CN115290562A - SERS detection method of 5-hydroxymethylfurfural - Google Patents
SERS detection method of 5-hydroxymethylfurfural Download PDFInfo
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 78
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 65
- 238000001514 detection method Methods 0.000 title claims abstract description 43
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 70
- 239000002077 nanosphere Substances 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000001069 Raman spectroscopy Methods 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 18
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- -1 PVP modified SiO 2 Nanospheres Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 238000001237 Raman spectrum Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 239000003223 protective agent Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 239000012086 standard solution Substances 0.000 claims description 3
- 101710134784 Agnoprotein Proteins 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 235000012907 honey Nutrition 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000020095 red wine Nutrition 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 3
- 238000002965 ELISA Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- WVMJEBICTINBRO-UHFFFAOYSA-N 5-Sulfoxymethylfurfural Chemical compound OS(=O)(=O)OCC1=CC=C(C=O)O1 WVMJEBICTINBRO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 231100000433 cytotoxic Toxicity 0.000 description 1
- 230000001472 cytotoxic effect Effects 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002972 pentoses Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
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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
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a SERS detection method of 5-hydroxymethylfurfural, which comprises PVP modified SiO 2 Preparation of nanospheres and SiO 2 And (3) preparing and detecting the @ Ag nanosphere. The invention has the beneficial effects that: by a simple method on SiO 2 Completely coating the surfaces of the nanospheres with uniform AgNPs to obtain SiO 2 @ Ag nanocomposite, which was then used as the SERS substrate for detection of 5-HMF. Due to SiO 2 The @ Ag nanosphere has high surface uniformity and is in SiO 2 Gaps among AgNPs coated on the surfaces of the nanospheres are smaller than 10nm, and a large number of hot spots can be formed, so that the SERS substrate has the advantages of good stability, good reproducibility and high sensitivity, and is suitable for detecting low concentration of 5-HMF and actual samples.
Description
Technical Field
The invention relates to an SERS detection method, in particular to an SERS detection method of 5-hydroxymethylfurfural, and belongs to the technical field of food safety detection.
Background
5-hydroxymethylfurfural (5-HMF), a six-carbon heterocyclic organic compound containing aldehyde and alcohol (hydroxymethyl) functionalities, is considered a ubiquitous food contaminant. Many food products undergo maillard and coking reactions during heat treatment processes, and when such reactions are carried out under acidic conditions, pentoses are dehydrated to form furfural and hexoses are dehydrated to form 5-HMF. It has been reported that 5-hydroxymethylfurfural exceeding the prescribed limit is not only cytotoxic in the human body but also irritating to mucous membranes of the eyes, skin, upper respiratory tract, and the like. In addition, 5-HMF accumulated in the human body for a long time is converted into 5-Sulphooxymethylfurfural (SMF), a carcinogen. Although 5-HMF is not present in fresh and untreated foods, it rapidly accumulates in heat-treated carbohydrate-rich foods. There are many methods for detecting 5-hydroxymethylfurfural, such as high performance liquid chromatography, liquid chromatography-tandem mass spectrometry, gas-liquid chromatography, spectrophotometry, capillary electrophoresis chromatography, enzyme-linked immunosorbent assay (ELISA), and the like. However, these methods generally have the disadvantages of complex detection procedures, long detection time, high detection cost, requirement of professional knowledge and operation techniques, and the like. Which limits their widespread use and is not suitable for the direct in situ detection of 5-hydroxymethylfurfural, it is important to develop a simple, rapid and sensitive means for detecting 5-HMF.
Surface Enhanced Raman Scattering (SERS) is a fast and ultra-sensitive detection technique that allows highly sensitive biological and chemical detection. SERS is mainly achieved by adsorbing molecules onto the surface of rough plasmonic nanostructures, achieving several orders of magnitude raman scattering enhancement. Because SERS has the sensitivity of single-molecule level detection, it has wide application in fields such as biochemistry, medical analysis, food safety, etc.
Disclosure of Invention
The present invention is directed to a method for SERS detection of 5-hydroxymethylfurfural to solve at least one of the above technical problems.
The invention realizes the purpose through the following technical scheme: the SERS detection method of 5-hydroxymethylfurfural comprises the following steps
Step one, PVP modified SiO 2 Preparation of nanospheres
Adding 4mL of ammonia water into 25mL of ethanol, performing ultrasonic treatment for 10min to obtain solution A, adding 2.5mL of tetraethyl orthosilicate into 25mL of ethanol, performing ultrasonic treatment for 10min to obtain solution B, dripping the solution B into the solution A for 40min, stirring for 6h to obtain pure white sol, washing with ethanol for several times, and drying to obtain SiO 2 A powder;
0.25g of SiO 2 Mixing the powder with 13mL pure water and performing ultrasonic treatment for 30min to obtain SiO 2 Adding 0.125g PVP powder into 10mL of pure water, ultrasonic treating until no white powder is seen on the upper layer of the pure water, and pouringInto SiO 2 Stirring for 2h in the dispersion to obtain PVP modified SiO 2 Nanosphere (PVP-SiO) 2 )；
Step two, siO 2 Preparation of @ Ag nanosphere
First, a silver ammonia solution, 0.105gAgNO, was prepared 3 Mixing with 10mL of pure water, performing ultrasonic treatment until the mixture is completely dissolved, slowly dripping 10% ammonia water until precipitate is generated, then removing the precipitate, pouring the silver ammonia solution into PVP-SiO 2 Stirring for 30min in the dispersion; heating the water bath kettle to 80 ℃, putting the water bath kettle into the water bath kettle for stirring, adding 0.1g/mL glucose solution when the temperature of the solution is increased to 80 ℃, reacting for 4 hours, and changing the solution from white to brown yellow, which indicates that the solution is already in SiO 2 Generating silver nano particles on the surface, and finally washing the silver nano particles for a plurality of times by pure water;
step three, detection
Taking 20 mu LSiO 2 The @ Ag solution is evenly dripped on a glass sheet and naturally dried; respectively taking 20 μ L of the extract at a concentration of 10 -1 M～10 - 8 Dropping the standard 5-HMF solution of M onto the dried substrate, and testing by Raman spectroscopy after the solution is naturally dried;
diluting the honey, red wine and other samples by a certain multiple, testing according to the operation, and calculating the content of the 5-hydroxymethylfurfural in the sample to be tested according to the standard curve.
As a still further scheme of the invention: in the second step, siO with uniform appearance and size 2 The preparation process of the @ Ag nanosphere is as follows:
first, PVP (polyvinylpyrrolidone) which plays the role of a protective agent and a stabilizing agent is coated on SiO 2 The surface of the nanosphere is electrostatically adsorbed on the PVP-SiO with electronegativity by using the positively charged silver ammonia ions as the silver source 2 Finally, reducing silver ammonia ions by glucose solution to generate coated SiO 2 AgNPs on the surface of the nanospheres.
As a still further scheme of the invention: in the third step, siO 2 The @ Ag solution is used for SERS detection of 5-HMF solutions with different concentrations, and specifically comprises the following steps:
SiO 2 with @ Ag as SERS substrate, for different concentrationsWhen the 5-HMF molecule is adsorbed on the SERS substrate, a Raman characteristic peak showing obvious change is taken as a standard peak for quantitatively analyzing the 5-HMF, a linear relation exists between the Raman signal intensity of the standard peak and the negative logarithm of the concentration of the 5-HMF, and a linear correlation coefficient (R) is obtained 2 ) It was 0.9918, and the detection limit was obtained by calculation.
As a still further scheme of the invention: the SiO 2 When the @ Ag solution is used for SERS detection of 5-HMF solutions with different concentrations, pure water (without 5-HMF) and SiO are adopted 2 The SERS spectrum obtained by directly mixing and drying the @ Ag powder is used as a blank control group.
As a still further scheme of the invention: in the third step, siO 2 @ Ag is used for detecting reproducibility and stability of 5-HMF SERS, and the reproducibility of SERS signals is an important index for evaluating the practical application of SERS substrates 2 The Raman spectrogram is obtained by randomly detecting 5-HMF molecules at 15 different positions on the @ Ag SERS substrate so as to prove the reproducibility of the Raman spectrogram.
The beneficial effects of the invention are: by a simple method on SiO 2 Completely coating the surfaces of the nanospheres with uniform AgNPs to obtain SiO 2 @ Ag nanocomposite, which was then used as the SERS substrate for detection of 5-HMF. Due to SiO 2 The @ Ag nanosphere has high surface uniformity and is in SiO 2 Gaps among AgNPs coated on the surfaces of the nanospheres are smaller than 10nm, and a large number of hot spots can be formed, so that the SERS substrate has the advantages of good stability, good reproducibility and high SERS enhancement performance, and is suitable for low concentration of 5-HMF and detection in actual samples.
Drawings
FIG. 1 is a schematic flow diagram of the present invention;
FIG. 2 is a schematic representation of a large area SiO of the present invention 2 SEM image of nanospheres;
FIG. 3 shows diffraction peaks and amorphous SiO of the present invention 2 The characteristic peak correspondence map of (a);
FIG. 4 is a schematic representation of Ag and SiO in accordance with the present invention 2 Ultraviolet pattern of @ Ag;
FIG. 5 shows a concentration of 10 according to the present invention -8 ～10 -1 The SERS spectrogram of the 5-HMF solution of M and the linear relation between the Raman signal intensity and the negative logarithm of the 5-HMF concentration exist;
FIG. 6 shows the present invention on SiO 2 The Raman spectrogram is obtained by randomly detecting 5-HMF molecules at 15 different positions on the @ Ag SERS substrate.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
As shown in figure 1, the SERS detection method of 5-hydroxymethylfurfural comprises the following steps
Step one, PVP modified SiO 2 Preparation of nanospheres
Adding 4mL of ammonia water into 25mL of ethanol, performing ultrasonic treatment for 10min to obtain solution A, adding 2.5mL of tetraethyl orthosilicate into 25mL of ethanol, performing ultrasonic treatment for 10min to obtain solution B, dripping the solution B into the solution A for 40min, stirring for 6h to obtain pure white sol, washing with ethanol for several times, and drying to obtain SiO 2 Powder;
0.25g of SiO 2 Mixing the powder with 13mL pure water and performing ultrasonic treatment for 30min to obtain SiO 2 Adding 0.125g PVP powder into 10mL of pure water, ultrasonic treating until no white powder is seen on the upper layer of the pure water, pouring into SiO 2 Stirring for 2h in the dispersion to obtain PVP modified SiO 2 Nanosphere (PVP-SiO) 2 )；
Step two, siO 2 Preparation of @ Ag nanosphere
First, a silver ammonia solution, 0.105gAgNO, was prepared 3 Mixing with 10mL of pure water, performing ultrasonic treatment until the mixture is completely dissolved, slowly dripping 10% ammonia water until precipitate is generated, then removing the precipitate, pouring the silver ammonia solution into PVP-SiO 2 Stirring for 30min in the dispersion liquid; heating the water bath kettle to 80 ℃, and putting the water bath kettle into waterStirring in a bath pot, adding 0.1g/mL glucose solution when the temperature of the solution rises to 80 ℃, reacting for 4 hours, and changing the solution from white to brown yellow, which shows that the solution is already in SiO 2 Silver nanoparticles were generated on the surface, and finally washed several times with pure water.
Step three, detection
Taking 20 mu LSiO 2 The @ Ag solution is evenly dripped on a glass sheet and naturally dried; respectively taking 20 μ L of the extract at a concentration of 10 -1 M～10 - 8 Dropping the 5-HMF standard solution of M on an air-dried substrate, and testing by using a Raman spectrum after the air-dried substrate is naturally dried;
diluting the honey, red wine and other samples by a certain multiple, testing according to the operation, and calculating the content of the 5-hydroxymethylfurfural in the sample to be tested according to the standard curve.
In the embodiment of the invention, in the second step, siO with uniform appearance and uniform size 2 The preparation process of the @ Ag nanosphere comprises the following steps:
first, PVP (polyvinylpyrrolidone) which plays the role of a protective agent and a stabilizing agent is coated on SiO 2 The surface of the nanosphere is electrostatically adsorbed on the PVP-SiO with electronegativity by using the positively charged silver ammonia ions as the silver source 2 Finally, reducing silver ammonia ions by glucose solution to generate coated SiO 2 AgNPs on the surface of the nanospheres.
In the embodiment of the invention, in the third step, siO 2 The @ Ag solution is used for SERS detection of 5-HMF solutions with different concentrations, and specifically comprises the following steps:
SiO 2 when @ Ag is used as the SERS substrate, the SERS spectrogram of 5-HMF solution with different concentrations is analyzed, when 5-HMF molecules are adsorbed on the SERS substrate, for Raman characteristic peaks showing obvious changes and used as standard peaks for quantitatively analyzing 5-HMF, a linear relation exists between the Raman signal intensity of the standard peaks and the negative logarithm of the 5-HMF concentration, and a linear correlation coefficient (R) is obtained 2 ) And 0.9918, the detection limit was obtained by calculation.
In the embodiment of the invention, the SiO 2 When the @ Ag solution is used for SERS detection of 5-HMF solutions with different concentrations, pure water (without 5-HMF) and SiO are adopted 2 The SERS spectrum obtained after the @ Ag powder is directly mixed and dried is used as a blank control group.
In the embodiment of the invention, in the third step, siO 2 @ Ag is used for detecting reproducibility and stability of 5-HMF SERS, and the reproducibility of SERS signals is an important index for evaluating the SERS substrate in practical application 2 The Raman spectrogram is obtained by randomly detecting 5-HMF molecules at 15 different positions on the @ Ag SERS substrate so as to prove the reproducibility of the Raman spectrogram.
Example two
As shown in fig. 2 to fig. 6, a method for SERS detection of 5-hydroxymethylfurfural includes the following steps
Step one, PVP modified SiO 2 Preparation of nanospheres
Adding 4mL of ammonia water into 25mL of ethanol, performing ultrasonic treatment for 10min to obtain solution A, adding 2.5mL of tetraethyl orthosilicate into 25mL of ethanol, performing ultrasonic treatment for 10min to obtain solution B, dripping the solution B into the solution A for 40min, stirring for 6h to obtain pure white sol, washing with ethanol for several times, and drying to obtain SiO 2 A powder;
0.25g of SiO 2 Mixing the powder with 13mL pure water and performing ultrasonic treatment for 30min to obtain SiO 2 Dispersing liquid, 0.125g PVP powder is added into 10mL of pure water, ultrasonic treatment is carried out until no white powder can be seen on the upper layer of the pure water, and the dispersion liquid is poured into SiO 2 Stirring for 2h in the dispersion to obtain PVP modified SiO 2 Nanosphere (PVP-SiO) 2 )；
Step two, siO 2 Preparation of @ Ag nanosphere
First, a silver ammonia solution, 0.105gAgNO, was prepared 3 Mixing with 10mL of pure water, performing ultrasonic treatment until the mixture is completely dissolved, slowly dripping 10% ammonia water until precipitate is generated, then removing the precipitate, pouring the silver ammonia solution into PVP-SiO 2 Stirring for 30min in the dispersion; heating the water bath kettle to 80 ℃, putting the water bath kettle into the water bath kettle for stirring, adding 0.1g/mL glucose solution when the temperature of the solution is increased to 80 ℃, reacting for 4 hours, and changing the solution from white to brown yellow, which indicates that the solution is already in SiO 2 Generating silver nano particles on the surface, and finally washing the silver nano particles for a plurality of times by pure water;
step three, detection
Taking 20 mu LSiO 2 The @ Ag solution is evenly dripped on a glass sheet and naturally dried; respectively taking 20 μ L of the extract at a concentration of 10 -1 M～10 - 8 Dropping the 5-HMF standard solution of M on an air-dried substrate, and testing by using a Raman spectrum after the air-dried substrate is naturally dried;
diluting the honey, red wine and other samples by a certain multiple, testing according to the operation, and calculating the content of the 5-hydroxymethylfurfural in the sample to be tested according to the standard curve.
Wherein FIGS. 2 (a) and (b) are large-area SiO prepared 2 SEM image of the nanospheres, it is seen that the size is highly uniform, and the particle size distribution diagram is obtained by counting the particle sizes of more than 100 nanoparticles by using Nano Measurer software, and SiO is calculated 2 The average particle size of the nanospheres was 471nm; FIGS. 2 (c) and (d) are SiO 2 SEM image of @ Ag composite nanosphere, siO can be seen 2 The surface of the @ Ag nanospheres is relatively rough, although SiO 2 @ Ag nanospheres of AgNPs in SiO 2 The composite material obtained by in-situ surface growth is uniform in size, and the average particle size is calculated to be 500 nm.
XRD
SiO 2 Nanospheres and SiO 2 @ Ag composite nanospheres were characterized by XRD. The diffraction peak at a 2 theta value of 21.8 deg. is seen in FIG. 3 together with amorphous SiO 2 The characteristic peaks of (a) correspond to (b). The four diffraction peaks appearing at 2 θ values of 38.1 °, 44.3 °, 64.4 °, and 77.5 °, respectively corresponding to the reflections of the (111), (200), (220), and (311) crystal planes of face centered cubic silver (JCPDS card No. 04-0783), are shown in SiO 2 AgNPs are successfully synthesized on the surfaces of the nanospheres in situ, and amorphous SiO can be seen after silver nanoparticles are generated 2 The characteristic peaks of (a) are relatively reduced.
UV-vis
FIG. 4 shows Ag and SiO 2 Ultraviolet diagram of @ Ag, from which AgNPs and SiO can be seen 2 The @ Ag nanospheres show typical Surface Plasmon Resonance (SPR) absorption bands of metal nanoparticles at 412nm and 436nm, respectively, and half of the surface plasmon resonance absorption peak of AgNPsThe narrow peak width and high symmetry indicate that the AgNPs synthesized by the method have uniform particle size distribution. SiO 2 2 The maximum absorption wavelength of the @ Ag nanosphere is red-shifted compared to that of AgNPs, and the peak shape is significantly broadened due to reduction in SiO 2 The AgNPs on the surface of the nanosphere generate a local plasmon coupling effect, so that the AgNPs can be coated on SiO 2 The surface of the nanosphere.
SiO 2 SERS detection of @ Ag on 5-HMF
Using SiO 2 SERS detection of @ Ag on 5-HMF solutions with different concentrations
SiO 2 @ Ag as SERS substrate, concentration is 10 -8 ～10 -1 The SERS spectrum of the 5-HMF solution of M is shown in FIG. 5.
It can be seen that 1509cm when the 5-HMF molecule is adsorbed on the SERS substrate -1 The Raman characteristic peak at (A) shows a significant change, so 1509cm was chosen here -1 The Raman peak at (A) was used as a standard peak for quantitative analysis of 5-HMF. In the inset of FIG. 5 (a) it can be seen that even the concentration of the 5-HMF solution is as low as 10 -8 When M is used, a distinguishable Raman characteristic peak can be still seen, which indicates that the SERS substrate can detect 5-HMF as low as 10nM, and blank refers to pure water (without 5-HMF) and SiO 2 And the SERS spectrum is obtained after the @ Ag powder is directly mixed and dried. It can be seen from FIG. 5 (b) that there is a good linear relationship between the Raman signal intensity of the standard peak and the negative logarithm of the concentration of 5-HMF, and that there is a linear correlation coefficient (R) 2 ) Reaching 0.9918. The detection limit of this method was calculated to be 4.8nM (3N/S).
FIG. 5 (a) concentration of 10 -8 ～10 -1 SERS spectrum of 5-HMF solution of M; (b) There is a good linear relationship between the intensity of the Raman signal and the negative logarithm of the concentration of 5-HMF (inset: concentration 10.) -8 SERS spectrogram of M5-HMF solution
SiO 2 Reproducibility and stability of @ Ag to 5-HMF SERS detection
Reproducibility of the SERS signal is an important indicator for evaluating the actual application of the SERS substrate. In SiO 2 15 different positions on @ Ag SERS substrateThe Raman spectrogram is obtained by randomly detecting the 5-HMF molecules so as to prove the reproducibility of the Raman spectrogram. From FIG. 6, it can be seen that the distance is 1509cm -1 The Relative Standard Deviation (RSD) at the peak position was only 2.2%, indicating that the SERS substrate had very good uniformity.
The working principle is as follows: firstly, a simple method is utilized to prepare SiO 2 Completely coating the surfaces of the nanospheres with uniform AgNPs to obtain SiO 2 @ Ag nanocomposite, which was then used as a SERS substrate for detection of 5-HMF. Due to SiO 2 The @ Ag nanosphere has high surface uniformity and is in SiO 2 Gaps among AgNPs coated on the surfaces of the nanospheres are smaller than 10nm, and a large number of hot spots can be formed, so that the SERS substrate has the advantages of good stability, good reproducibility and high SERS enhancement performance, and is suitable for low concentration of 5-HMF and detection in actual samples.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (5)
1. The SERS detection method of 5-hydroxymethylfurfural is characterized by comprising the following steps: comprises the following steps
Step one, PVP modified SiO 2 Nano meterPreparation of the balls
Adding ammonia water into ethanol for ultrasonic treatment to obtain solution A, adding tetraethyl orthosilicate into ethanol for ultrasonic treatment to obtain solution B, then dripping the solution B into the solution A, stirring to obtain pure white sol, washing with ethanol, and drying to obtain SiO 2 Powder;
mixing SiO 2 Mixing powder and pure water and ultrasonically obtaining SiO 2 Adding dispersion liquid, PVP powder into pure water, performing ultrasonic treatment until no white powder is seen on the upper layer of the pure water, pouring into SiO 2 Stirring the dispersion to obtain PVP modified SiO 2 Nanospheres;
step two, siO 2 Preparation of @ Ag nanosphere
Preparation of silver Ammonia solution, agNO 3 Mixing with pure water, ultrasonic treating to dissolve completely, slowly dropping ammonia water until precipitate is formed, and pouring silver ammonia solution into PVP-SiO 2 Stirring in the dispersion liquid; heating the water bath, stirring in the water bath, adding glucose solution when the solution temperature is 80 deg.C, and reacting to obtain solution with color changed from white to brown yellow 2 Generating silver nano particles on the surface, and finally washing the silver nano particles for a plurality of times by pure water;
step three, detection
Taking SiO 2 The @ Ag solution is evenly dripped on a glass sheet and naturally dried; respectively taking 20 μ L of the extract at a concentration of 10 -1 M～10 -8 Dropping the 5-HMF standard solution of M on an air-dried substrate, and testing by using a Raman spectrum after the air-dried substrate is naturally dried;
and (3) diluting the sample by a certain multiple, testing according to the operation, and calculating the content of the 5-hydroxymethylfurfural in the sample to be tested according to the standard curve.
2. The SERS detection method of 5-hydroxymethylfurfural according to claim 1, characterized in that: in the second step, siO with uniform appearance and size 2 The preparation process of the @ Ag nanosphere comprises the following steps:
first, PVP and polyvinylpyrrolidone which play the roles of a protective agent and a stabilizing agent are coated on SiO 2 Nanosphere surface, then positive as silver sourceElectrostatic adsorption of silver ammonia ion to PVP-SiO with electronegativity 2 Finally, reducing silver ammonia ions by glucose solution to generate coated SiO 2 AgNPs on the surface of the nanospheres.
3. The SERS detection method of 5-hydroxymethylfurfural according to claim 1, characterized by comprising the following steps: in the third step, siO 2 The @ Ag solution is used for SERS detection of 5-HMF solutions with different concentrations, and specifically comprises the following steps:
SiO 2 when @ Ag is used as the SERS substrate, the SERS spectrogram of a 5-HMF solution with different concentrations is analyzed, when a 5-HMF molecule is adsorbed on the SERS substrate, a Raman characteristic peak showing obvious change is used as a standard peak for quantitatively analyzing the 5-HMF, a linear relation exists between the Raman signal intensity of the standard peak and the negative logarithm of the 5-HMF concentration, and a linear correlation coefficient R 2 It was 0.9918, and the detection limit was obtained by calculation.
4. The SERS detection method of 5-hydroxymethylfurfural according to claim 4, characterized by comprising the following steps: the SiO 2 When the @ Ag solution is used for SERS detection of 5-HMF solutions with different concentrations, pure water (without 5-HMF) and SiO are adopted 2 The SERS spectrum obtained by directly mixing and drying the @ Ag powder is used as a blank control group.
5. The SERS detection method of 5-hydroxymethylfurfural according to claim 1, characterized by comprising the following steps: in the third step, siO 2 @ Ag is used for detecting reproducibility and stability of 5-HMF SERS, and the reproducibility of SERS signals is an important index for evaluating the practical application of SERS substrates 2 The Raman spectrogram is obtained by randomly detecting 5-HMF molecules at 15 different positions on the @ Ag SERS substrate so as to prove the reproducibility of the Raman spectrogram.
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