CN114252426A - Composite flexible SERS substrate and preparation method and application thereof - Google Patents
Composite flexible SERS substrate and preparation method and application thereof Download PDFInfo
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- CN114252426A CN114252426A CN202111394535.8A CN202111394535A CN114252426A CN 114252426 A CN114252426 A CN 114252426A CN 202111394535 A CN202111394535 A CN 202111394535A CN 114252426 A CN114252426 A CN 114252426A
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- sepiolite
- chitosan
- composite flexible
- silver
- sulfamethoxazole
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- 239000000758 substrate Substances 0.000 title claims abstract description 83
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- 229960005404 sulfamethoxazole Drugs 0.000 claims abstract description 46
- 229920001661 Chitosan Polymers 0.000 claims abstract description 44
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000001514 detection method Methods 0.000 claims abstract description 30
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- 238000012360 testing method Methods 0.000 claims description 22
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- 238000002156 mixing Methods 0.000 claims description 4
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
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- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 2
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- SKIVFJLNDNKQPD-UHFFFAOYSA-N sulfacetamide Chemical compound CC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 SKIVFJLNDNKQPD-UHFFFAOYSA-N 0.000 description 1
- 229960002673 sulfacetamide Drugs 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 229960004306 sulfadiazine Drugs 0.000 description 1
- BRBKOPJOKNSWSG-UHFFFAOYSA-N sulfaguanidine Chemical compound NC(=N)NS(=O)(=O)C1=CC=C(N)C=C1 BRBKOPJOKNSWSG-UHFFFAOYSA-N 0.000 description 1
- 229960004257 sulfaguanidine Drugs 0.000 description 1
- JNMRHUJNCSQMMB-UHFFFAOYSA-N sulfathiazole Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CS1 JNMRHUJNCSQMMB-UHFFFAOYSA-N 0.000 description 1
- 229960001544 sulfathiazole Drugs 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Images
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention discloses a composite flexible SERS substrate and a preparation method and application thereof. The composite flexible SERS substrate comprises a nylon microfiltration membrane and a sepiolite/chitosan/nano-silver crosslinked composite loaded on the surface of the nylon microfiltration membrane. The invention relates to aThe surface of sepiolite is modified with chitosan to provide Ag+Combining the sites, and obtaining the sepiolite/chitosan/nano silver cross-linked compound through in-situ reduction and cross-linking. The composite flexible SERS substrate composite material effectively overcomes the problems that a precious metal sol substrate is easy to agglomerate, poor in stability and poor in enrichment. The method for SERS detection of sulfamethoxazole has the advantages of simple operation, high sensitivity, good selectivity and the like, the detection limit is as low as 15.5 mu g/L, the recovery rate is between 91.4% and 101.4%, and the method has high accuracy and strong practicability in actual sample determination.
Description
Technical Field
The invention belongs to the technical field of Raman spectrum detection, and particularly relates to a composite flexible SERS substrate and a preparation method and application thereof.
Background
The Surface Enhanced Raman Spectroscopy (SERS) is a spectrum detection technology presenting molecular characteristic fingerprint spectra, and has the characteristics of rapidness, convenience, good sensitivity, nondestructive detection and the like. The method has wide application in various fields such as food safety, environmental detection, medical analysis, public safety and the like. However, the actual sample matrix component is complex, the content of the target substance is low, and the SERS signal generated by the matrix component seriously interferes with the SERS detection of target substance molecules, which directly affects the application of the SERS technology in the actual detection. The precious metal sol base is a SERS substrate which is commonly used at present, the preparation process is simple, but the defects of easy agglomeration, poor stability, poor enrichment, complicated pretreatment process and the like exist, and the detection requirement of an actual complex sample is difficult to meet. Therefore, the development of the integrated SERS substrate combined with the high-efficiency sample pretreatment method is an effective way for eliminating matrix interference, enriching target objects and improving the accuracy of SERS analysis.
The sulfonamide antibiotics are artificially synthesized antibacterial drugs with relatively early application, have the advantages of wide antibacterial spectrum, convenient use, low price and the like, and are more applied to aquaculture and poultry culture. However, abuse of sulfonamide antibiotics may induce the strains to generate drug resistance in the organism, and residues of the antibiotics easily enter the human body through a food chain to damage the health of the human body, and even have the hazards of carcinogenesis, teratogenesis, mutagenesis and the like. At present, methods such as main liquid chromatography, liquid-mass chromatography and the like are mainly used for detecting sulfonamide antibiotics, but the methods are long in time consumption and complex in pretreatment process. Therefore, establishing a rapid, accurate and efficient quantitative analysis method for sulfanilamide antibiotics has important significance on food safety.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. To this end, the present invention provides a composite flexible SERS substrate.
The invention also provides a preparation method of the composite flexible SERS substrate.
The invention also provides application of the composite flexible SERS substrate.
The invention also provides a method for detecting sulfamethoxazole by SERS.
The invention provides a composite flexible SERS substrate, which comprises a nylon microfiltration membrane and a sepiolite/chitosan/nano-silver crosslinked composite loaded on the surface of the nylon microfiltration membrane.
The invention relates to a technical scheme of a composite flexible SERS substrate, which at least has the following beneficial effects:
firstly, the invention provides Ag by modifying chitosan on the surface of sepiolite+Combining the sites, and obtaining the sepiolite/chitosan/nano silver cross-linked compound through in-situ reduction and cross-linking. The composite flexible SERS substrate composite material effectively solves the problems that a precious metal sol substrate is easy to agglomerate, poor in stability and poor in enrichment property; when the SERS film substrate is used for SERS detection of target molecules, separation, enrichment and detection of target objects are concentrated on the film substrate, so that the analysis speed is high, the sulfonamide antibiotics can be directly detected, and the requirement of on-site rapid detection can be met.
Secondly, the composite flexible SERS film substrate has good uniformity and reproducibility, and the Relative Standard Deviation (RSD) of the test results of the same batch of SERS film substrates at different positions and the test results of the different batches of SERS film substrates is less than 10% when the composite flexible SERS film substrate is used for detecting sulfamethoxazole with the same concentration.
Finally, the composite flexible SERS film substrate has good stability, the surface of the film substrate is always kept uniform and complete through bending tests of different degrees, the phenomena of folding, falling off, breaking and the like do not occur, and the relative standard deviation of detection results obtained after the SERS film substrate is placed for different days is less than 10%.
According to some embodiments of the invention, the mass ratio of the sepiolite, the chitosan and the nano silver in the sepiolite/chitosan/nano silver cross-linked composite is 1 (0.5-3.0) to (1.0-5.0).
According to some embodiments of the invention, the mass ratio of the sepiolite, the chitosan and the nano silver in the sepiolite/chitosan/nano silver cross-linked composite is 1 (1.0-3.0) to (1.0-3.0).
According to some embodiments of the invention, the nylon microporous membrane is one of a nylon 66 membrane or a nylon 6 membrane.
According to some preferred embodiments of the present invention, the pore size of the nylon microporous filter membrane is 0.1 to 0.3 μm.
The second aspect of the invention provides a preparation method of a composite flexible SERS substrate, which comprises the following steps:
s1, reacting sepiolite with chitosan to obtain a sepiolite/chitosan compound;
s2, reacting the sepiolite/chitosan compound in the step S1 with silver salt and a reducing agent to obtain a sepiolite/chitosan/nano-silver compound;
and S3, mixing the sepiolite/chitosan/nano-silver compound obtained in the step S2 with a cross-linking agent for reaction to obtain the sepiolite/chitosan/nano-silver cross-linked compound.
According to some embodiments of the invention, the silver salt is a soluble silver salt.
According to some embodiments of the invention, the soluble silver salt includes, but is not limited to, silver nitrate.
According to some embodiments of the invention, the reducing agent is at least one of sodium borohydride, ascorbic acid or sodium citrate.
According to some preferred embodiments of the invention, the reducing agent is sodium borohydride.
According to some embodiments of the invention, the cross-linking agent is a thiol polyethylene glycol carboxyl group.
According to some embodiments of the invention, in step S2, the sepiolite/chitosan/Ag+Middle Ag+The mass ratio of the reducing agent to the reducing agent is 1: (1-3).
According to some embodiments of the invention, the mass ratio of the sepiolite/chitosan/nano silver to the cross-linking agent is 1 (0.005-0.025).
According to some embodiments of the invention, the temperature of the reaction in step S1 is 70-100 ℃.
According to some embodiments of the invention, in step S1, the reaction time is 12-24 h.
According to some embodiments of the invention, the temperature of the reaction in step S2 is 15 to 35 ℃.
According to some embodiments of the invention, in step S2, the reaction time is 0.2 to 1.0 h.
According to some embodiments of the invention, the temperature of the reaction in step S3 is 15 to 35 ℃.
According to some embodiments of the invention, in step S3, the reaction time is 0.2 to 1.0 h.
The third aspect of the invention provides an application of the composite flexible SERS substrate in detection of sulfonamide antibiotics.
According to some embodiments of the invention, the sulfonamide antibiotic is sulfamethoxazole.
The fourth aspect of the invention provides a method for detecting sulfamethoxazole by SERS, which comprises the following steps:
(1) dripping standard sulfamethoxazole solutions with different concentrations into the composite flexible substrate, and performing SERS (surface enhanced Raman scattering) test to obtain the relation between the characteristic Raman displacement intensity and the concentration of sulfamethoxazole;
(2) enriching a sulfamethoxazole solution to be detected into the composite flexible substrate, carrying out SERS detection to obtain the characteristic Raman displacement intensity of sulfamethoxazole, and calculating according to the relation between the characteristic Raman displacement intensity and the concentration of sulfamethoxazole in the step (1) to obtain the concentration of sulfamethoxazole in the product to be detected; the composite flexible SERS substrate is the composite flexible SERS substrate as claimed in any one of claims 1-3.
According to some embodiments of the invention, the sulfamethoxazole standard solution has a pH value of 1-2.
According to some embodiments of the invention, the sulfamethoxazole standard solution has a concentration of 0.05-2.0 mg/L.
The composite flexible SERS film substrate provided by the invention is used for SERS detection of sulfamethoxazole, and has the advantages of simple operation, high sensitivity, good selectivity and the like, the detection limit is as low as 15.5 mu g/L, the recovery rate is between 91.4% and 101.4%, the accuracy is high in actual sample determination, and the practicability is strong.
Drawings
FIG. 1 is a schematic diagram of the working principle of the composite flexible SERS substrate of the present invention, wherein 1-sepiolite composite flexible SERS substrate, 2-surface enhanced Raman spectrometer, 3-computer;
FIG. 2 is a scanning electron micrograph of the sepiolite/chitosan/nano-silver composite of example 1;
FIG. 3 is a pictorial view of a composite flexible SERS substrate of example 1;
FIG. 4 is a SERS spectrum obtained by performing uniformity and reproducibility tests on the composite flexible SERS substrate of example 1;
FIG. 5 is a SERS spectrum obtained from the stability test of the composite flexible SERS substrate of example 1;
FIG. 6 is a schematic representation of a bend test of the composite flexible SERS substrate of example 1;
FIG. 7 is a SERS spectrum of different antibiotic species on the composite flexible SERS substrate of example 1;
FIG. 8 is a SERS spectrum of sulfamethoxazole standard solutions with different concentrations;
FIG. 9 is 1078cm-1A standard curve of Raman signal intensity-sulfamethoxazole concentration;
FIG. 10 shows SERS spectra measured on crucian carp sample, sulfamethoxazole and spiked sample.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.
The following examples and comparative examples employ the following starting materials:
all antibiotics were purchased from: shanghai Aladdin Biotechnology GmbH;
crucian, chicken and gizzard are purchased from: a local market;
surface enhanced raman spectroscopy was purchased from: delta Nu, USA;
high performance liquid chromatography was purchased from: shimadzu, Japan.
Example 1
pre-treating sepiolite: and (3) fully grinding 2.0g of sepiolite, adding the sepiolite into 50mL of 2.0mol/L hydrochloric acid, stirring for 4 hours at 40 ℃, washing with deionized water after the reaction is finished, filtering, and washing until the pH value of a supernatant is neutral. And (3) drying the filter cake in vacuum at 105 ℃ for 12h, fully grinding, and sieving by using a 200-mesh separation screen to obtain the purified sepiolite.
S1, adding 100mg of purified sepiolite into 30.0mL of 5.0mg/mL chitosan acetic acid solution, reacting for 21h in an oil bath at 85 ℃, centrifuging after the reaction is finished, washing with deionized water, washing until the pH value of a supernatant is neutral, and vacuum-drying the obtained product at 60 ℃ for 12h to obtain a sepiolite/chitosan compound;
s2, taking 20mg of the sepiolite/chitosan compound obtained in the step S1, dispersing the sepiolite/chitosan compound in 40mL of deionized water, and adding 40mg of AgNO3Stirring the solid at room temperature for 1h, slowly adding 480 mu L of 1.0mol/L sodium borohydride, and continuing the reaction for 1h after the dropwise addition is finished. After the reaction, centrifugally washing for 3 times, and re-dispersing in 20mL of deionized water to obtain sepiolite/chitosan/nano-silver composite dispersion, wherein a scanning electron microscope is shown in figure 2.
S3, taking 11mL of the sepiolite/chitosan/nano-silver compound dispersion liquid obtained in the step S2, diluting the sepiolite/chitosan/nano-silver compound dispersion liquid in 33mL, adding 1mL of sulfhydryl polyethylene glycol carboxyl with the concentration of 0.05mg/mL, continuously stirring for 0.5h at room temperature to obtain a sepiolite/chitosan/nano-silver cross-linked compound, and preparing the composite flexible SERS substrate by adopting a vacuum filtration technology and a nylon 66 membrane as a carrier. The prepared composite flexible SERS substrate is shown in figure 3.
Example 2
Example 2 provides a composite flexible SERS substrate, prepared in the same manner and using the same amount as in example 1, except that the mass ratio of sepiolite, chitosan and nano-silver is 1:1.5: 1.5.
Example 3
Example 3 provides a composite flexible SERS substrate prepared in the same manner and using the same amount as in example 1, except that the mass ratio of sepiolite, chitosan and nano-silver is 1:1.5: 2.5.
Test example 1
The testing principle of the surface-enhanced Raman spectroscopy is shown in figure 1, and a disposable injector is adopted to enrich a sample liquid to be tested to a membrane substrate 1 for filtration, an SERS signal is obtained under the laser scanning of a surface-enhanced Raman spectrometer 2, and the SERS signal is output and displayed in a computer 3.
Evaluation of the uniformity and reproducibility tests for the composite flexible SERS substrate prepared in example 1:
2mL of sulfamethoxazole solution (pH1.8) with the concentration of 1mg/L is filtered onto the composite flexible SERS substrate in the embodiment 1 by using a syringe, and SERS responses at 9 different positions on the same film substrate are tested; and preparing 9 different batches of composite flexible SERS substrates according to the method in example 1, and testing the SERS response of the different batches of composite flexible SERS film substrates. The SERS tests of different positions of the same film substrate and different batches of film substrates both adopt 785nm laser as a light source, the integration time is 5s, and the obtained SERS spectrogram is shown in figure 4. At 1078cm-1The intensity of the characteristic peak is taken as a reference, scanning is carried out for 3 times continuously, and an RSD value is calculated. As can be seen from the results in fig. 4, a in fig. 4 is the SERS response at different positions on the same film substrate, and the relative standard deviation of the analytical signal on the same composite flexible SERS substrate is 5.5% (n ═ 9); b in figure 5 is the SERS response of different batches of composite flexible SERS substrates,the relative standard deviation of the analyzed signal was 7.1% (n-9). Therefore, the composite flexible SERS substrate has good uniformity and reproducibility, and can meet the requirement of the precision of quantitative SERS analysis.
Test example 2
Evaluation of stability test of composite flexible SERS substrate prepared in example 1:
the composite flexible SERS film substrate in example 1 was subjected to different degree of bending tests, and the overall state of the film surface was observed. 2mL of sulfamethoxazole solution with the concentration of 1mg/L is enriched on the composite flexible SERS film substrate of the example 1 which is placed for different days by using an injector, SERS test is carried out, 785nm laser is used as a light source, and the integration time is 5 s. At 1078cm-1The intensity of the characteristic peak is taken as a reference, and the relative standard deviation is calculated by continuously scanning three times. A graph (A) of the bending test and a graph (B) of the results of the stability test on different days are shown in FIG. 6. The results of fig. 6 show that the surface of the film substrate of the composite flexible SERS substrate remains uniform and complete in the bending process, and the phenomena of fracture, shedding, breakage and the like do not occur, and the relative standard deviation of SERS detection results obtained by placing the composite flexible SERS substrate for different days is 5.6% (n is 3), which indicates that the composite flexible SERS substrate has good stability.
Test example 3
The composite flexible SERS substrate prepared in example 1 is used for SERS test of common antibiotics with similar structures, including sulfacetamide, sulfaguanidine, o-toluenesulfonamide, sulfadiazine, sulfadimetrazine and sulfathiazole, the concentration of each antibiotic is 1.0mg/L, and the corresponding SERS spectrogram is shown in FIG. 7. The results of fig. 7 show that the composite flexible SERS substrate of example 1 has a better enhancing effect on sulfamethoxazole, but does not have an obvious SERS enhancing effect on other common antibiotics with similar structures, which indicates that the composite flexible SERS substrate prepared in example 2 can be used for accurately determining sulfamethoxazole.
Test example 4
The composite flexible SERS substrate prepared in the embodiment 1 is used for detecting sulfamethoxazole in aquatic products and poultry, and specifically comprises the following steps:
(1) drawing of standard curve
Preparing sulfamethoxazole standard solutions with different concentrations, wherein the concentrations are 0.05, 0.1, 0.2, 0.5, 0.75, 1.0, 1.5 and 2.0mg/L respectively. 2mL of sulfamethoxazole standard solution with different concentrations is enriched on the SERS substrate prepared in the embodiment 1 through an injector, SERS test is carried out, 785nm laser is used as a light source, the integration time is 5s, the obtained SERS spectrogram is shown in figure 8, each concentration is tested for 3 times continuously, and the relative standard deviation is calculated. The measurement result shows that the SERS signal of sulfamethoxazole with the concentration is clearly visible on the film substrate, and a linear relation exists between the SERS signal and the concentration. At 1078cm-1The intensity at the Raman shift was used as a reference, and a standard curve of Raman signal intensity-sulfamethoxazole concentration was established (as shown in FIG. 9). The lowest concentration capable of detecting 3 times of signal-to-noise ratio signals is taken as a detection limit, the detection limit of sulfamethoxazole is 15.5 mu g/L (n is 3), and both the linear range and the detection limit of the method can meet the requirements of actual sample analysis.
(2) Detection of actual samples
Weighing 5.0g of fully-stirred crucian sample, chicken sample and gizzard sample, adding 5.0g of anhydrous sodium sulfate and 20mL of ethyl acetate, vortex, uniformly mixing, ultrasonically extracting for 5min, centrifuging at 4000r/min for 5min to obtain supernatant, adding n-hexane, vortex, carrying out rotary evaporation-nitrogen blowing concentration to nearly dry, adding 3mL of water/acetonitrile solution (water: acetonitrile is 7:3, pH is 1.8), filtering with a 0.22 mu m filter membrane, and collecting filtrate. 2mL of the filtrate was enriched on the SERS film substrate prepared in example 2 by means of a syringe to conduct SERS measurement, and SERS signals were measured as shown in FIG. 10, continuously measured 3 times, and 1078cm of 3 data was calculated-1Substituting the average value and the relative standard deviation of the intensity into a sulfamethoxazole standard curve, calculating to obtain the sulfamethoxazole concentration in the actual sample, and converting to obtain the sulfamethoxazole content in the actual sample. The measurement results are shown in Table 1, the sulfamethoxazole content in the crucian carp sample is 12.95 mug/kg, and the sulfamethoxazole content in the chicken sample and the chicken gizzard sample is not detected.
Then, a labeling experiment is carried out on the sample, the same pretreatment steps are adopted for SERS detection, the SERS detection is carried out for 3 times continuously, and 1078cm is calculated-1Relative standard deviation of off-peak valueRespectively substituting the standard curve of sulfamethoxazole into the standard curve of sulfamethoxazole, and calculating the concentration of sulfamethoxazole in the standard sample to obtain the crucian sample with the recovery rate of 99.1-101.4% and the RSD of 6.3-8.7%; the recovery rate of sulfamethoxazole in the chicken sample is 91.5-96.1%, and the RSD is 7.7-7.9%; the recovery rate of sulfamethoxazole in the gizzard sample is 91.4-97.6%, and the RSD is 6.1-6.3%. The results of the spiking experiments are shown in Table 1.
The detection accuracy of the SERS analysis method is verified through a High Performance Liquid Chromatography (HPLC) comparison experiment. Respectively weighing 5.0g of fully stirred crucian sample, chicken sample and gizzard sample, respectively adding 5.0g of anhydrous sodium sulfate and 20mL of ethyl acetate, vortex, uniformly mixing, ultrasonically extracting for 5min, centrifuging at 4000r/min for 5min to obtain supernatant, adding n-hexane, vortex, carrying out rotary evaporation-nitrogen blowing concentration to nearly dry, adding 3mL of water/acetonitrile solution (water: acetonitrile 7:3) for redissolution, purifying the redissolution through an HLB column, and collecting and testing the eluent through a 0.22 mu m filter membrane. The HPLC equipped with UV detector (Shimadzu corporation, Japan) has a detection wavelength of 270nm, and the selected column is ODS C18 column (250 mm. times.4.5 mm, 5.0 μm), the column temperature is 35 deg.C, and the mobile phase is acetonitrile-2% acetic acid aqueous solution (volume ratio 30:70), and the flow rate is 0.8 mL/min. HPLC detection shows that the sulfamethoxazole content in the crucian sample is 12.37 mu g/kg, the relative deviation with the SERS detection result is 4.7%, and the HPLC comparison experiment result is shown in Table 1, which shows that the SERS analysis method provided by the invention has high reliability.
TABLE 1 Sulfamethoxazole assay results and spiking test results in actual samples
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The composite flexible SERS substrate is characterized by comprising a nylon microfiltration membrane and a sepiolite/chitosan/nano-silver crosslinked composite loaded on the surface of the nylon microfiltration membrane.
2. The composite flexible SERS substrate according to claim 1, wherein the mass ratio of sepiolite, chitosan and nano-silver in the sepiolite/chitosan/nano-silver cross-linked composite is 1 (0.5-3.0) to (1.0-5.0).
3. The composite flexible SERS substrate according to claim 2, wherein the mass ratio of sepiolite, chitosan and nano-silver in the sepiolite/chitosan/nano-silver cross-linked composite is 1 (1.0-3.0) to (1.0-3.0).
4. The method for preparing the composite flexible SERS substrate according to any one of claims 1 to 3, comprising the following steps:
s1, reacting sepiolite with chitosan to obtain a sepiolite/chitosan compound;
s2, reacting the sepiolite/chitosan compound in the step S1 with silver salt and a reducing agent to obtain a sepiolite/chitosan/nano-silver compound;
and S3, mixing the sepiolite/chitosan/nano-silver compound obtained in the step S2 with a cross-linking agent for reaction to obtain the sepiolite/chitosan/nano-silver cross-linked compound.
5. The method for preparing a composite flexible SERS substrate according to claim 4, wherein the silver salt is a soluble silver salt in step S2.
6. The method for preparing the composite flexible SERS substrate according to claim 4, wherein in step S2, the reducing agent is at least one of sodium borohydride, ascorbic acid or sodium citrate.
7. The method for preparing the composite flexible SERS substrate according to claim 4, wherein in step S3, the cross-linking agent is thiol-polyethylene glycol carboxyl.
8. The method for preparing the composite flexible SERS substrate according to claim 4, wherein in the step S3, the mass ratio of the sepiolite, the chitosan and the nano silver to the cross-linking agent is 1 (0.005-0.025).
9. The application of the composite flexible SERS substrate according to any one of claims 1 to 3 in detection of sulfanilamide antibiotics.
10. The use according to claim 9, characterized in that a method for detecting sulfamethoxazole by SERS comprises the following steps:
(1) dripping standard sulfamethoxazole solutions with different concentrations into the composite flexible substrate, and performing SERS (surface enhanced Raman scattering) test to obtain the relation between the characteristic Raman displacement intensity and the concentration of sulfamethoxazole;
(2) enriching a sulfamethoxazole solution to be detected into the composite flexible substrate, carrying out SERS detection to obtain the characteristic Raman displacement intensity of sulfamethoxazole, and calculating according to the relation between the characteristic Raman displacement intensity and the concentration of sulfamethoxazole in the step (1) to obtain the concentration of sulfamethoxazole in the product to be detected; the composite flexible SERS substrate is the composite flexible SERS substrate as claimed in any one of claims 1-3.
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