CN112666149A - Rubber substrate paper-based SERS sensor based on gold and silver alloy nano-star - Google Patents
Rubber substrate paper-based SERS sensor based on gold and silver alloy nano-star Download PDFInfo
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- CN112666149A CN112666149A CN202011489478.7A CN202011489478A CN112666149A CN 112666149 A CN112666149 A CN 112666149A CN 202011489478 A CN202011489478 A CN 202011489478A CN 112666149 A CN112666149 A CN 112666149A
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Abstract
The invention provides a rubber substrate paper-based SERS sensor based on gold and silver alloy nano-star, which can be used for detecting trace substances. The waterproof paper base comprises a paper base, one surface of the paper base is compounded with a waterproof material, one surface of the paper base, which is not provided with the waterproof material, is printed with a template pattern, and blank areas in the template pattern are coated with gold-silver alloy nano-star particles. During detection, the solution of the substance to be detected is only required to be dripped or the powder is dipped, and laser Raman equipment is used for detection. The paper-based sensor has the advantages of simple structure, low cost, good reinforcing effect, convenience in long-term storage and transportation, and difficulty in damage, and is suitable for the field of trace monomolecular substance detection.
Description
Technical Field
The invention belongs to the technical field of nano-materials science and laser Raman detection, and particularly relates to a rubber substrate paper-based SERS (surface enhanced Raman scattering) sensor based on a gold-silver nano-star alloy.
Background
Surface Enhanced Raman Scattering (SERS) is a micro-analysis technique with extremely high sensitivity, and because the SERS technique greatly improves the raman spectrum detection sensitivity and detection range, and it is a rapid detection means without processing samples, it has wide application in the research fields of single molecule detection, food safety detection, biochemical analysis, medical detection, and art identification. The noble metals gold, silver, copper and alkali metal have stronger SERS effect, wherein the enhancement capability of silver is strongest, and gold and copper are second to each other. The preparation of the substrate is a prerequisite to obtain stable and uniform SERS signals, so that the preparation of uniform and stable SERS active substrates becomes a key point of current research.
There are three types of active substrates commonly used in current SERS assays: (1) a sol-type substrate. The sol-type substrate is a substrate widely applied in SERS research. Its preparation method can be divided into chemical reduction method and physical method. The chemical reduction method is mainly to reduce metal ions in a solution to obtain metal sol. The physical methods mainly comprise a laser etching method, a mechanical ball milling method, a ray irradiation method and the like. (2) A "hard" type substrate. From the discovery of the SERS effect, to date, such substrates have gradually become the mainstream substrate in SERS research. The method mainly comprises the steps of preparing and assembling a metal nano-structure substrate on the surfaces of a metal electrode, a silicon chip, a glass sheet, a polymer and the like through a physical or chemical method. The substrate prepared by the method is more complex and diversified in structure, so that the obtained substrate has more excellent SERS performance, and the SESR theoretical research and practical application are more convenient. (3) Flexible substrates, which are emerging and developing in recent years, are also favored by researchers. Such substrates often require other flexible substrate materials as supports, such as filter membranes, carbon nanotubes, graphene oxide, certain flexible polymers, and the like. The substrate can be used for testing a non-planar structure, is convenient to package and transport, and is a substrate material with excellent SERS performance.
Paper substrates have received much attention from researchers as a flexible, inexpensive and portable SERS substrate developed in recent years, but are susceptible to water-swelling and wrinkling of paper fibers when drop coated with a metal sol. In the invention, the flexible substrate SERS sensor based on the gold-silver alloy nano-star rubber substrate is provided, and the characteristics of easiness in damage and water-exposure wrinkling caused by the material of the paper substrate are overcome while the paper substrate SERS sensor with uniform coating and stable performance is prepared. The carbon powder is printed on the surface of the paper base according to the designed shape, so that the nano sol is limited in a specified small area, leakage is prevented, and the utilization rate of the gold-silver alloy nano star is improved; the use of the rubber bottom ensures that the nano particles and indicator molecules cannot seep out of a detection area, thereby being more convenient for the consistency of detection results and overcoming the defects that the paper base absorbs water, folds and is easy to damage; the gold-silver alloy nano star serving as the SERS enhancement particle has the stability of gold and strong SERS enhancement of silver, a sharp tip can limit and enhance a local electromagnetic field, so that a plurality of hot points are generated, a sharp point serves as a nano-scale antenna, high charge density and charge polarization are provided at a small-radius tip of the sharp point, and the local electromagnetic field is enhanced and excited. The alloy prepared by doping part of silver into gold improves the optical performance of the gold. In addition, nanoalloys exhibit better performance than the single metallic elements of their composition due to a bifunctional or synergistic effect resulting from intermetallic charge transfer.
Disclosure of Invention
The invention aims to provide a gold-silver alloy nano star-based rubber substrate paper-based SERS sensor, which has the advantages of firm combination of Raman active particles and a substrate, high particle utilization rate, low price and high consistency, and can be used for SERS detection.
The scheme adopted by the invention for solving the technical problems is as follows:
the rubber substrate paper-based SERS sensor based on the gold-silver alloy nano-star comprises a paper substrate, one surface of the paper substrate is compounded with a waterproof material, a template pattern is printed on the surface, without the waterproof material, of the paper substrate, and gold-silver alloy nano-star particles are coated on blank areas among the template patterns.
Preferably, the waterproof material is transparent adhesive tape; the template pattern is a carbon film.
Preferably, the gold-silver alloy nano-star particles are solid or hollow, and the solid or hollow gold-silver alloy nano-star particles can be prepared according to a method reported in the literature, such as a method for preparing hollow gold-silver nano-star alloy sol reported in the literature of Zhen Liu and the like. A preparation method of a solid gold-silver nano star alloy reported in Liang-Chien Cheng et al.
The invention also aims to provide a preparation method of the gold-silver alloy nano-star based rubber substrate paper-based SERS sensor, which comprises the following steps:
(1) printing a template: printing a pre-edited template pattern on a paper sheet on a printer, wherein printing raw materials use carbon powder;
(2) adhering a rubber bottom: sticking a transparent adhesive tape on the back of the paper sheet printed with the template pattern to obtain a paper base with the adhesive base;
(3) preparing gold-silver alloy nano-star particle sol: carrying out centrifugal washing on multi-sharp star-shaped gold-silver alloy nano particles, dispersing the multi-sharp star-shaped gold-silver alloy nano particles in an aqueous solution, and carrying out centrifugal concentration to prepare gold-silver alloy nano star particle sol;
(4) preparing an SERS sensor: and (3) dropwise adding the gold-silver alloy nano star particle sol prepared in the step (3) into the blank part in the glue base paper-based template pattern prepared in the step (2), drying after dropwise adding, and repeating for a plurality of times to obtain the SERS sensor.
Preferably, the paper sheet of step (1) comprises filter paper, standard printing paper, kraft paper.
Compared with the prior art, the invention has the advantages that:
1. the paper-based material is used as the flexible substrate, so that the manufacturing is simple, the price is low, and the packaging and the transportation are convenient.
2. The template pattern is printed by using carbon powder, a hydrophobic layer can be formed on the surface of the paper base, the nano particles can be effectively limited in a blank area, the leakage of the nano particles is avoided, and the SERS substrate with the uniform SERS enhanced particles is prepared.
3. Use the rubber bottom, avoid later stage indicator to follow the detection difference that the seepage of the different degree of bottom surface leads to, simultaneously, avoid the waste of SERS reinforcing particle.
4. The gold-silver alloy nano star has the stability of gold and the enhancement effect of partial silver. Because the sharp tip can limit and enhance the local electromagnetic field, the SERS enhancement effect of the gold-silver alloy particle is stronger than that of the common gold-silver alloy particle.
Drawings
FIG. 1 is a template pattern printed on a paper substrate;
FIG. 2 is a model of a rubber-based paper-based SERS sensor;
FIG. 3 is a Scanning Electron Microscope (SEM) image at 500 times magnification of the surface of the hollow gold-silver nano-star alloy substrate paper-based SERS sensor obtained in example 1, wherein the inset at the upper right corner is a Transmission Electron Microscope (TEM) image of the hollow gold-silver nano-star;
FIG. 4 is a SEM image of the surface of the solid gold-silver nano-star alloy substrate paper-based SERS sensor obtained in example 2 at 500 times magnification, wherein the insert at the upper right corner is a TEM image of the solid gold-silver nano-star;
FIG. 5 is an SERS spectrum of example 1, in which different layers of hollow gold-silver nano-star alloy are added dropwise and crystal violet is used as a probe molecule;
FIG. 6 is an SERS spectrum of example 2, in which different layers of solid gold-silver nano-star alloy are added dropwise and crystal violet is used as a probe molecule;
FIG. 7 is the SERS spectra of crystal violet of different concentrations measured by dropping 2 layers of hollow gold-silver nano-star alloy in example 1;
FIG. 8 is the SERS spectra of crystal violet measured at different concentrations by adding 5 layers of solid gold-silver nano-star alloy dropwise in example 2.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
Example 1
A preparation method of a rubber substrate paper-based SERS sensor based on hollow gold-silver nano-star alloy comprises the following three steps:
paper sheet pretreatment
a, printing a template: printing the A4 paper with a pre-edited template, and printing with carbon powder;
b, adhering a rubber bottom: and (5) sticking transparent adhesive on the back of the A4 paper printed with the template for standby.
(II) preparing hollow gold-silver nano star alloy sol:
a. and (3) silver seed synthesis: 9mg of silver nitrate was added to a 50ml Erlenmeyer flask and 50ml of deionized water was added. After the solution was boiled, 1.2ml of 1% sodium citrate was added. The mixture was boiled for 4min and the solution turned dark to dark yellow-gray. And cooling the solution to room temperature to obtain 20-30 nm silver particles. Meanwhile, the dark yellow gray solution gradually changed to a gray green color. The solution was collected and its volume was fixed at 50 ml.
b. In order to synthesize hollow gold-silver alloy nano star with the diameter less than 100nm, 2.4ml of HAuCl is added4The aqueous solution (10mM) was mixed with 4.3ml of deionized water in a 25ml glass vial. 3.0ml of seeds were added to the solution at room temperature, followed by 2.4ml of levodopa solution. After 1min, the rotation speed was slowed to 100rpm, and the clear yellow solution immediately turned opaque black-green with the addition of levodopa, followed by a dark black color.
c. Centrifuging the synthesized hollow gold-silver nano star alloy solution twice at 4000r/min, removing upper-layer liquid, respectively adding acetic acid, ammonia water and deionized water for washing, and finally concentrating the solution to prepare nano sol with the volume of 1 mL.
(III) preparing an SERS sensor:
dripping the gold-silver nano star alloy sol prepared in the step (II) into a blank part in the paper sheet obtained in the step (I), wherein the blank part is a circle with the diameter of 6mm, dripping 20 mu L of concentrated sol each time, drying, and dripping 2-10 layers to obtain a paper-based SERS sensor, and the figure is 3; the raman spectra of different layers are measured to obtain fig. 5, and comparing the raman spectra of different layers shows that 2 layers have the strongest raman signals, because the more layers the signals are scattered, the stronger the signal is, and the raman signal is weakened.
Selecting 2 layers as the number of the particle coating layers, then dropwise adding 100 mu L of crystal violet solutions with different concentrations to the paper-based SERS sensor, and testing to obtain a Raman spectrum, as shown in FIG. 7. Comparing the Raman characteristic peak of the crystal violet, the hollow gold and silver nano-scale can be seenThe limit concentration which can be measured by the paper-based SERS sensor with the star alloy as the nano particles is 10-6mol/L。
Example 2
A preparation method of a solid gold-silver nano-star alloy based rubber substrate paper-based SERS sensor comprises the following three steps:
paper sheet pretreatment
a. Printing a template: printing the A4 paper with a pre-edited template, and printing with carbon powder;
b. adhering a rubber bottom: and (5) sticking transparent adhesive on the back of the A4 paper printed with the template for standby.
(II) preparing a solid gold-silver nano star alloy:
a. stirring 10mL of deionized water, 240 mu L of 10mM chloroauric acid and 40 mu L of 10mM silver nitrate solution for three minutes, fully and uniformly mixing, adding 80 mu L of 100mM ascorbic acid, starting reaction, and stirring for two minutes;
b. and adding 0.005g of polyvinylpyrrolidone into the synthesized solid gold-silver nano star alloy solution, centrifuging twice at 4000r/min, and concentrating the solution to 1mL for later use.
(III) preparing an SERS sensor:
dropwise adding the gold-silver nano star alloy concentrated solution prepared in the step (II) into a blank part in the paper sheet in the step (I), wherein the blank part is a circle with the diameter of 6mm, dropwise adding 20 mu L of concentrated sol each time, drying, and dropwise adding 5-25 layers to obtain a paper-based SERS sensor, and the figure is 4; the raman spectra of different layers are measured to obtain fig. 6, and comparing the raman spectra of different layers shows that 5 layers have the strongest raman signals, because the more layers the signals are scattered, the stronger the signal is, and the raman signal is weakened.
Selecting 5 layers as the number of the particle coating layers, then dropwise adding 100 mu L of crystal violet solutions with different concentrations to the paper-based SERS sensor, and testing to obtain a Raman spectrum, as shown in FIG. 8. Comparing the Raman characteristic peak of the crystal violet, the limit concentration which can be measured by the paper-based SERS sensor taking the solid gold-silver nano-star alloy as the nano particles is 10-10mol/L。
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (5)
1. The rubber substrate paper-based SERS sensor based on the gold-silver alloy nano-star is characterized by comprising a paper substrate, one surface of the paper substrate is compounded with a waterproof material, one surface of the paper substrate, which is not provided with the waterproof material, is printed with a template pattern, and blank areas among the template pattern are coated with gold-silver alloy nano-star particles.
2. The gold-silver alloy nanostar-based rubber-based paper-based SERS sensor as claimed in claim 1, wherein the waterproof material is a transparent adhesive tape; the template pattern is a carbon film.
3. The gold-silver alloy nano-star-based rubber-based paper-based SERS sensor as claimed in claim 1, wherein the gold-silver alloy nano-star particles are solid or hollow.
4. A preparation method of a gold-silver alloy nano-star based rubber substrate SERS sensor is characterized by comprising the following steps:
(1) printing a template: printing a pre-edited template pattern on a paper sheet on a printer, wherein printing raw materials use carbon powder;
(2) adhering a rubber bottom: sticking a transparent adhesive tape on the back of the paper sheet printed with the template pattern to obtain a paper base with the adhesive base;
(3) preparing gold-silver alloy nano-star particle sol: carrying out centrifugal washing on multi-sharp star-shaped gold-silver alloy nano particles, dispersing the multi-sharp star-shaped gold-silver alloy nano particles in an aqueous solution, and carrying out centrifugal concentration to prepare gold-silver alloy nano star particle sol;
(4) preparing an SERS sensor: and (3) dropwise adding the gold-silver alloy nano star particle sol prepared in the step (3) into the blank part in the glue base paper-based template pattern prepared in the step (2), drying after dropwise adding, and repeating for a plurality of times to obtain the SERS sensor.
5. The method of claim 4, wherein the sheet of paper of step (1) comprises filter paper, standard printing paper, kraft paper.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113533301A (en) * | 2021-07-23 | 2021-10-22 | 江南大学 | A method for detecting organophosphorus using surface-enhanced Raman flexible substrates |
| CN115464134A (en) * | 2022-09-30 | 2022-12-13 | 南通大学 | A kind of gold-silver composite nano star and its preparation method and application |
| CN115876745A (en) * | 2022-11-30 | 2023-03-31 | 安徽中科赛飞尔科技有限公司 | Copovidone modified SERS substrate and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180080878A1 (en) * | 2015-06-02 | 2018-03-22 | University-Industry Cooperation Group Of Kyung Hee University | Paper-Based Surface-Enhanced Raman Scattering Substrate, and Preparation Method Therefor |
| CN109128152A (en) * | 2018-09-29 | 2019-01-04 | 南京农业大学 | A kind of high activity Venus@gold-silver alloy Raman substrate material and preparation method thereof |
| CN109900911A (en) * | 2019-03-11 | 2019-06-18 | 西安交通大学 | A method for detecting liver cancer tumor marker AFP using core-shell structured nanostars |
| CN110132940A (en) * | 2019-06-26 | 2019-08-16 | 重庆大学 | A kind of array type flexible SERS substrate and preparation method thereof |
| CN110441282A (en) * | 2019-07-19 | 2019-11-12 | 盐城工学院 | A kind of Pesticide Residues in Tea detection method based on Surface enhanced Raman spectroscopy and papery micro-fluidic chip |
| CN111299570A (en) * | 2020-03-20 | 2020-06-19 | 中国科学院合肥物质科学研究院 | A LSPR-tunable gold@silver core-shell nanostar and its preparation method |
-
2020
- 2020-12-16 CN CN202011489478.7A patent/CN112666149A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180080878A1 (en) * | 2015-06-02 | 2018-03-22 | University-Industry Cooperation Group Of Kyung Hee University | Paper-Based Surface-Enhanced Raman Scattering Substrate, and Preparation Method Therefor |
| CN109128152A (en) * | 2018-09-29 | 2019-01-04 | 南京农业大学 | A kind of high activity Venus@gold-silver alloy Raman substrate material and preparation method thereof |
| CN109900911A (en) * | 2019-03-11 | 2019-06-18 | 西安交通大学 | A method for detecting liver cancer tumor marker AFP using core-shell structured nanostars |
| CN110132940A (en) * | 2019-06-26 | 2019-08-16 | 重庆大学 | A kind of array type flexible SERS substrate and preparation method thereof |
| CN110441282A (en) * | 2019-07-19 | 2019-11-12 | 盐城工学院 | A kind of Pesticide Residues in Tea detection method based on Surface enhanced Raman spectroscopy and papery micro-fluidic chip |
| CN111299570A (en) * | 2020-03-20 | 2020-06-19 | 中国科学院合肥物质科学研究院 | A LSPR-tunable gold@silver core-shell nanostar and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| ZHEN LIU ETAL: "Highly Sensitive, Uniform, and Reproducible Surface-Enhanced Raman Spectroscopy from Hollow Au-Ag Alloy Nanourchins", ADV. MATER, vol. 26, 30 April 2014 (2014-04-30), pages 2431 - 2432 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113533301A (en) * | 2021-07-23 | 2021-10-22 | 江南大学 | A method for detecting organophosphorus using surface-enhanced Raman flexible substrates |
| CN115464134A (en) * | 2022-09-30 | 2022-12-13 | 南通大学 | A kind of gold-silver composite nano star and its preparation method and application |
| CN115876745A (en) * | 2022-11-30 | 2023-03-31 | 安徽中科赛飞尔科技有限公司 | Copovidone modified SERS substrate and preparation method and application thereof |
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