CN114088486A - Preparation of high-sensitivity SERS substrate and application of high-sensitivity SERS substrate in trace DECMP detection - Google Patents
Preparation of high-sensitivity SERS substrate and application of high-sensitivity SERS substrate in trace DECMP detection Download PDFInfo
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- 238000001514 detection method Methods 0.000 title claims abstract description 22
- 239000000758 substrate Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052709 silver Inorganic materials 0.000 claims abstract description 43
- 239000004332 silver Substances 0.000 claims abstract description 43
- FWAXWNOGOQKLTC-UHFFFAOYSA-N chloromethyl diethyl phosphate Chemical compound CCOP(=O)(OCC)OCCl FWAXWNOGOQKLTC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002105 nanoparticle Substances 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 10
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 18
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229960005070 ascorbic acid Drugs 0.000 claims description 13
- 235000010323 ascorbic acid Nutrition 0.000 claims description 13
- 239000011668 ascorbic acid Substances 0.000 claims description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 12
- 239000012498 ultrapure water Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 3
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
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- 239000011550 stock solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GRXKLBBBQUKJJZ-UHFFFAOYSA-N Soman Chemical compound CC(C)(C)C(C)OP(C)(F)=O GRXKLBBBQUKJJZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005843 halogen group Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 231100000225 lethality Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
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- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- LJWSOZVTIHSXQZ-UHFFFAOYSA-L sodium 3-carboxy-3,5-dihydroxy-5-oxopentanoate chlorosilver Chemical compound [Cl-].[Na+].C(CC(O)(C(=O)O)CC(=O)O)(=O)[O-].[Ag+] LJWSOZVTIHSXQZ-UHFFFAOYSA-L 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
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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
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a preparation method of a high-sensitivity SERS substrate and a method for detecting trace chloromethyl diethyl phosphate by using the same, which comprises the following steps: (1) synthesizing silver nanoparticles with higher concentration and high sensitivity in a sol system by improving the existing synthesis technology; (2) adding silver nanoparticle sol and high-concentration inorganic salt solution into the solution to be detected, and detecting and identifying the concentration of chloromethyl diethyl phosphate molecules in the aqueous solution by using a portable Raman spectrometer. The detection sensitivity of the invention to the diethyl chloromethyl phosphate molecule can reach 50mg/L, and the invention has the advantages of simplicity, rapidness, low cost, high stability and the like.
Description
Technical Field
The invention relates to the field of synthesis and detection methods, in particular to a synthetic high-sensitivity SERS substrate and a method for rapidly detecting trace chloromethyl diethyl phosphate (DECMP).
Background
Chemical warfare agents are highly lethal chemicals used as chemical weapons to kill opposing parties in war sessions. In the peaceful age, however, the high toxicity and fast fatality are characterized by terrorist threat to human life safety. And chloromethyl diethyl phosphate is used as a nerve poison with the strongest toxicity and the largest lethality, namely a soman simulator, of chemical warfare agents, and the quick detection of the chloromethyl diethyl phosphate has great significance for national defense safety.
The SERS method has the advantages of simplicity and convenience in operation, high sensitivity, low detection cost, high analysis speed and the like, and has great application potential in various fields such as environmental monitoring, biological analysis and detection, food science and the like. The prior art lacks an SERS method for detecting chloromethyl diethyl phosphate, is difficult to detect low-concentration chloromethyl diethyl phosphate molecules, and restricts the application and popularization of the SERS method for detecting chloromethyl diethyl phosphate molecules.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a synthetic high-sensitivity SERS substrate and a method for rapidly detecting trace chloromethyl diethyl phosphate by using the same.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a preparation method of a high-sensitivity SERS substrate comprises the following steps:
1) mixing 0.5-1.5 wt% of sodium citrate aqueous solution, 0.5-1.5 wt% of silver nitrate aqueous solution, 15-25 mM of sodium chloride aqueous solution and ultrapure water according to a volume ratio of 0.5-1.5: 0.1-0.4: 0.1-0.3: 0.8-1.5 to obtain a mixed solution A; adding the mixed solution A into boiling water containing 10-30 mM ascorbic acid, continuously heating and stirring for 40-80 min, and cooling to room temperature to obtain a first silver nanoparticle sol;
2) mixing the first silver nanoparticle sol with the volume of V1 and the first silver nanoparticle sol with the volume of 0.5 multiplied by 10-3～2×10-3M NaBr solution is prepared by mixing the following components in a volume ratio of 3-5: 1, mixing, centrifuging, removing supernatant, adding ultrapure water, and metering the volume to V1 again to obtain silver seeds;
3) silver seeds with the volume of V2, ultrapure water with the volume of V3 and 0.1M ascorbic acid solution are mixed according to the volume ratio of 5-15: 5-15: 0.1-0.8, slowly adding 30-50 mM silver-ammonia complex solution into the mixed solution B under the stirring state, fully reacting for more than 1h, centrifugally removing supernatant, adding ultrapure water, and fixing the volume to V2+ V3 again to obtain second silver nanoparticle sol serving as a high-sensitivity SERS substrate.
Optionally, the silver nanoparticle particle size of the first silver nanoparticle sol is 15-50 nm.
Optionally, the silver nanoparticle particle size of the second silver nanoparticle sol is 40-120 nm.
Optionally, in the step 1), the volume ratio of the mixed solution a to boiling water containing 0.05-0.15M ascorbic acid is 1: 15 to 25.
Optionally, in step 3), the volume ratio of the silver-ammonia complex solution to the mixed solution B is 1: 25 to 35.
A detection method of trace chloromethyl diethyl phosphate comprises the following steps:
1) mixing the second silver nanoparticle sol with a sample to be detected, and then adding a halogen salt solution with the concentration of 0.3-3M to form a mixed solution to be detected;
2) placing the mixed solution to be detected in a Raman spectrometer for detection at 1073cm-1According to the characteristic Raman peak, the qualitative and quantitative detection is carried out on the chloromethyl diethyl phosphate in the sample to be detected according to the peak position and the peak intensity.
Optionally, the volume ratio of the second silver nanoparticle sol to the sample to be detected to the halogen salt solution is 1: 3-5: 0.5 to 1.5.
Optionally, the halide salt solution comprises an aqueous solution of NaF, NaCl, NaBr, KF, KCl, or KBr.
Optionally, the concentration of the halogen salt solution is 0.3-1M.
Optionally, the lowest detectable concentration of chloromethyl diethyl phosphate is 50 mg/L.
The invention has the beneficial effects that:
the pH of the nano silver sol improved by the preparation method is higher, and H adsorbed on the surface of Ag NPs+Less, so that target molecules are easier to adsorb to the surfaces of the nano particles, and the detection of chloromethyl diethyl phosphate molecules in the environment can be conveniently, quickly, low in cost, high in sensitivity and high in stability. The inventionThe detection sensitivity of the diethyl chloromethyl phosphate molecule can reach 50ppm, the online monitoring is convenient, and the method has potential market value.
Drawings
FIG. 1 is a detection schematic diagram of a chloromethyl diethyl phosphate molecule detection method based on SERS technology disclosed in the present invention;
FIG. 2 is an SEM photograph of 75nm Ag NPs synthesized in example 1;
FIG. 3 is a Raman spectrum (left) corresponding to different concentrations of chloromethyl diethyl phosphate molecules detected by Ag NPs synthesized in the comparative example and a Raman spectrum (right) corresponding to different concentrations of chloromethyl diethyl phosphate molecules in the detection method for chloromethyl diethyl phosphate molecules established in example 1;
FIG. 4 is 1073cm-1The SERS intensity and chloromethyl diethyl phosphate molecule concentration relation curve chart of department, the linear correlation coefficient is 0.995.
Detailed Description
The invention is further explained below with reference to the figures and the specific embodiments.
The invention discloses a method for synthesizing a high-sensitivity SERS substrate, which mainly comprises the following steps:
(1) preparing a mixed solution, and reducing the mixed solution by using ascorbic acid to synthesize silver seeds; the mixed solution comprises 0.5-1.5 wt% of sodium citrate aqueous solution, 0.5-1.5 wt% of silver nitrate aqueous solution and 15-25 mM of sodium chloride aqueous solution; the ascorbic acid is prepared by mixing an ascorbic acid aqueous solution with the concentration of 0.05-0.15M and boiling water according to the volume ratio of 0.08: 40-60 mixing to obtain;
(2) removing impurities of the silver seeds synthesized in the step (1) by using NaBr; specifically, after silver seeds are transferred to a centrifugal tube, 0.5 multiplied by 10 silver seed volume 1/3-1/5 is added into the centrifugal tube-3～2×10-3M NaBr, fully oscillating and uniformly mixing, centrifuging to remove supernatant, and adding ultrapure water with the same amount as the supernatant;
(3) reducing the slowly dropwise added silver-ammonia complex by using ascorbic acid to grow Ag NPs on the basis of the silver seeds obtained in the step (2) after impurity removal; the ascorbic acid is ascorbic acid aqueous solution with the concentration of 0.05-0.15M, and the slow dripping is to drip the silver-ammonia complex over 1 hour by a peristaltic pump.
The method for rapidly detecting trace chloromethyl diethyl phosphate molecules disclosed by the invention has the detection principle shown in a figure 1, and mainly comprises the following steps of:
(1) the Ag NPs prepared by the method and chloromethyl diethyl phosphate molecules are adsorbed on the surfaces of the silver nanoparticles through the action between halogen bonds; the particle size of the silver nanoparticle sol is adjustable within the range of 40-120 nm;
(2) adding high-concentration inorganic salt to induce the silver nanoparticle sol to agglomerate; the high-concentration inorganic salt is a halogen salt solution with sodium and potassium ions as cations and with a concentration of 0.3-3M.
(3) And performing Raman spectrum detection to obtain a characteristic Raman peak of the chloromethyl diethyl phosphate molecule, and performing qualitative and quantitative analysis on the chloromethyl diethyl phosphate molecule according to the peak position and the peak intensity. Here to be at 1073cm-1And (3) performing qualitative and quantitative analysis on chloromethyl diethyl phosphate molecules in the sample to be detected by taking the characteristic Raman peaks of the left and right P-O as a reference.
Examples
1. Reagent preparation
Sodium bromide (analytically pure) and chloromethyl diethyl phosphate (analytically pure) are all produced by chemical reagents of national drug group, ltd; polystyrene 96-well plate for detection (Corning corporation, USA)
2. Instrument preparation
The method comprises the following steps:
(1) synthesizing silver nanoparticles:
and (3) synthesis of silver species: 1mL of an aqueous sodium citrate solution (1 wt%), 0.25mL of an aqueous silver nitrate solution (1 wt%), and 0.2mL of an aqueous sodium chloride solution (20mM) were sequentially added to 1.05mL of water at room temperature and sonicated in a sonicator for 5 minutes to give solution A. Add 80. mu.L of 0.1M AA aqueous solution to 47.5mL boiling water and mix well for 1 minute to obtain solution B. And quickly adding the solution A into the solution B, continuously heating and stirring for 1h, and cooling to room temperature to obtain the bright yellow Ag NPs sol.
Removing impurities of silver seeds: 10mL of this bright yellow Ag NPs sol was added to a centrifuge tube, and then 2.5mL10 was added to the centrifuge tube-3And M NaBr, fully mixing, centrifuging to remove supernatant, adding ultrapure water, and re-metering to 10mL, wherein the sol is used as a silver seed, and the particle size of the silver is about 34 nm.
Preparation of silver-ammonia complex: 2mL of AgNO3The aqueous solution (1 wt%) was mixed with 800. mu.L of aqueous ammonia (25-28%) to prepare a silver-ammonia complex stock solution.
Preparation of Ag NPs: at room temperature, 10mL of silver seed was added to the round-bottom flask, 10mL of ultrapure water and 500. mu.L of 0.1M ascorbic acid solution were added to the round-bottom flask, and then 700. mu.L of 43mM silver ammonia complex solution was slowly added to the round-bottom flask by a peristaltic pump under magnetic stirring. After the reaction is carried out for more than 1h, supernatant liquor is removed by centrifugation, ultrapure water is added, the volume is increased to 20mL again, silver nanoparticle sol for the SERS substrate is obtained, and the particle size of the silver nanoparticles is about 75 nm. Assembling the nano particles on a silicon wafer, and placing the silicon wafer under a scanning electron microscope to obtain an SEM image shown in figure 2;
(2) six chloromethyl diethyl phosphate solutions with different concentration gradients of 1000mg/L, 500mg/L, 200mg/L, 100mg/L, 50mg/L and 10mg/L are respectively prepared and are shaken by hand to be uniformly mixed;
(3) taking 50 mu L of the silver nanoparticle sol for the SERS substrate, putting the silver nanoparticle sol into a 96-well plate, adding 200 mu L of chloromethyl diethyl phosphate solution with different concentrations, and finally adding 50 mu L of sodium bromide solution to form a mixed solution to be detected;
(4) placing the mixture to be tested in a Raman spectrometer to obtain a Raman spectrogram shown in figure 3 and a curve chart shown in figure 4 at 1073cm-1Is a characteristic Raman peak of chloromethyl diethyl phosphate molecule P-O, the lowest detectable concentration is 50mg/L, the linearity is good in the range of 50-1000mg/L, R2The qualitative and quantitative analysis of chloromethyl diethyl phosphate molecules in the samples to be tested was carried out at 0.995.
Comparative example
Preparation method of silver nanoparticles
And (3) synthesis of silver species: 1mL of an aqueous sodium citrate solution (1 wt%), 0.25mL of an aqueous silver nitrate solution (1 wt%), and 0.2mL of an aqueous sodium chloride solution (20mM) were successively added to 1.05mL of water with stirring at room temperature. After 5 minutes of premixing, the silver citrate sodium chloride premix was quickly added to 47.5mL of boiling water. Note that 80. mu.L of aqueous AA (0.1M) must be added to boiling water 1 minute before the premix is added. After heating and stirring for 1 hour, the resulting solution was allowed to cool to room temperature to finally obtain a bright yellow sol as a silver seed.
Preparation of Ag NPs: 200 μ L of the silver nanoparticle stock solution was added to water (4.73mL) and stirred at room temperature in a 10mL glass vial. Subsequently, an aqueous solution of silver ammonia complex (70 μ L, 43mM) and an aqueous AA solution (2mL, 2.5mM) were added successively to a 10mL glass bottle. After stirring for 1h, the resulting Ag NPs were concentrated by centrifugation and redispersed in an aqueous solution of sodium citrate (0.02 wt%) for storage; the particle size of the obtained silver nano particles is about 85 nm;
the silver nanoparticle sol of the comparative example was used as the SERS substrate, and the detection method for diethyl chloromethyl phosphate was the same as in example 1.
Referring to FIG. 3, it can be seen from example 1 and comparative example that chloromethyl diethyl phosphate showed only a weak signal at 1000ppm in the comparative example, whereas chloromethyl diethyl phosphate showed a clear signal at 50ppm in the example.
The above examples are only used to further illustrate the preparation method and application of the high-sensitivity SERS substrate of the present invention, but the present invention is not limited to the examples, and any simple modification, equivalent change and modification made to the above examples according to the technical spirit of the present invention fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a high-sensitivity SERS substrate is characterized by comprising the following steps:
1) mixing 0.5-1.5 wt% of sodium citrate aqueous solution, 0.5-1.5 wt% of silver nitrate aqueous solution, 15-25 mM of sodium chloride aqueous solution and ultrapure water according to a volume ratio of 0.5-1.5: 0.1-0.4: 0.1-0.3: 0.8-1.5 to obtain a mixed solution A; adding the mixed solution A into boiling water containing 10-30 mM ascorbic acid, continuously heating and stirring for 40-80 min, and cooling to room temperature to obtain a first silver nanoparticle sol;
2) mixing the first silver nanoparticle sol with the volume of V1 and the first silver nanoparticle sol with the volume of 0.5 multiplied by 10-3～2×10-3M NaBr solution is prepared by mixing the following components in a volume ratio of 3-5: 1, mixing, centrifuging, removing supernatant, adding ultrapure water, and metering the volume to V1 again to obtain silver seeds;
3) silver seeds with the volume of V2, ultrapure water with the volume of V3 and 0.1M ascorbic acid solution are mixed according to the volume ratio of 5-15: 5-15: 0.1-0.8, slowly adding 30-50 mM silver-ammonia complex solution into the mixed solution B under the stirring state, fully reacting for more than 1h, centrifugally removing supernatant, adding ultrapure water, and fixing the volume to V2+ V3 again to obtain second silver nanoparticle sol serving as a high-sensitivity SERS substrate.
2. The method for preparing the high-sensitivity SERS substrate according to claim 1, wherein: the particle size of the silver nanoparticles of the first silver nanoparticle sol is 15-50 nm.
3. The method for preparing the high-sensitivity SERS substrate according to claim 1, wherein: the silver nanoparticle particle size of the second silver nanoparticle sol is 40-120 nm.
4. The method for preparing the high-sensitivity SERS substrate according to claim 1, wherein: in the step 1), the volume ratio of the mixed solution A to boiling water containing 0.05-0.15M ascorbic acid is 1: 15 to 25.
5. The method for preparing the high-sensitivity SERS substrate according to claim 1, wherein: in the step 3), the volume ratio of the silver-ammonia complex solution to the mixed solution B is 1: 7 to 440.
6. A detection method of trace chloromethyl diethyl phosphate is characterized by comprising the following steps:
1) mixing the second silver nanoparticle sol of any one of claims 1 to 5 with a sample to be tested, and then adding a halogen salt solution with a concentration of 0.3-3M to form a mixed solution to be tested;
2) placing the mixed solution to be detected in a Raman spectrometer for detection at 1073cm-1According to the characteristic Raman peak, the qualitative and quantitative detection is carried out on the chloromethyl diethyl phosphate in the sample to be detected according to the peak position and the peak intensity.
7. The method for detecting trace chloromethyl diethyl phosphate according to claim 6, characterized in that: the volume ratio of the second silver nanoparticle sol to the sample to be detected to the halogen salt solution is 1: 3-5: 0.5 to 1.5.
8. The method for detecting trace chloromethyl diethyl phosphate according to claim 6, characterized in that: the halide salt solution comprises an aqueous solution of NaF, NaCl, NaBr, KF, KCl or KBr.
9. The method for detecting trace chloromethyl diethyl phosphate according to claim 8, characterized in that: the concentration of the halogen salt solution is 0.3-1M.
10. The method for detecting trace chloromethyl diethyl phosphate according to claim 6, characterized in that: the lowest detectable concentration of chloromethyl diethyl phosphate was 50 mg/L.
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| CN102259190A (en) * | 2011-06-16 | 2011-11-30 | 浙江科创新材料科技有限公司 | Method for quickly preparing nano silver wires with high length-diameter ratio in large batch |
| CN109500404A (en) * | 2018-12-24 | 2019-03-22 | 山东大学 | The synthetic method of water-soluble mono dispersion large scale spherical shape silver nano-grain |
| WO2020252042A1 (en) * | 2019-06-13 | 2020-12-17 | The Board Of Trustees Of The Leland Stanford Junior University | Surface enhanced raman scattering nanoparticles and their use in detecting and imaging oxidative stress |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102259190A (en) * | 2011-06-16 | 2011-11-30 | 浙江科创新材料科技有限公司 | Method for quickly preparing nano silver wires with high length-diameter ratio in large batch |
| CN109500404A (en) * | 2018-12-24 | 2019-03-22 | 山东大学 | The synthetic method of water-soluble mono dispersion large scale spherical shape silver nano-grain |
| WO2020252042A1 (en) * | 2019-06-13 | 2020-12-17 | The Board Of Trustees Of The Leland Stanford Junior University | Surface enhanced raman scattering nanoparticles and their use in detecting and imaging oxidative stress |
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