CN115753731B - Flexible wearable glove-based SERS substrate, preparation method and application thereof - Google Patents
Flexible wearable glove-based SERS substrate, preparation method and application thereof Download PDFInfo
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Abstract
A flexible wearable glove-based SERS substrate, a preparation method and application thereof in detection of controlled drugs and drugs belong to the technical field of biosensing detection. According to the invention, a liquid-liquid interface self-assembly technology is utilized to assemble the gold trioctahedron on the adhesive tape, and then the gold trioctahedron and the wearable glove are integrated together to obtain the flexible adhesive tape substrate; and then uniformly and compactly adhering polystyrene microsphere protein Dan Guangzi crystals on the flexible adhesive tape substrate, and secondarily enhancing a Raman signal, thereby obtaining the flexible wearable glove-based SERS substrate. The invention uses the application of improving SERS field portable analysis as an access point, utilizes the capability of the flexible adhesive tape substrate to efficiently draw a sample, combines uniform and compact polystyrene microsphere Dan Guangzi crystals, solves the problems of difficult sample extraction, low sensitivity, poor detection repeatability and the like of the existing general planar rigid substrate field, and prepares the wearable and high-sensitivity glove-based SERS substrate.
Description
Technical Field
The invention belongs to the technical field of biosensing detection, and particularly relates to a flexible wearable glove-based SERS substrate, a preparation method and application thereof in detection of controlled drugs and drugs.
Background
In recent years, efficient integration of SERS substrates with wearable platforms has attracted interest to many researchers, including in situ biological fluid detection, in situ pesticide residue analysis, wearable anti-counterfeit identification, and the like. For example, epidermal microfluidic and glove-based sensing platforms have demonstrated that wearable biotechnology can continuously detect electrolytes and organophosphates, explosives, and the like. Bringing laboratory-based analytical equipment directly to the body of the inspector provides great convenience for target identification in point of care testing (POCT) applications.
There are two important factors to consider for a SERS detection platform fabricated using a plasmonic nanostructure: (1) A flexible substrate convenient for sampling, thereby improving the sampling efficiency; (2) And strong local surface plasmon resonance is formed, so that the detection sensitivity is improved. Currently, a number of flexible materials have been developed for preparing SERS substrates, such as polymers, paper, carbon fibers, and the like. However, most of these materials require complex surface modification techniques and SERS analysis is made difficult by optical opacity. In this case, it is a good choice to prepare the SERS sensor with the tape as a supporting substrate. The adhesive tape is a low-cost, flexible and adhesive backing material that can be integrated with a variety of sensing elements without creating background interference. In addition, researchers have made much work on how to improve SERS detection sensitivity, such as preparing multi-tipped abnormal nanoparticles, constructing three-dimensional high-density electromagnetic hot spots, and the like. The photonic crystal is a periodic dielectric structure with photonic band gap characteristics, and through the interaction of the photonic crystal and a plasma material, an enhanced electromagnetic field can be generated in a larger volume, so that the SERS performance is further enhanced.
Therefore, to enhance applications of SERS substrate-based field-portable analysis, it is important to combine photonic crystal-plasma hybrid resonance with flexible wearable substrates to design flexible wearable SERS substrates with high sensitivity, high reproducibility.
Disclosure of Invention
The invention aims to solve the problems of difficult sampling, low sensitivity and the like in a complex environment, and provides a flexible wearable glove-based SERS substrate, a preparation method and application thereof in detection of controlled drugs (tramadol, midazolam or paracetamol and the like) and drugs (methamphetamine and the like).
A flexible wearable glove-based SERS substrate, characterized by: the gold trioctahedron is assembled on an adhesive tape by utilizing a liquid-liquid interface self-assembly technology, and then is integrated with a wearable glove to obtain a flexible adhesive tape substrate; and then uniformly and compactly adhering polystyrene microsphere protein Dan Guangzi crystals on the flexible adhesive tape substrate, and secondarily enhancing a Raman signal, thereby obtaining the flexible wearable glove-based SERS substrate.
The gold trioctahedral is marked as Au TOH; the solutions according to the invention are all aqueous solutions, unless otherwise specified.
The invention relates to a preparation method of a flexible wearable glove-based SERS substrate, which comprises the following steps:
(1) Preparing Au TOH by using a seed growth method: mixing 2-2.5 mL of 0.1M hexadecyl trimethyl ammonium chloride (CTAC) solution with 5-20 mu L of 9-12 nm gold nanosphere seed solution, then adding 130-150 mu L of 0.1M Ascorbic Acid (AA) solution, adding 2-2.5 mL of 0.5 multiplied by 10 -3M HAuCl4 solution after the reactant is completely dissolved, reacting for 15-20 min at 25-30 ℃, centrifuging at 5500-6500 rpm for 10-15 min, dispersing the obtained precipitate into 0.5-1 mL of ethanol solution with mass fraction of 1% polyvinylpyrrolidone (PVP), centrifuging at 5500-6000 rpm for 10-15 min, dispersing the obtained precipitate into 0.5-1 mL of ethanol to obtain Au TOH ethanol solution, and preserving at 4 ℃;
(2) Preparing a flexible adhesive tape substrate: mixing 100-300 mu L of the Au TOH ethanol solution prepared in the step (1) with 1.5-2.5 mL of dichloromethane, adding 3.5-4.5 mL of ultrapure water, and shaking vigorously for 30-50 seconds; then slowly adding 700-900 mu L of normal hexane, forming a layer of uniform gold nanoparticle film at the liquid-liquid interface, slowly removing normal hexane, then fishing out one layer of gold nanoparticles by using an adhesive tape, then fishing out a second layer of gold nanoparticles by using the adhesive tape after waiting for the adhesive tape to be dried, and so on, so that the assembly of 1-3 layers of gold nanoparticles can be realized to obtain a flexible adhesive tape substrate;
(3) Preparation of polystyrene microglobulin Dan Guangzi crystals: polystyrene microsphere solution with the size of 300-500 nm (the concentration is 2.5% w/v) is centrifuged for 15-20 minutes at the rotating speed of 6500-7500 rpm, and then the polystyrene microsphere solution is redispersed in the volume ratio of 1:1 in a mixed solution of water and ethanol; then placing the hydrophilically treated glass slide in a culture dish at an angle of 15-45 degrees, filling water in the culture dish, and slowly dripping 3-8 mu L of polystyrene microsphere dispersion liquid on the glass slide by using a liquid transfer device; adding the next drop after the previous drop of microsphere solution is completely diffused until the whole water/air interface is covered by a color grating caused by diffraction of the polystyrene microsphere nanostructure array; finally, slowly fishing out the nanostructure array by using a hydrophilically treated silicon wafer, slightly pressing the nanostructure array for 3-10 seconds by using another transparent adhesive tape, and then stripping the nanostructure array from the silicon wafer, thereby obtaining ordered polystyrene microglobulin Dan Guangzi crystals on the transparent adhesive tape;
(4) Preparation of glove-based SERS substrate and SERS test
Centrifuging fresh human blood at 3000-4000 rpm for 10-15 min to obtain serum, and diluting with water to 10% (volume ratio) to obtain serum solution; preparing tramadol and midazolam sample solutions with different concentrations by using the serum solution to obtain a liquid sample; two powder samples of methamphetamine and paracetamol are mixed according to a volume ratio of 1:1, uniformly mixing to obtain a solid sample;
Fixing the flexible adhesive tape substrate obtained in the step (2) on fingertips of wearable gloves, extracting samples to be detected with different concentrations by simple wiping, adhering polystyrene microsphere protein Dan Guangzi crystals on the flexible adhesive tape substrate after the samples to be detected are extracted to construct a glove-based SERS substrate, and carrying out SERS test to obtain SERS spectra, so that qualitative and quantitative analysis of the samples is realized.
Further, 2 to 2.5mL of 200 multiplied by 10 -3 M cetyltrimethylammonium chloride (CTAC) solution is mixed with 40 to 60 mu L of cetyltrimethylammonium bromide (CTAB) coated gold nanocluster solution, then 1.5 to 3mL of 0.1M ascorbic acid solution is added, after the reactants are completely dissolved, 2 to 2.5mL of 0.5X10 -3M HAuCl4 solution is added, the mixture is reacted for 15 to 20 minutes at 25 to 30 ℃, and then the mixture is centrifuged for 20 to 40 minutes at 14000 to 15500rpm and resuspended in 1 to 2mL of 20 multiplied by 10 -3 M CTAC solution, thus obtaining gold nanosphere seed solution;
Further, 0.3 to 0.4g of cetyltrimethylammonium bromide is weighed and dissolved in 4 to 6mL of water, and the mixture is slightly stirred at the temperature of between 25 and 30 ℃; 4-6 mL of 0.5mM HAuCl 4 solution is added into the solution, then 0.5-0.8 mL of 10 multiplied by 10 -3M NaBH4 solution is rapidly added at 500-900 rpm, the solution is vigorously stirred for 1.5-3.0 min, and the solution is placed at 25-30 ℃ for 2-5 h to ensure that the reaction is complete, thus obtaining the gold nanocluster solution coated with CTAB.
The principle of the invention is as follows: the invention uses the application of improving SERS field portable analysis as an access point, utilizes the capability of the flexible adhesive tape substrate to efficiently draw a sample, combines uniform and compact polystyrene microglobulin Dan Guangzi crystals, and secondarily enhances a Raman signal, so as to solve the problems of difficult sample extraction, low sensitivity, poor detection repeatability and the like of the existing general planar rigid substrate field, and prepare the wearable and high-sensitivity glove-based SERS substrate. The invention has the beneficial effects that:
(1) The granularity of the prepared gold trioctahedron can reach the nanometer level, the average size can reach about 73nm, and the particle size distribution is uniform;
(2) Regular hot spots are arranged between the gold trioctahedrons assembled on the flexible adhesive tape, so that the sensitivity of SERS detection can be remarkably enhanced, the optimal assembly layer number is 2 (2 layers can be realized by fishing out one layer of gold nanoparticles by using a 3M adhesive tape, then fishing out a second layer of gold nanoparticles by using the adhesive tape after the adhesive tape is dried in the air;
(3) The golden trioctahedral assembled on the flexible adhesive tape is tightly arranged and uniformly distributed, so that the detection uniformity can be effectively improved, and the relative standard Deviation (RELATIVE STANDARD detection) of 50 times of random detection on the same glove-based SERS substrate can be controlled to be about 5.08%;
(4) The prepared adhesive tape substrate has good flexibility, the repeatability of the chiral base SERS substrate cannot be obviously affected by bending and stretching of different degrees, and the RSD after bending and stretching is less than 6%;
(5) The obtained glove-based SERS substrate is more convenient for drawing a sample and cannot cause background interference on a detection result;
(6) The repeatability of SERS trace detection is high, and the change rate of the detection limit is not more than 5% by repeating the results obtained by two experiments.
The invention can directly assemble compact and uniform gold nano particles on the adhesive tape by utilizing the liquid-liquid interface self-assembly technology, effectively improves the repeatability of signals, and has the optimal assembly layer number of 2 layers. More importantly, the introduction of the polystyrene microsphere opal photonic crystal can further enhance the Raman signal, and meanwhile, the glove-based SERS substrate is more convenient for drawing a sample and is not easy to pollute, so that the sensitivity of SERS detection is further improved.
Drawings
FIG. 1 is a transmission electron microscope image of Au TOH obtained in example 1 of the present invention; as shown in FIG. 1, au TOH was shown to be of a trioctahedral structure with an average particle size of about 73nm.
FIG. 2 is a scanning electron microscope image of the adhesive tape substrate obtained in example 2 of the present invention; as shown in fig. 2, the tape was uniformly covered with 2 layers of Au TOH.
FIG. 3 is a scanning electron microscope image of the polystyrene microsphere opal photonic crystal obtained in example 3 of the present invention; as shown in FIG. 3, the polystyrene microspheres are arranged in a regular and compact manner without stacking or void generation.
FIG. 4 is a SERS spectrum of the glove-based SERS substrate of example 4 of the present invention for detecting tramadol (a) and midazolam (b) in serum with detection limits as low as 69.19ng mL -1 and 35.03ng mL -1, respectively (detection limits are calculated according to the formula specified by the International Association of theory and applied chemistry (IUPAC): LOD=kS b/m, where S b is the standard deviation of the blank multiple measurements; m is the slope of the analytical calibration curve in the low concentration range; k is 3).
Fig. 5 is a SERS spectrum chart of a glove-based SERS substrate obtained in example 4 of the present invention for randomly detecting a mixed sample of 10-methamphetamine and paracetamol, and the raman characteristic peaks of each of methamphetamine and paracetamol can be clearly seen.
Detailed Description
Example 1: preparation of gold trioctahedral (Au TOH)
(1) Preparation of 3nm gold nanocluster solution:
0.365g of cetyltrimethylammonium bromide (CTAB) was weighed out in 5mL of water and stirred slightly at 27 ℃. 5mL of 0.5mM chloroauric acid solution (HAuCl 4) was added to the above solution, followed by rapid addition of 0.6mL of 10X 10 - 3 M sodium borohydride solution (NaBH 4) at 600rpm, stirring for 2 minutes, and standing at 27℃for 3 hours to ensure completion of the reaction, resulting in a CTAB-coated gold nanocluster solution.
(2) Preparation of a 10nm gold nanosphere seed solution:
2mL of 200×10 -3 M cetyltrimethylammonium chloride solution (CTAC) was mixed with 50. Mu.L of the CTAB coated gold nanocluster solution obtained in the step (1), then 1.5mL of 0.1M ascorbic acid solution (AA) was added, after the reactants were completely dissolved, 2mL of 0.5×10 -3M HAuCl4 solution was added, and reacted at 27℃for 15 minutes, and then centrifuged at 14500rpm for 30 minutes to re-suspend in 1mL of 20×10 -3 M CTAC solution, thereby obtaining a gold nanosphere seed solution having a particle size of 10 nm.
(3) Preparation of 75nm Au TOH:
Mixing 2mL of 0.1M CTAC solution with 5 mu L of the 10nm gold nanosphere seed solution obtained in the step (2), adding 130 mu L of 0.1M AA solution, adding 2mL of 0.5X 10 -3M HAuCl4 solution after the reactant is completely dissolved, reacting for 15min at 27 ℃ and centrifuging at 6000rpm for 15min, dispersing the precipitate into 0.5mL of ethanol solution of polyvinylpyrrolidone (PVP) with the mass fraction of 1%, centrifuging at 6000rpm for 15min, dispersing the obtained precipitate into 0.5mL of ethanol again to obtain Au TOH ethanol solution, and storing at 4 ℃.
Example 2: preparation of tape substrate
200. Mu.L of the Au TOH ethanol solution prepared in example 1 was mixed with 2mL of methylene chloride, followed by addition of 4mL of ultrapure water and vigorous shaking for 35 seconds; then adding 800 mu L of normal hexane slowly, forming a layer of uniform gold nanoparticle film at the liquid-liquid interface, slowly removing the normal hexane, then fishing out one layer of gold nanoparticles by using a 3M adhesive tape, and then fishing out a second layer of gold nanoparticles by using the 3M adhesive tape after waiting for the 3M adhesive tape to air, thereby realizing the assembly of 2 layers of gold nanoparticles and obtaining the flexible adhesive tape substrate.
Example 3: preparation of polystyrene microsphere opal photonic crystal
A300 nm size solution of polystyrene microspheres (concentration 2.5% w/v) was centrifuged at 7000rpm for 15 minutes and dispersed in a mixed solution of water and ethanol (volume ratio 1:1). Then, the hydrophilically treated slide glass was placed in a petri dish at an angle of 25℃and 5. Mu.L of a polystyrene microsphere dispersion was slowly dropped onto the slide glass with a pipette. After the previous drop of microsphere solution is completely diffused into the water/air interface, the next drop is added until the whole interface is covered by the color grating caused by diffraction of the polystyrene microsphere nano-structure array. And finally, slowly fishing out the nanostructure array by using a hydrophilically treated silicon wafer, slightly pressing the nanostructure array for 5 seconds by using another transparent adhesive tape, and then stripping the nanostructure array from the silicon wafer, thereby obtaining the ordered polystyrene microsphere protein Dan Guangzi crystals on the transparent adhesive tape.
Example 4: preparation and detection of glove-based SERS substrates
(1) Preparation of tramadol and midazolam serum samples:
Centrifuging human fresh blood at 3000rpm for 10 min to obtain serum, and diluting with water to 10% (volume ratio) to obtain serum solution; tramadol hydrochloride injection (50 mg/mL) was diluted with this serum solution to different concentrations (20. Mu.g/mL, 10. Mu.g/mL, 5. Mu.g/mL, 2. Mu.g/mL, 1. Mu.g/mL, 500ng/mL, 200 ng/mL) to prepare tramadol serum sample 1 of different concentrations.
Serum sample 2 of midazolam was prepared at different concentrations according to the same method.
(2) Preparation of a mixed sample of methamphetamine and oxycodone:
Solid mixing sample two solid powder samples were directly mixed according to a volume ratio of 1:1, uniformly mixing.
(3) Preparation of glove-based SERS substrates:
The flexible adhesive tape substrate obtained in example 2 was fixed on the fingertip of a wearable glove, tramadol serum sample 1, midazolam serum sample 2 and solid powder mixed sample 3 of different concentrations were extracted by simple wiping, then the polystyrene microsphere protein Dan Guangzi crystal obtained in example 3 was adhered on the flexible adhesive tape substrate after the sample to be measured was extracted to construct a glove-based SERS substrate, SERS detection was performed (each sample was measured 5 times and then averaged) using 785nm laser to obtain SERS spectra, and the results are shown in fig. 4 and 5, respectively.
It can be observed in the spectrum of fig. 4 that the raman characteristic peaks of tramadol are mainly located at 712cm -1 and 995cm -1 and that of midazolam are mainly located at 688cm -1、827cm-1 and 1033cm -1. As expected, as the analyte concentration increases, the raman signal intensity also increases. The concentrations of tramadol and midazolam samples were monitored indirectly using the intensities of the characteristic peaks at 995cm -1 and 688cm -1 (as the sample concentration increases, the intensity of the characteristic peak increases, so a "characteristic peak intensity (tramadol is the characteristic peak at 995cm -1 position, midazolam is the characteristic peak at 688cm -1 position) -analyte concentration" relationship curve was established, and then the detection limit was calculated according to the formula prescribed by the international union of theory and applied chemistry (IUPAC): LOD lod=ks b/m, where S b is the standard deviation of the blank multiple measurements; m is the slope of the analytical calibration curve in the low concentration range; k is 3), and the detection limit can be as low as 69.19ng mL -1 and 35.03ng mL -1, respectively.
Fig. 5 shows 10 random SERS tests on mixed samples, in which the raman characteristic peaks of methamphetamine and paracetamol are clearly seen, with the characteristic peaks at 1002cm -1、1030cm-1 and 1204cm -1 being methamphetamine and the remainder paracetamol. It is noted that when signals of different positions of the mixed sample are collected (the mixed sample is a powder sample, and laser is focused to different positions of the sample for random detection during detection), the intensities of characteristic peaks of the two samples are different, but the characteristic peaks of the two samples are displayed, so that the substrate has good sensitivity and discrimination capability, and the practical application possibility is provided for sensitive and portable drug trace detection.
Claims (7)
1. A preparation method of a flexible wearable glove-based SERS substrate comprises the following steps:
(1) Preparing Au TOH by using a seed growth method: mixing 2-2.5 mL of 0.1M cetyltrimethylammonium chloride solution with 5-20 mu L of 9-12 nm gold nanosphere seed solution, then adding 130-150 mu L of 0.1M ascorbic acid solution, adding 2-2.5 mL of 0.5X10 -3M HAuCl4 solution after the reactant is completely dissolved, reacting for 15-20 min at 25-30 ℃, centrifuging for 10-15 min at 5500-6500 rpm, dispersing the obtained precipitate into 0.5-1 mL of ethanol solution of polyvinylpyrrolidone with mass fraction of 1%, centrifuging for 10-15 min at 5500-6000 rpm, dispersing the obtained precipitate into 0.5-1 mL of ethanol to obtain Au TOH ethanol solution, and preserving at 4 ℃;
(2) Preparing a flexible adhesive tape substrate: mixing 100-300 mu L of the Au TOH ethanol solution prepared in the step (1) with 1.5-2.5 mL of dichloromethane, adding 3.5-4.5 mL of ultrapure water, and shaking vigorously for 30-50 seconds; then slowly adding 700-900 mu L of normal hexane, forming a layer of uniform gold nanoparticle film at the liquid-liquid interface, slowly removing normal hexane, then fishing out one layer of gold nanoparticles by using an adhesive tape, then fishing out a second layer of gold nanoparticles by using the adhesive tape after waiting for the adhesive tape to be dried, and so on, so that the assembly of 1-3 layers of gold nanoparticles can be realized to obtain a flexible adhesive tape substrate;
(3) Preparation of polystyrene microglobulin Dan Guangzi crystals: polystyrene microsphere solution with the size of 300-500 nm and the concentration of 2.5% w/v is centrifuged for 15-20 minutes at the rotating speed of 6500-7500 rpm, and then the polystyrene microsphere solution is redispersed in the volume ratio of 1:1 in a mixed solution of water and ethanol; then placing the hydrophilically treated glass slide in a culture dish at an angle of 15-45 degrees, filling water in the culture dish, and slowly dripping 3-8 mu L of polystyrene microsphere dispersion liquid on the glass slide by using a liquid transfer device; adding the next drop after the previous drop of microsphere solution is completely diffused until the whole water/air interface is covered by a color grating caused by diffraction of the polystyrene microsphere nanostructure array; finally, slowly fishing out the nanostructure array by using a hydrophilically treated silicon wafer, slightly pressing the nanostructure array for 3-10 seconds by using another transparent adhesive tape, and then stripping the nanostructure array from the silicon wafer, thereby obtaining ordered polystyrene microglobulin Dan Guangzi crystals on the transparent adhesive tape;
(4) Preparation of glove-based SERS substrate and SERS test
Fixing the flexible adhesive tape substrate obtained in the step (2) on fingertips of wearable gloves, extracting samples to be detected with different concentrations by simple wiping, adhering polystyrene microsphere protein Dan Guangzi crystals on the flexible adhesive tape substrate after the samples to be detected are extracted to construct a glove-based SERS substrate, and carrying out SERS test to obtain SERS spectra, so that qualitative and quantitative analysis of the samples is realized.
2. A method of making a flexible wearable glove-based SERS substrate of claim 1, wherein: mixing 2-2.5 mL of 200X 10 -3 M cetyltrimethylammonium chloride solution with 40-60 mu L of cetyltrimethylammonium bromide coated gold nanocluster solution, then adding 1.5-3 mL of 0.1M ascorbic acid solution, adding 2-2.5 mL of 0.5X 10 -3M HAuCl4 solution after the reactants are completely dissolved, reacting for 15-20 minutes at 25-30 ℃, and then centrifuging for 20-40 minutes at 14000-15500 rpm, and re-suspending in 1-2 mL of 20X 10 -3 M CTAC solution to obtain gold nanosphere seed solution.
3. A method of making a flexible wearable glove-based SERS substrate of claim 2, wherein: 0.3 to 0.4g of hexadecyl trimethyl ammonium bromide is weighed and dissolved in 4 to 6mL of water, and the mixture is slightly stirred at the temperature of between 25 and 30 ℃; 4-6 mL of 0.5mM HAuCl 4 solution is added into the solution, then 0.5-0.8 mL of 10 multiplied by 10 -3M NaBH4 solution is rapidly added at 500-900 rpm, the solution is vigorously stirred for 1.5-3.0 min, and the solution is placed at 25-30 ℃ for 2-5 h to ensure that the reaction is complete, thus obtaining the hexadecyl trimethyl ammonium bromide coated gold nanocluster solution.
4. A method of making a flexible wearable glove-based SERS substrate of claim 1, wherein: the method comprises the steps of centrifuging fresh human blood at a rotating speed of 3000-4000 rpm for 10-15 minutes to obtain serum, and diluting the serum with water to a volume ratio of 10% to obtain a serum solution; preparing tramadol and midazolam sample solutions with different concentrations by using the serum solution to obtain a liquid sample; two powder samples of methamphetamine and paracetamol are mixed according to a volume ratio of 1:1, uniformly mixing to obtain a solid sample; liquid samples and solid samples were used as samples to be tested.
5. A flexible wearable glove-based SERS substrate, characterized by: is prepared by the method of any one of claims 1 to 4.
6. Use of a flexible wearable glove-based SERS substrate as claimed in claim 5 in the detection of controlled drugs or drugs.
7. The use of a flexible wearable glove-based SERS substrate in the detection of controlled drugs or drugs according to claim 6, wherein: the controlled drug is tramadol, midazolam or paracetamol, and the drug is methamphetamine.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010014045A1 (en) * | 2008-08-01 | 2010-02-04 | Agency For Science, Technology And Research | Method of modifying a substrate for deposition of charged particles thereon |
| CN103641059A (en) * | 2013-12-30 | 2014-03-19 | 中国人民解放军国防科学技术大学 | Silicon-pillared metal film nano-structure array and preparation method thereof |
| CN109030453A (en) * | 2018-07-04 | 2018-12-18 | 浙江工业大学 | A kind of preparation method and application of flexible and transparent SERS substrate |
| CN113125409A (en) * | 2021-03-25 | 2021-07-16 | 云南省烟草质量监督检测站 | Method for rapidly detecting butralin in tobacco by surface enhanced Raman scattering |
| WO2022006520A1 (en) * | 2020-07-02 | 2022-01-06 | Carnegie Mellon University | Electrochemical biosensors for rapid and sensitive detection of pathogens and pathogenic biomarkers |
| CN114034682A (en) * | 2021-11-10 | 2022-02-11 | 山东省科学院新材料研究所 | Preparation method and application of ultrathin skin/glove-based wearable SERS sensor |
| CN114577778A (en) * | 2022-03-02 | 2022-06-03 | 中国科学院合肥物质科学研究院 | Preparation method of self-assembled flexible SERS substrate and application of self-assembled flexible SERS substrate in pesticide residue detection |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2913428A1 (en) * | 2014-12-03 | 2016-06-03 | Bubble Technology Industries Inc. | System and method for detection of contaminants |
| US9876183B2 (en) * | 2015-01-30 | 2018-01-23 | Northwestern University | Charge-transporting metal oxide-polymer blend thin films |
-
2022
- 2022-11-21 CN CN202211453704.5A patent/CN115753731B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010014045A1 (en) * | 2008-08-01 | 2010-02-04 | Agency For Science, Technology And Research | Method of modifying a substrate for deposition of charged particles thereon |
| CN103641059A (en) * | 2013-12-30 | 2014-03-19 | 中国人民解放军国防科学技术大学 | Silicon-pillared metal film nano-structure array and preparation method thereof |
| CN109030453A (en) * | 2018-07-04 | 2018-12-18 | 浙江工业大学 | A kind of preparation method and application of flexible and transparent SERS substrate |
| WO2022006520A1 (en) * | 2020-07-02 | 2022-01-06 | Carnegie Mellon University | Electrochemical biosensors for rapid and sensitive detection of pathogens and pathogenic biomarkers |
| CN113125409A (en) * | 2021-03-25 | 2021-07-16 | 云南省烟草质量监督检测站 | Method for rapidly detecting butralin in tobacco by surface enhanced Raman scattering |
| CN114034682A (en) * | 2021-11-10 | 2022-02-11 | 山东省科学院新材料研究所 | Preparation method and application of ultrathin skin/glove-based wearable SERS sensor |
| CN114577778A (en) * | 2022-03-02 | 2022-06-03 | 中国科学院合肥物质科学研究院 | Preparation method of self-assembled flexible SERS substrate and application of self-assembled flexible SERS substrate in pesticide residue detection |
Non-Patent Citations (5)
| Title |
|---|
| "Flexible and wearable glove-based SERS sensor for rapid sampling and sensitive detection of controlled drugs";Meiling Zhanga, et al;Sensors and Actuators: B. Chemical;20230328;第386卷;全文 * |
| Abbas Barfidokht， et al."Wearable electrochemical glove-based sensor for rapid and on-site detection of fentanyl ".Sensors and Actuators, B. Chemical.第296卷全文. * |
| 胶带快速转移水油液液界面自组装纳米金制备透明柔性SERS基底;章裕超;滕渊洁;施倩玮;刘文涵;;光谱学与光谱分析;20181015(第S1期);全文 * |
| 表面增强拉曼光谱技术在食品安全检测中的应用;梁营芳;周化岚;王燕;王锋;;理化检验(化学分册);20200418(第04期);全文 * |
| 金纳米颗粒的可控制备及其光学性能研究;叶天宇;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20180115;全文 * |
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