CN115753731A - 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. The method utilizes a liquid-liquid interface self-assembly technology to assemble the gold trioctahedron on the adhesive tape, and then integrates the gold trioctahedron and the wearable glove together to obtain a flexible adhesive tape substrate; then adhering uniform and compact polystyrene microsphere opal photonic crystals on the flexible adhesive tape substrate, and secondarily enhancing Raman signals to obtain the flexible wearable glove-based SERS substrate. The wearable glove-based SERS substrate with high sensitivity is prepared by taking the application of improving portable SERS field analysis as an entry point, utilizing the capability of efficiently absorbing a sample by using a flexible adhesive tape substrate and combining uniform and compact polystyrene microsphere opal photonic crystals to solve the problems of difficulty in field sample extraction, low sensitivity, poor detection repeatability and the like of a plane rigid substrate commonly adopted at present.
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, the effective integration of SERS substrates with wearable platforms has attracted the interest of many researchers, including in situ biological fluid detection, in situ pesticide residue analysis, wearable anti-counterfeiting identification, and the like. For example, epidermal microfluidics 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 test person provides great convenience for target identification in point-of-care testing (POCT) applications.
The SERS detection platform prepared by utilizing the plasma nano structure has two important factors which need to be considered: (1) The flexible substrate is convenient for sampling, so that the sampling efficiency is improved; (2) Strong local surface plasma resonance is formed, and the detection sensitivity is further improved. Currently, many flexible materials have been developed for preparing SERS substrates, such as polymers, paper, and carbon fibers. However, most of these materials require complicated surface modification techniques and SERS analysis becomes difficult due to optical opacity. In this case, it is a good choice to use the tape as a supporting substrate to prepare the SERS sensor. The adhesive tape is a low-cost substrate material with flexibility and adhesiveness, can be integrated with various sensing elements, and does not generate background interference. In addition, researchers also do much work on how to improve the sensitivity of SERS detection, such as preparing multi-tip heterotype 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 an enhanced electromagnetic field can be generated in a larger volume through the interaction between the photonic crystal and a plasma material, so that the SERS performance is further enhanced.
Therefore, in order to enhance the application of field portable analysis based on the SERS substrate, the photonic crystal-plasma hybrid resonance and the flexible wearable substrate are combined, and it is important to design a flexible wearable SERS substrate with high sensitivity and 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 aminophenol oxycodone and the like) and drugs (methamphetamine and the like).
A flexible wearable glove-based SERS substrate, comprising: assembling gold trioctahedron on an adhesive tape by using a liquid-liquid interface self-assembly technology, and then integrating the gold trioctahedron and a wearable glove together to obtain a flexible adhesive tape substrate; and then adhering uniform and compact polystyrene microsphere opal photonic crystals on the flexible adhesive tape substrate, and secondarily enhancing Raman signals, thereby obtaining the flexible wearable glove-based SERS substrate.
The gold trioctahedron is marked as Au TOH; the solutions according to the invention are all aqueous solutions, if not stated otherwise.
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 hexadecyltrimethylammonium chloride (CTAC) solution with 5-20 mu L of gold nanosphere seed solution with the particle size of 9-12 nm, then adding 130-150 mu L of Ascorbic Acid (AA) solution with 0.1M, and adding 2-2.5 mL of Ascorbic Acid (AA) solution with the particle size of 0.5X 10 after the reactants are completely dissolved -3 M HAuCl 4 Reacting the solution at 25-30 ℃ for 15-20min, centrifuging at 5500-6500 rpm for 10-15 min, dispersing the obtained precipitate into 0.5-1 mL of ethanol solution of polyvinylpyrrolidone (PVP) with the mass fraction of 1%, 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 storing at 4 ℃;
(2) Preparing a flexible adhesive tape substrate: mixing 100-300 mu L of Au TOH ethanol solution prepared in the step (1) with 1.5-2.5 mL of dichloromethane, then adding 3.5-4.5 mL of ultrapure water and violently shaking 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 the normal hexane, fishing out a layer of gold nanoparticles by using an 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, and so on, so that the assembly of 1-3 layers of gold nanoparticles can be realized to obtain the flexible adhesive tape substrate;
(3) Preparing polystyrene microsphere opal photonic crystals: centrifuging a polystyrene microsphere solution (with a concentration of 2.5% w/v) having a size of 300 to 500nm for 15 to 20 minutes at a rotation speed of 6500 to 7500rpm, and redispersing it in a solvent having a volume ratio of 1:1 in a mixed solution of water and ethanol; then, placing the hydrophilic glass slide in a culture dish at an angle of 15-45 degrees, filling the culture dish with water, and slowly dripping 3-8 mu L of polystyrene microsphere dispersion liquid onto the glass slide by using a liquid transfer machine; adding the next drop after the previous drop of microsphere solution is completely diffused until the whole water/air interface is covered by the color grating caused by diffraction of the polystyrene microsphere nano-structure array; finally, slowly fishing out the nano-structure array by using the silicon wafer subjected to hydrophilic treatment, slightly pressing the silicon wafer by using another transparent adhesive tape for 3-10 seconds, and then stripping the nano-structure array from the silicon wafer, thereby obtaining the ordered polystyrene microsphere opal photonic crystal 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 minutes to obtain serum, and diluting the serum to 10% (volume ratio) by water to obtain a serum solution; preparing tramadol and midazolam sample solutions with different concentrations by using the serum solution to obtain liquid samples; samples of two powders, namely methamphetamine and aminophenol oxycodone, 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 the fingertip of a wearable glove, extracting samples to be detected with different concentrations by simply wiping, then adhering the polystyrene microsphere opal photonic crystal on the flexible adhesive tape substrate after the samples to be detected are extracted to construct a glove substrate SERS substrate, and performing SERS test to obtain an SERS spectrum, thereby realizing qualitative and quantitative analysis of the samples.
Further, 2 to 2.5mL of 200X 10 -3 Mixing M Cetyl Trimethyl Ammonium Chloride (CTAC) solution with 40-60 μ L Cetyl Trimethyl Ammonium Bromide (CTAB) coated gold nanocluster solution, adding 1.5-3 mL and 0.1M ascorbic acid solution, adding 2-2.5 mL and 0.5 × 10 -3 M HAuCl 4 The solution reacts for 15 to 20 minutes at the temperature of between 25 and 30 ℃, and then is centrifuged for 20 to 40 minutes at 14000 to 15500rpm and resuspended in 1 to 2mL of solution with the volume ratio of 20 multiplied by 10 -3 Obtaining gold nanosphere seed solution from the M CTAC solution;
further, 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 HAuCl with a concentration of 0.5mM 4 Adding the solution into the solution, and then quickly adding 0.5-0.8 mL of 10 multiplied by 10 at 500-900 rpm -3 M NaBH 4 The solution is stirred vigorously for 1.5 to 3.0 minutes and is placed for 2 to 5 hours at the temperature of 25 to 30 ℃ to ensure complete reaction, and the gold nanocluster solution coated by CTAB is obtained.
The principle of the invention is as follows: the wearable glove-based SERS substrate with high sensitivity is prepared by taking the application of improving portable analysis of an SERS field as an entry point, utilizing the capability of efficiently absorbing a sample by using a flexible adhesive tape substrate, combining uniform and compact polystyrene microsphere opal photonic crystals and secondarily enhancing Raman signals to solve the problems of difficulty in field sample extraction, low sensitivity, poor detection repeatability and the like of the currently and commonly used planar rigid substrate. The invention has the beneficial effects that:
(1) The granularity of the prepared Jinsanoctahedron can reach the nanometer level, the average size can reach about 73nm, and the particle size distribution is uniform;
(2) Regular hot spots exist among the gold trioctahedra assembled on the flexible adhesive tape, the sensitivity of SERS detection can be obviously enhanced, and the optimal assembling layer number is 2 (2 layers are obtained by fishing out a layer of gold nanoparticles with 3M adhesive tape, and then fishing out a second layer of gold nanoparticles with the adhesive tape after the adhesive tape is dried in the air, so that the assembly of 2 layers can be realized);
(3) The gold trioctahedral assembled on the flexible adhesive tape is tightly arranged and uniformly distributed, the detection uniformity can be effectively improved, and the Relative Standard Deviation (Relative Standard development) of random detection for 50 times on the same glove base SERS substrate can be controlled to be about 5.08%;
(4) The prepared adhesive tape substrate has good flexibility, the bending and stretching of different degrees can not generate obvious influence on the repeatability of the SERS substrate of the glove substrate, 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 can not cause background interference on a detection result;
(6) The SERS trace detection has high repeatability, and the detection limit change rate does not exceed 5 percent according to the results obtained by repeating the experiment twice.
The invention can directly assemble the gold nanoparticles on the adhesive tape by using the liquid-liquid interface self-assembly technology, thereby effectively improving the signal repeatability, and the optimal assembly layer number is 2. More importantly, the introduction of the polystyrene microsphere opal photonic crystal can further enhance Raman signals, and meanwhile, the glove-based SERS substrate is more convenient for drawing samples and is not easy to pollute, so that the sensitivity of SERS detection is further improved.
Drawings
FIG. 1 is a transmission electron micrograph of Au TOH obtained in example 1 of the present invention; as shown in FIG. 1, it was revealed that Au TOH has a trioctahedral structure and an average particle diameter of about 73nm.
FIG. 2 is a scanning electron microscope image of the tape substrate obtained in example 2 of the present invention; as shown in fig. 2, the tape was uniformly covered with 2 Au TOH layers.
FIG. 3 is a scanning electron microscope image of polystyrene microsphere opal photonic crystals obtained in example 3 of the present invention; as shown in FIG. 3, the polystyrene microspheres are regularly and tightly arranged, and no packing or voids are generated.
FIG. 4 is a SERS spectrum of tramadol (a) and midazolam (b) in serum detected by the glove-based SERS substrate obtained in example 4 of the present invention, wherein the detection limit can be respectively as low as 69.19ng mL in serum -1 And 35.03ng mL -1 (the limit of detection is calculated according to the formula defined by the International Union of theory and applied chemistry (IUPAC): LOD = kS b M, wherein S b Standard deviation of 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 of a 10-fold mixture of methamphetamine and aminophenol oxycodone randomly detected by the glove-based SERS substrate obtained in example 4 of the present invention, and raman characteristic peaks of the methamphetamine and the aminophenol oxycodone 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 and dissolved in 5mL of water, and stirred gently at 27 ℃.5mL of a 0.5mM chloroauric acid solution (HAuCl) 4 ) Added to the above solution, and then rapidly added at 600rpm with 0.6mL of 10X 10 - 3 M sodium borohydride solution (NaBH) 4 ) Stirred for 2 minutes and placed at 27 ℃ for 3 hours to ensure complete reaction to obtain a CTAB coated gold nanocluster solution.
(2) Preparing a 10nm gold nanosphere seed solution:
2mL of the solution was mixed with 200X 10 -3 Mixing the M hexadecyl trimethyl ammonium chloride solution (CTAC) with 50 mu L of CTAB coated gold nanocluster solution obtained in the step (1), adding 1.5mL of 0.1M ascorbic acid solution (AA), and adding 2mL of 0.5X 10 after the reactant is completely dissolved -3 M HAuCl 4 The solution was reacted at 27 ℃ for 15 minutes and then resuspended in 1mL of 20X 10 medium by centrifugation at 14500rpm for 30 minutes -3 Obtaining gold nanosphere seed solution with the particle size of 10nm from the M CTAC solution.
(3) Preparation of 75nm Au TOH:
mixing 2mL of 0.1M CTAC solution with 5 μ L of 10nm gold nanosphere seed solution obtained in step (2), adding 130 μ L of 0.1M AA solution, adding 2mL of 0.5 × 10 AA solution after the reactant is completely dissolved -3 M HAuCl 4 Reacting the solution at 27 deg.C for 15min, centrifuging at 6000rpm for 15min, dispersing the precipitate into 0.5mL of ethanol solution containing polyvinylpyrrolidone (PVP) with a mass fraction of 1%, centrifuging at 6000rpm for 15min, and collecting the precipitateThe precipitate was redispersed in 0.5mL ethanol to give Au TOH ethanol solution, which was stored at 4 ℃.
Example 2: preparation of adhesive tape base
Mixing 200. Mu.L of the Au TOH ethanol solution prepared in example 1 with 2mL of dichloromethane, followed by adding 4mL of ultrapure water and vigorously shaking for 35 seconds; and then slowly adding 800 mu L of n-hexane, forming a layer of uniform gold nanoparticle film at the liquid-liquid interface, slowly removing the n-hexane, fishing out a 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 the 3M adhesive tape is aired, so that the assembly of 2 layers of gold nanoparticles is realized, and the flexible adhesive tape substrate is obtained.
Example 3: preparation of polystyrene microsphere opal photonic crystal
A polystyrene microsphere solution (concentration: 2.5% w/v) having a size of 300nm was centrifuged at 7000rpm for 15 minutes, and dispersed in a mixed solution of water and ethanol (volume ratio 1. Then, the hydrophilically treated slide glass was placed in a petri dish at an angle of 25 °, and 5 μ L of the polystyrene microsphere dispersion was slowly dropped onto the slide glass using a pipette. After the previous drop of microsphere solution is completely diffused to the water/air interface, the next drop is added until the whole interface is covered by the color grating caused by the diffraction of the polystyrene microsphere nano-structure array. And finally, slowly fishing out the nanostructure array by using the silicon wafer subjected to hydrophilic treatment, slightly pressing the silicon wafer by using another transparent adhesive tape for 5 seconds, and then stripping the nanostructure array from the silicon wafer, thereby obtaining the ordered polystyrene microsphere opal photonic crystal on the transparent adhesive tape.
Example 4: preparation and detection of glove-based SERS substrate
(1) Preparation of tramadol and midazolam serum samples:
centrifuging fresh human 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 the 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 samples 1 of different concentrations.
Different concentrations of midazolam serum sample 2 were prepared according to the same method.
(2) Preparation of a mixed sample of methamphetamine and aminophenol oxycodone:
solid mixed sample two solid powder samples were directly mixed in a volume ratio of 1:1, mixing uniformly.
(3) Preparation of glove-based SERS substrate:
fixing the flexible adhesive tape substrate obtained in the embodiment 2 on fingertips of wearable gloves, extracting a tramadol serum sample 1, a midazolam serum sample 2 and a solid powder mixed sample 3 with different concentrations by simply wiping, then adhering the polystyrene microsphere opal photonic crystal obtained in the embodiment 3 on the flexible adhesive tape substrate after extracting a sample to be detected to construct a glove substrate SERS substrate, and performing SERS detection on the flexible adhesive tape substrate (measuring each sample for 5 times and then averaging) by using 785nm laser to obtain an SERS spectrum, wherein the results are respectively shown in fig. 4 and fig. 5.
It can be observed in the spectrum of FIG. 4 that the Raman characteristic peak of tramadol is mainly located at 712cm -1 And 995cm -1 The Raman characteristic peak of midazolam is mainly positioned at 688cm -1 、827cm -1 And 1033cm -1 To (3). As expected, as the analyte concentration increases, the raman signal intensity also increases. Using 995cm -1 And 688cm -1 The intensity of the characteristic peak is used for indirectly monitoring the concentration of the tramadol and midazolam samples (the intensity of the characteristic peak is increased along with the increase of the concentration of the samples, so that the characteristic peak intensity can be established (the tramadol is 995 cm) -1 Characteristic peak of position, midazolam is 688cm -1 Characteristic peak of location) -analyte concentration ", and the limit of detection is then calculated according to the formula specified by the international union of theory and applied chemistry (IUPAC): LOD = kS b M, wherein S b Standard deviation of blank multiple measurements; m is the slope of the analytical calibration curve in the low concentration range; k is 3), the detection limit can be respectively reduced to 69.19ng mL -1 And 35.03ng mL -1 。
FIG. 5 shows that the Raman spectra of the mixed sample can be clearly seen after 10 random SERS testsCharacteristic peak, wherein 1002cm -1 、1030cm -1 And 1204cm -1 The characteristic peak is methamphetamine, and the rest is aminophenol oxycodone. It is worth noting that when signals of different positions of a mixed sample are collected (the mixed sample is a powder sample, and laser is focused on 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 is proved to have good sensitivity and identification capability, and the possibility of practical application 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 hexadecyltrimethylammonium 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, and adding 2-2.5 mL of 0.5 multiplied by 10 solution after reactants are completely dissolved -3 M HAuCl 4 Reacting the solution at 25-30 ℃ for 15-20min, centrifuging at 5500-6500 rpm for 10-15 minutes, then dispersing the obtained precipitate into 0.5-1 mL of ethanol solution of polyvinylpyrrolidone with the mass fraction of 1%, centrifuging at 5500-6000 rpm for 10-15 minutes, re-dispersing the obtained precipitate into 0.5-1 mL of ethanol to obtain Au TOH ethanol solution, and storing at 4 ℃;
(2) Preparing a flexible adhesive tape substrate: mixing 100-300 mu L of Au TOH ethanol solution prepared in the step (1) with 1.5-2.5 mL of dichloromethane, then adding 3.5-4.5 mL of ultrapure water and violently shaking for 30-50 seconds; then slowly adding 700-900 mu L of normal hexane, forming a layer of uniform gold nanoparticle film at a liquid-liquid interface, slowly removing the normal hexane, fishing out a layer of gold nanoparticles by using an adhesive tape, then fishing out a second layer of gold nanoparticles by using the adhesive tape after the adhesive tape is aired, and so on, so that the assembly of 1-3 layers of gold nanoparticles can be realized to obtain the flexible adhesive tape substrate;
(3) Preparing polystyrene microsphere opal photonic crystals: centrifuging the polystyrene microsphere solution with the size of 300-500 nm and the concentration of 2.5% w/v at the rotating speed of 6500-7500 rpm for 15-20 minutes, and then dispersing the polystyrene microsphere solution in a solvent with the volume ratio of 1:1 in a mixed solution of water and ethanol; then, placing the hydrophilic glass slide in a culture dish at an angle of 15-45 degrees, filling the culture dish with water, and slowly dripping 3-8 mu L of polystyrene microsphere dispersion liquid onto the glass slide by using a liquid transfer machine; adding the next drop after the previous drop of microsphere solution is completely diffused until the whole water/air interface is covered by the color grating caused by diffraction of the polystyrene microsphere nano-structure array; finally, slowly fishing out the nano-structure array by using the silicon wafer subjected to hydrophilic treatment, slightly pressing the silicon wafer by using another transparent adhesive tape for 3-10 seconds, and then stripping the nano-structure array from the silicon wafer, thereby obtaining the ordered polystyrene microsphere opal photonic crystal 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 the fingertip of a wearable glove, extracting samples to be detected with different concentrations by simply wiping, then adhering the polystyrene microsphere opal photonic crystal on the flexible adhesive tape substrate after the samples to be detected are extracted to construct a glove substrate SERS substrate, and performing SERS test to obtain an SERS spectrum, thereby realizing qualitative and quantitative analysis of the samples.
2. The method for preparing a flexible wearable glove-based SERS substrate according to claim 1, wherein: 2-2.5 mL of a solution of 200X 10 -3 Mixing M hexadecyl trimethyl ammonium chloride solution with 40-60 mu L of hexadecyl trimethyl ammonium bromide coated gold nanocluster solution, then adding 1.5-3 mL of ascorbic acid solution with 0.1M, and adding 2-2.5 mL of ascorbic acid solution with the concentration of 0.5 multiplied by 10 after reactants are completely dissolved -3 M HAuCl 4 The solution reacts for 15 to 20 minutes at the temperature of between 25 and 30 ℃, and then is centrifuged for 20 to 40 minutes at 14000 to 15500rpm and resuspended in 1 to 2mL of solution with the volume ratio of 20 multiplied by 10 -3 And obtaining gold nanosphere seed solution in the M CTAC solution.
3. The method for preparing a flexible wearable glove-based SERS substrate according to claim 2, wherein: weighing 0.3-0.4 g sixteenDissolving alkyl trimethyl ammonium bromide in 4-6 mL of water, and slightly stirring at 25-30 ℃; 4-6 mL of HAuCl solution and 0.5mM of HAuCl solution are added 4 Adding the solution into the solution, and quickly adding 0.5-0.8 mL and 10 multiplied by 10 at 500-900 rpm -3 M NaBH 4 The solution is stirred vigorously for 1.5 to 3.0 minutes and is placed for 2 to 5 hours at the temperature of between 25 and 30 ℃ to ensure complete reaction, and the gold nanocluster solution coated by the hexadecyl trimethyl ammonium bromide is obtained.
4. The method for preparing a flexible wearable glove-based SERS substrate according to claim 1, wherein: fresh human blood is centrifuged for 10 to 15 minutes at the rotating speed of 3000 to 4000rpm to obtain serum, and the serum is diluted to 10 percent of volume ratio by water to obtain serum solution; preparing tramadol and midazolam sample solutions with different concentrations by using the serum solution to obtain liquid samples; samples of two powders, namely methamphetamine and aminophenol oxycodone, 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 measured.
5. A flexible wearable glove-based SERS substrate, comprising: is prepared by the process of any one of claims 1 to 4.
6. Use of a flexible wearable glove-based SERS substrate according to claim 5 for the detection of controlled drugs or drugs.
7. The use of a flexible wearable glove-based SERS substrate according to claim 6 for the detection of controlled drugs or drugs, wherein: the controlled drug is tramadol, midazolam or amfenol oxycodone, and the drug is methamphetamine.
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