a 96-hole kit to obtain the internal reference surface enhanced Raman detection kit.
Example 7
(1) The mixed solution of 12g of oleic acid, 6g of methanol and 10g of deionized water was slowly stirred, and a uniform mixed solution of oleic acid was obtained by mechanical stirring.
(2) And adding 18g of 10% sodium hydroxide aqueous solution into the oleic acid mixed solution, and mechanically stirring for 30min to obtain a uniform mixed solution.
(3) Adding 14g of 1% calcium chloride aqueous solution and 20g of 2% sodium dihydrogen phosphate aqueous solution into the oleic acid sodium hydroxide mixed solution, and stirring and mixing uniformly to obtain a uniform solution.
(4) Transferring the mixed solution to a 250mL tetrafluoroethylene reaction kettle, heating to 180 ℃ for reaction for 24h to obtain a suspended particle solution, centrifuging the product, washing the product with deionized water and methanol for several times, and storing the product in water for later use.
(5) And (3) mixing 50g of the suspension obtained in the step (4) with 110g of a 40% silver nitrate aqueous solution, mechanically stirring for 4 hours under illumination to obtain a uniformly mixed gray suspension, and performing vacuum filtration to obtain the internal reference surface enhanced Raman test paper.
The length of the hydroxyapatite ultralong nanowire prepared in the embodiment is 200 μm, the diameter of the hydroxyapatite ultralong nanowire is 20nm, the thickness of the internal reference surface enhanced raman test paper is 0.2mm, and the content of silver nanoparticles modified on the hydroxyapatite ultralong nanowire is 7.8%.
(6) And (4) cutting the test paper obtained in the step (5) to obtain test paper of 4mm multiplied by 4mm, and storing the test paper into a 96-hole kit to obtain the internal reference surface enhanced Raman detection kit.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. An application of an internal reference surface enhanced Raman test paper which takes a hydroxyapatite super-long nanowire as a medium and also comprises silver nanoparticles modified on the hydroxyapatite super-long nanowire in preparing a kit for rapidly detecting organic matters is provided;
wherein the organic matter is 4-nitrothiophenol, 4-aminothiophenol or benzidine;
the internal reference surface enhanced Raman test paper is prepared by the preparation method comprising the following steps:
dispersing oleic acid in a mixed solution of deionized water and methanol, and mechanically stirring and uniformly mixing to obtain a uniformly mixed solution of oleic acid;
secondly, uniformly stirring and mixing the mixed solution obtained in the first step with a sodium hydroxide aqueous solution with the concentration of 8-10% to obtain uniformly mixed liquid;
thirdly, adding a calcium chloride aqueous solution with the concentration of 1-3% and a sodium dihydrogen phosphate aqueous solution with the concentration of 2-7% into the mixed solution obtained in the second step, and stirring and mixing uniformly to obtain a uniformly mixed liquid;
step four, heating the mixed solution obtained in the step three for reaction to obtain a suspended particle solution, centrifuging a product, washing the product with deionized water and methanol, and storing the product in water;
and fifthly, uniformly stirring and mixing the solution obtained in the fourth step with a silver nitrate solution with the concentration of 40-60% to obtain a suspension, and performing vacuum filtration to obtain the target product.
2. The use according to claim 1, wherein the hydroxyapatite ultralong nanowires have a length of 100 μm to 300 μm and a diameter of 10nm to 30 nm.
3. The use of claim 1, wherein the internal reference surface enhanced raman test strip has a thickness of 0.1mm to 0.5 mm.
4. The use according to claim 1, wherein the content of the silver nanoparticles modified on the hydroxyapatite ultralong nanowire is 5.0% to 10%.
5. The method of claim 1, wherein the mass ratio of the oleic acid, the methanol and the deionized water is (8-12): 2-6): 5-15, the mass ratio of the mixed solution obtained in the first step to the aqueous solution of sodium hydroxide is (26-28): 14-18, and the mass ratio of the mixed solution obtained in the second step to the aqueous solution of calcium chloride and the aqueous solution of sodium dihydrogen phosphate is (40-50): 10-14): 15-20.
6. The application of claim 1, wherein the heating reaction temperature in the fourth step is 100-250 ℃, the reaction time is 12-36 h, the mass ratio of the solution obtained in the fourth step to the silver nitrate solution in the fifth step is (30-50): 90-110, and the size of the internal reference surface enhanced Raman test paper is (2-20 mm) × (2-20 mm).
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| CN106012677A (en) * | 2016-05-31 | 2016-10-12 | 中国科学院上海硅酸盐研究所 | Nano-silver compounded hydroxyapatite super-long nanowire antibacterial paper |
| CN106596528A (en) * | 2016-11-08 | 2017-04-26 | 中国科学院上海硅酸盐研究所 | Detection test paper based on hydroxyapatite ultra-long nano-wire/metal organic coordination compound |
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| GB0606891D0 (en) * | 2006-04-05 | 2006-05-17 | Council Cent Lab Res Councils | Raman Analysis Of Pharmaceutical Tablets |
| WO2008028194A2 (en) * | 2006-09-01 | 2008-03-06 | Cornell Research Foundation, Inc. | Calcium phosphate nanofibers |
| US20100050901A1 (en) * | 2008-09-04 | 2010-03-04 | Biris Alexandru S | Multi-level anticounterfeit, security and detection taggant |
| SG11201702715UA (en) * | 2014-07-02 | 2017-04-27 | Univ Singapore | Raman spectroscopy system, apparatus, and method for analyzing, characterizing, and/or diagnosing a type or nature of a sample or a tissue such as an abnormal growth |
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| CN106012677A (en) * | 2016-05-31 | 2016-10-12 | 中国科学院上海硅酸盐研究所 | Nano-silver compounded hydroxyapatite super-long nanowire antibacterial paper |
| CN106596528A (en) * | 2016-11-08 | 2017-04-26 | 中国科学院上海硅酸盐研究所 | Detection test paper based on hydroxyapatite ultra-long nano-wire/metal organic coordination compound |
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