CN110455714B - SERS substrate capable of naturally eliminating fluorescence background and preparation method thereof - Google Patents
SERS substrate capable of naturally eliminating fluorescence background and preparation method thereof Download PDFInfo
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- CN110455714B CN110455714B CN201910623162.3A CN201910623162A CN110455714B CN 110455714 B CN110455714 B CN 110455714B CN 201910623162 A CN201910623162 A CN 201910623162A CN 110455714 B CN110455714 B CN 110455714B
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- 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
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Abstract
The invention discloses an SERS substrate capable of naturally eliminating fluorescence background and a preparation method thereof, belonging to the technical field of molecular recognition, wherein a chemical precipitation method is adopted, zinc nitrate hexahydrate, neodymium nitrate hexahydrate and ammonium bicarbonate are used as raw materials, and the molar ratio of various substances is ammonium bicarbonate: metal cation (Nd)3+、Zn2+) The total of (1: 1) and the bicarbonate is used as a precursor to prepare the target product, namely the echinoid neodymium-doped zinc oxide material, the material naturally eliminates the fluorescence background and enhances the SERS activity, has good stability and repeatability, is an ideal SERS substrate, and can be applied to the fields of chemistry, materials science, biomedicine and the like.
Description
Technical Field
The invention belongs to the technical field of molecular recognition, and particularly relates to a preparation method of an SERS substrate capable of naturally eliminating a fluorescence background by a chemical precipitation method.
Background
Since 1928, the research of raman spectroscopy has continued. With the development of laser technology, the problem of weak signal intensity is improved by a high-energy radiation light source. The Surface-enhanced Raman Scattering (SERS) spectrum is used as a Surface analysis spectrum technology for effectively representing molecular structure, adsorption behavior, vibration mode and detection interface characteristics, has the advantages of no damage, ultra-sensitivity, fingerprint molecule identification capability and the like, arouses great interest of people, and is widely applied to the fields of food safety, analytical chemistry, environmental monitoring and the like. However, the current SERS technology has the outstanding problems in application that the substrate has poor activity, unstable structure and property, and the difficulty in substrate preparation limits people's understanding of the SERS phenomenon, which also results in imperfect understanding of the SERS mechanism. Therefore, the preparation of the SERS active substrate is always the most important research field of the SERS technology, and the design of the high-activity substrate can not only link the experiment with the theory, but also provide an ideal model for the theoretical research of SERS. Meanwhile, the development of the SERS substrate determines whether the application range of SERS can be continuously widened.
Although the research of SERS has been rapidly progressed, the SERS technology still has great difficulty for quantitative analysis so far, and a great deal of research shows that the SERS spectrum is usually accompanied by the generation of fluorescence background mainly derived from Photoluminescence (PL) of substrate and adsorbed molecules, which reduces the specificity of raman labeling. The first success of Buchanan et al demonstrated a method of directly correcting the background. In addition, Ren et al proposed a method for recovering the native chemistry information from SERS using plasma PL and quantitatively studied the relationship between PL and SERS background. While these methods can reasonably correct the SERS spectrum and eliminate the negative impact of PL on SERS, it suffers from secondary processing, affecting the accuracy of the analysis of experimental data. Therefore, there is a need for further research on SERS and PL, and it is an important subject in the field of SERS research to develop a method that can naturally eliminate the background of fluorescence rather than artificially eliminate the background of fluorescence.
Disclosure of Invention
The invention aims to provide an SERS substrate capable of naturally eliminating a fluorescence background and a preparation method thereof. The method adopts a chemical precipitation method to prepare sea urchin-shaped neodymium-doped zinc oxide (ZNO for short), has simple operation process and controllable preparation process, can effectively eliminate fluorescence background and improve the SERS activity of ZnO, and has good application prospect.
An SERS substrate capable of naturally eliminating fluorescence background is made of echinoid neodymium-doped zinc oxide, and its chemical composition is ZnO and Nd2％(ii) a The shape is sea urchin shape, and the particle size is 2 mu m.
The preparation method comprises the following specific steps:
1) weighing the following raw materials in parts by weight:
2) respectively dissolving zinc nitrate hexahydrate and neodymium nitrate hexahydrate in 50mL of deionized water, and uniformly mixing by magnetic stirring for 20 minutes to prepare a mixed solution.
3) And dissolving ammonium bicarbonate in 50mL of deionized water to prepare a solution, pouring the solution into the mixed solution, and magnetically stirring for 4 hours to obtain a white precipitate.
4) And (3) respectively centrifugally washing the white precipitate by using deionized water and absolute ethyl alcohol, drying the collected precipitate in a drying oven at 80 ℃ for 12 hours, and finally collecting the obtained white powder.
5) And (3) placing the white powder into a quartz boat, placing the quartz boat in a tube furnace, sintering at 590-610 ℃ for 0.8-1.2 h, and naturally cooling to obtain the SERS substrate capable of naturally eliminating the fluorescence background.
The invention has the advantages and positive effects that:
1. according to the invention, the echinoid neodymium-doped zinc oxide (ZNO) is prepared by adopting a chemical precipitation method with a simple process, the SERS substrate can naturally eliminate a fluorescence background, effectively improves the specificity identification capability of the SERS substrate, integrates the elimination of the fluorescence background and the enhancement of SERS performance, and is a novel SERS substrate for quenching fluorescence-enhanced molecular fingerprint information (shown in attached figures 3 and 4).
2. The target product of the invention has good SERS activity, stability and repeatability (as shown in figures 5 and 6). To our knowledge, no relevant literature reports exist at present. The rare earth doped ZnO is used as the SERS substrate, a new direction is provided for the research of the SERS substrate, and the method has important scientific value and significance in both experimental range and practical application.
3. The target product ZNO is used as the SERS substrate, the synthesis process is safe, the advantages of environmental protection, economy, convenience, simple operation and the like are realized, the large-scale production is easy to realize, the biocompatibility is realized, and the target product ZNO is an ideal SERS substrate and can be applied to the aspects of chemistry, material science, biophysics and the like.
Drawings
FIG. 1 is a flow chart for preparing a target product ZNO.
FIG. 2 is a scanning electron micrograph of the target product ZNO of the present invention;
FIG. 3 is a transmission electron micrograph of the ZNO object of the invention.
FIG. 4 (a) is a SERS contrast diagram showing the excitation wavelength of 514nm after pure ZnO and the target product ZNO of the present invention adsorb 4-mercaptopyridine molecules; (b) the SERS contrast chart shows that after pure ZnO and a target product ZNO adsorb 4-mercaptopyridine molecules, the excitation wavelength is 633 nm.
FIG. 5 (a) is a SERS contrast diagram of methylene blue with excitation wavelength of 514nm after pure ZnO and ZNO of the target product of the present invention are adsorbed; (b) the method is an SERS contrast diagram of pure ZnO and a target product ZNO of the invention with an excitation wavelength of 514nm after adsorbing malachite green.
Fig. 6 is a graph comparing SERS measurements of a target product of the present invention and a target product of the present invention after 60 days immersion in absolute ethanol.
FIG. 7 (a) is a graph showing SERS signals measured at 20 randomly selected spots on the surface of a target product ZNO substrate adsorbed with 4-mercaptopyridine molecules of the present invention, and (b) is a graph showing that the measured SERS signals are 1024 cm-1A graph of Relative Standard Deviation (RSD) analysis of the peaks at (a); (c) is 1121 cm-1A graph of Relative Standard Deviation (RSD) analysis of the peaks at (a); (d) is 1596cm-1The peaks at (a) were plotted for Relative Standard Deviation (RSD) analysis.
Detailed Description
The raw materials required by the invention are as follows:
zinc nitrate (Zn (NO)3)2·6H2O, shenyang national medicine group chemical reagent limited) as analytical grade;
neodymium nitrate (Nd (NO)3)3·6H2O, shanghai mclin biochemistry science and technology limited) as analytical grade;
ammonium bicarbonate (NH)4HCO3Shenyang national drug group chemical reagent, Inc.) as analytical grade;
4-mercaptopyridine (4-MPy, Shanghai Weifang Fine chemical Co., Ltd.) was analytically pure;
absolute ethyl alcohol (CH)3CH2OH, Shenyang national drug group chemical reagent Co., Ltd.) was used as an analytical grade.
The preparation method comprises the following specific steps:
1) weighing the following raw materials in parts by weight:
2) respectively dissolving zinc nitrate hexahydrate and neodymium nitrate hexahydrate in 50mL of deionized water, and magnetically stirring for 20 minutes to prepare a mixed solution.
3) And dissolving ammonium bicarbonate in 50mL of deionized water to prepare a solution, pouring the solution into the mixed solution, and magnetically stirring for 4 hours to obtain a white precipitate.
4) And (3) respectively centrifugally washing the white precipitate by using deionized water and absolute ethyl alcohol, drying the collected precipitate in a drying oven at 80 ℃ for 12 hours, and finally collecting the obtained white powder.
5) And putting the white powder into a quartz boat, sintering for 1h at 600 ℃, and naturally cooling to obtain the sea urchin-shaped neodymium-doped zinc oxide of the target product.
6) Dissolving 4-mercaptopyridine in absolute ethyl alcohol, and carrying out ultrasonic treatment for 5 minutes to prepare 1 × 10-3And (3) soaking the prepared ZNO powder in the solution with the concentration of M, shaking in a constant-temperature culture oscillator for 12 hours, taking out, and centrifugally washing with absolute ethyl alcohol to obtain a sample to be detected.
As shown in FIGS. 2 and 3, the chemical composition of sea urchin-like neodymium-doped zinc oxide is ZnO Nd2％(ii) a The shape is sea urchin shape, and the particle size is 2 mu m.
In order to compare the elimination effect of the fluorescence background, the applicant tests the SERS spectra of pure ZnO and ZNO, for example, as shown in FIG. 4, the SERS spectra adsorbing 4-mercaptopyridine molecules under the excitation of different excitation wavelengths and the SERS spectra adsorbing different probe molecules (methylene blue and malachite green) in FIG. 5, the SERS spectra well prove that the target product of the invention can naturally eliminate the fluorescence background, enhance the SERS activity and effectively improve the novel SERS substrate of the specificity identification capability.
As shown in fig. 6, the target product of the present invention has a stability of at least 60 days in solution. In practical applications, the ability to process and store a SERS substrate in solution for such a long time is a very important factor for an ideal SERS substrate.
As shown in fig. 7, for 1024, 1121 and 1596cm-1The peak at (a) was analyzed for Relative Standard Deviation (RSD) to give RSD of 8.14, 7.87 and 8.29%, respectively.
Claims (1)
1. The application of the sea urchin-shaped neodymium-doped zinc oxide material as the SERS substrate capable of naturally eliminating the fluorescence background is characterized in that the sea urchin-shaped neodymium-doped zinc oxide material has the particle size of 2 mu m, and the specific application method is as follows:
1) weighing the following raw materials in parts by weight:
1.4577g of zinc nitrate hexahydrate
Neodymium nitrate hexahydrate 0.0438g
1.5812g ammonium bicarbonate
4-mercaptopyridine 0.0111g
100mL of absolute ethyl alcohol
2) Respectively dissolving zinc nitrate hexahydrate and neodymium nitrate hexahydrate in 50mL of deionized water, and stirring and mixing uniformly to prepare a mixed solution;
3) dissolving ammonium bicarbonate in 50mL of deionized water to prepare a solution, pouring the solution into the mixed solution, and magnetically stirring for 4 hours to obtain a white precipitate;
4) centrifugally washing the white precipitate by using deionized water and absolute ethyl alcohol respectively, drying the collected precipitate in a drying box at 80 ℃ for 12 hours, and finally collecting the obtained white powder;
5) putting the white powder into a quartz boat, placing the quartz boat in a tube furnace, setting the temperature at 600 ℃, sintering for 1h, and naturally cooling to obtain a sea urchin-shaped neodymium-doped zinc oxide material;
6) dissolving 4-mercaptopyridine in absolute ethyl alcohol, and carrying out ultrasonic treatment for 5 minutes to prepare 1 × 10-3And (3) soaking the sea urchin-shaped neodymium-doped zinc oxide material prepared in the step 5) in the solution with the concentration of M, shaking the sea urchin-shaped neodymium-doped zinc oxide material in a constant-temperature culture oscillator for 12 hours, taking out the sea urchin-shaped neodymium-doped zinc oxide material, and centrifugally washing the sea urchin-shaped neodymium-doped zinc oxide material with absolute ethyl alcohol to obtain a sample to be detected.
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| WO2005079247A2 (en) * | 2004-02-19 | 2005-09-01 | Nuskin International, Inc. | Synthetic calibration standard for photonic response of tissues |
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| US7075642B2 (en) * | 2003-02-24 | 2006-07-11 | Intel Corporation | Method, structure, and apparatus for Raman spectroscopy |
| BRPI0809138B8 (en) * | 2007-03-20 | 2021-07-27 | Becton Dickinson Co | method for detecting the presence or amount of one or more analytes in a biological sample |
| US20080239307A1 (en) * | 2007-03-30 | 2008-10-02 | The Regents Of The University Of California | Sequencing single molecules using surface-enhanced Raman scattering |
| US20150204790A1 (en) * | 2014-01-23 | 2015-07-23 | Canon Kabushiki Kaisha | Stimulated raman scattering measurement apparatus |
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| Hydroquinone Sensor Based on Neodymium (Nd) Doped ZnO Hexagonal Nanorods;Al-Hadeethi Yas et al.;《Nanoscience and Nanotechnology Letters》;20180331;第10卷(第3期);351-357 * |
| 钕、镧掺杂氧化锌薄膜的制备及形貌;文军;《河北师范大学学报／自然科学版》;20090930;第33卷(第5期);617-619 * |
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