CN116539584A - Ultra-high sensitivity SERS hydrogen sulfide detection method - Google Patents
Ultra-high sensitivity SERS hydrogen sulfide detection method Download PDFInfo
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 70
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 55
- 238000001514 detection method Methods 0.000 title claims abstract description 50
- 230000035945 sensitivity Effects 0.000 title claims abstract description 27
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000004332 silver Substances 0.000 claims abstract description 38
- 229910052709 silver Inorganic materials 0.000 claims abstract description 37
- 239000013081 microcrystal Substances 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 6
- 229910052946 acanthite Inorganic materials 0.000 claims abstract description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 31
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 23
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 22
- 239000012279 sodium borohydride Substances 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 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 16
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 claims description 13
- 239000003446 ligand Substances 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 108010024636 Glutathione Proteins 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- 229960003180 glutathione Drugs 0.000 claims description 8
- 235000003969 glutathione Nutrition 0.000 claims description 8
- 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 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- 229960001790 sodium citrate Drugs 0.000 claims description 8
- 235000011083 sodium citrates Nutrition 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000005580 one pot reaction Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
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- 201000010099 disease Diseases 0.000 abstract description 4
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 abstract description 3
- 230000005672 electromagnetic field Effects 0.000 abstract description 3
- 229940056910 silver sulfide Drugs 0.000 abstract description 2
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000012544 monitoring process Methods 0.000 abstract 1
- 210000003296 saliva Anatomy 0.000 description 9
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
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Classifications
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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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/2202—Preparing specimens therefor
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/225—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion
- G01N23/2251—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion using incident electron beams, e.g. scanning electron microscopy [SEM]
-
- 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
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses an ultra-high sensitivity SERS hydrogen sulfide detection method, and belongs to the field of analysis and detection. According to the invention, by rapidly and quantitatively etching the SERS substrate by trace hydrogen sulfide in the sample, ultrahigh-sensitivity detection of hydrogen sulfide which is inversely related to a reporter SERS signal is realized without sample pretreatment. According to the invention, large-area silver microcrystals based on solvent assistance and lattice constraint are used as SERS substrates, the surface nanoparticles are uniform in particle size and interval, ultrahigh SERS signal enhancement is realized, and the reporter molecules with high Raman activity can be detected at a molecular level. The invention utilizes more than 10 49 The silver sulfide binding constant of the substrate is etched by the ultra-trace hydrogen sulfide, the distance is linearly increased along with the concentration of the hydrogen sulfide, the surface electromagnetic field enhancement is exponentially reduced, and the ultra-high sensitivity detection of the hydrogen sulfide in the sample is realized. The sample remover of the inventionThe consumption is as low as mu L, the sensitivity is as high as pmol/L, and the method has wide application prospect in the fields of environmental water quality detection, human disease monitoring and the like.
Description
Technical Field
The invention relates to an ultra-high sensitivity SERS hydrogen sulfide detection method, and belongs to the field of analysis and detection.
Background
Hydrogen sulfide has been demonstrated clinically and biomedicine as an important marker in the diagnosis of cardiovascular and nervous system related diseases, such as circulatory shock, diabetes, pancreatitis, hemorrhagic shock, endotoxin shock, and the like. The existing detection methods such as etiology, immunological detection, gas chromatography and the like have high requirements on samples, and complex methods such as marrow puncture and the like are required to sample, so that the pain of a patient is increased, the diagnosis of diseases is hindered, and the burden of the patient is increased. As one of the bedside tests, saliva examination by hydrogen sulfide can provide a noninvasive and simple diagnosis of these diseases. However, due to the high cytotoxicity of hydrogen sulfide, which affects normal physiological activities of cells even at nmol/L level, the required saliva detection method needs to have high sensitivity, and the current novel detection methods such as fluorescence spectrum and electrochemical detection are difficult to be applied to hydrogen sulfide breath analysis due to large sample size, insufficient sensitivity and the like.
As a novel detection means, the surface enhanced Raman spectrum (surface enhanced Raman scattering) has the advantages of no damage, high detection speed, high sensitivity, no need of complex sample pretreatment, capability of providing molecular fingerprint information and the like, and has wide application prospects in the aspects of food safety, environment detection, biological medicine and the like. Compared with the common Raman spectrum, the high sensitivity of the surface enhanced Raman scattering method is generated largely due to the optical resonance characteristics of the nano-structured coinage metal as the surface enhanced Raman scattering substrate: excitation of surface plasmon resonance can significantly enhance the surrounding local electromagnetic field strength. The process of local electromagnetic field enhancement generation has the following two steps: 1. under the irradiation of incident light, the nano particles are used as plasmonsLocal plasma enhancement is generated. The nanoparticles act as an optical receiving antenna to convert the far field into the near field; 2. raman polarizability derivations from molecular-nanoparticle systems. By reasonably designing the size (20-200 nm) of the material to improve the coupling of the material to the frequency of incident light, designing a highly-limited gap structure (1-10 nm), and distributing high-density nano particles under light spots, the surface enhanced Raman scattering substrate can realize the maximum of 10% of molecules to be detected compared with the original Raman signal 8 Enhancement of magnification.
The existing surface enhanced Raman scattering method for detecting hydrogen sulfide has low sensitivity and is difficult to be applied to hydrogen sulfide saliva inspection, and the reason is that 1. The recognition probe on the surface of the surface enhanced Raman scattering substrate is combined with hydrogen sulfide through intermolecular force, the combination constant is low (log Ka range 3-5), and trace and ultra trace hydrogen sulfide molecules in the solution are difficult to recognize; 2. the raman activity of the reporter molecule specifically selected for hydrogen sulfide or hydrogen sulfide recognition probes can also reduce the sensitivity to hydrogen sulfide detection due to limited selection range; 3. the common nano silver sol is used as a surface enhanced Raman scattering substrate, and is aggregated after an aggregation agent (generally high-concentration salt solution) is added, so that the polymer with a nano gap is formed, but the aggregation depends on coulomb force, the gap is unstable in the process of generating Brownian motion, the standard deviation of a surface enhanced Raman scattering signal obtained through surface enhanced Raman scattering enhancement is larger, and the sensitivity of a detection method is further reduced.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an ultrahigh-sensitivity SERS hydrogen sulfide detection method.
The invention provides an ultra-high sensitivity SERS hydrogen sulfide detection technology, which comprises the following steps:
1) Mixing silver microcrystals with a solution containing dissolved oxygen and a reporter molecule to obtain a hydrogen sulfide detection SERS substrate; the surface of the silver microcrystal in the step 1) is distributed with nano silver particles with uniform particle size and uniform interval; the grain diameter of the nano silver particles on the surface of the silver microcrystal ranges from 20 nm to 200nm; the interval value range of the nano silver particles on the surface of the silver microcrystal is 1-10nm; the silver crystallite size is 1-10 mu m;
2) Mixing standard samples with different concentrations and containing molecules to be detected of hydrogen sulfide with the hydrogen sulfide detection SERS substrate obtained in the step 1), placing the mixed standard samples under a Raman spectrometer for SERS detection, and establishing a quantitative curve according to the linear relation between the Raman signal intensity of the reporter molecule and the concentration of hydrogen sulfide;
3) Mixing a sample to be detected containing hydrogen sulfide with unknown concentration with the hydrogen sulfide detection SERS substrate obtained in the step 1), placing the mixture under a Raman spectrometer for SERS detection, and calculating the corresponding hydrogen sulfide concentration in the sample to be detected according to the Raman signal intensity of the reporter molecule according to the quantitative curve established in the step 2).
As a preferred embodiment of the present invention, the hydrogen sulfide detection SERS substrate in the step 1) is prepared by the following method:
a) The silver chloride cubic microcrystal is prepared by a one-pot method: mixing tetrapropylammonium chloride aqueous solution with ethylene glycol, then adding silver nitrate aqueous solution, and controlling the adding amount to ensure that the molar ratio of the silver nitrate to the tetrapropylammonium chloride is 0.05-0.2; after the reaction is finished, centrifuging the obtained product, and cleaning to obtain silver chloride cubic microcrystals;
b) Preparation of solvent-assisted and silver chloride lattice-constrained array SERS substrates: preparing a sodium borohydride solution containing a ligand modifier under magnetic stirring, wherein the ligand modifier comprises polyvinylpyrrolidone, sodium citrate, ascorbic acid and glutathione, and the concentration of the polyvinylpyrrolidone is 10 -4 -5×10 -4 M, the concentration ratio of each component is 10:100:1:1, a step of; the molar ratio of the sodium borohydride to the polyvinylpyrrolidone is 2 multiplied by 10 2 -2 x 10; adding the cubic silver chloride microcrystal prepared in the step a into the sodium borohydride solution containing the ligand modifier, and directly reducing silver chloride by sodium borohydride to generate nano silver particles with uniform particle size and uniform interval, wherein the molar ratio of the cubic silver chloride microcrystal to the sodium borohydride is 0.2-1; and stirring until the reaction is finished, and cleaning to obtain the hydrogen sulfide detection SERS substrate.
As a preferred scheme of the invention, in the step a), the concentration of tetrapropylammonium chloride in the tetrapropylammonium chloride aqueous solution is 0.1-0.2M; the volume ratio of the tetrapropylammonium chloride aqueous solution to the ethylene glycol is 0.05-0.1. Preferably, the reaction time described in step a) is from 10 to 30 minutes.
As a preferable scheme of the invention, the silver chloride cubic microcrystals prepared in the step a) have uniform morphology and dimension and the side length is 1-5 mu m.
As a preferred embodiment of the invention, the reaction time in step b) is from 10 to 30 minutes.
As a preferable mode of the present invention, in the step 1), the concentration of the dissolved oxygen is 3mg/L to 8mg/L; the reporter molecule is one of rhodamine, crystal violet and methyl orange, and the concentration is 10 -6 -10 -10 M。
Compared with the prior art, the hydrogen sulfide detection SERS substrate provided by the invention has the nano silver particle polymer with the fixed nano gap. This means that the SERS enhancement effect is stable and highly sensitive. The gap is enlarged under the etching of hydrogen sulfide, so that the SERS enhancement effect is attenuated rapidly, and the whole attenuation process liquid is observed to be stable. There are many reported methods for preparing such immobilization site nanoparticles, such as photolithography on existing immobilization carriers, or sputter growth, etc.
The ability to generate high intensity localized plasmon resonance also requires that the metal possess an imaginary dielectric constant close to 0 and a suitable real power saving constant. The metallic materials satisfying the above conditions have been reported to be limited to silver, gold, copper, and arranged in descending order according to the reinforcing effect. Hydrogen sulfide is incapable of inducing covalent precipitation of gold and copper. Thus, the SERS substrate material employed in the present invention needs to be metallic silver.
The invention can generate local plasma resonance in the gaps of the nano silver particles at the fixed sites to form hot spots, and can stably enhance the Raman signals of the report molecules in the gaps. When an oxidizing agent such as oxygen dissolved in water is present in the solution, the silver sulfide has an ultra-high binding constant (10) 49 ) The covalent precipitation reaction of the nano particles and the dissolved oxygen can be quickened, and the spacing between the particles is enlarged when the surfaces of the nano silver particles are etched. Due to SERS enhancementThe effect can exponentially decrease along with the increase of the spacing of the nano particles, the invention changes the spacing of the nano particles through oxidation etching, and the concentration of hydrogen sulfide contained in the solution is quantitatively detected with high sensitivity according to the linear relation between the signal change of the reporter molecule such as rhodamine added in the solution and the concentration of hydrogen sulfide contained in the object to be detected.
The invention uses nano silver to replace supermolecule as recognition probe, and has higher binding constant (log K) a =49 > 5), a lower concentration of hydrogen sulfide can be identified.
According to the invention, the fixed point silver nanoparticle spacing is changed through etching of hydrogen sulfide, so that the Raman signal is exponentially changed, and the sensitivity detection is realized. The invention does not need an aggregating agent to aggregate the nano silver particles, the operation is simpler, and the detection time is greatly shortened.
According to the invention, any reporter molecule can be used without a recognition probe specific to hydrogen sulfide or hydrogen sulfide, for example, rhodamine capable of realizing single-molecule detection is selected, so that the sensitivity is further improved.
Drawings
Fig. 1 shows an SEM image of the synthesized silver chloride;
fig. 2 shows an SEM image of the synthesized silver crystallites;
FIG. 3 shows the detection 10 of the crystallites of the synthesized silver -14 -10 -10 A Raman spectrum obtained by M rhodamine;
FIG. 4 shows a schematic diagram of the present invention;
FIG. 5 shows the detection of different concentrations of Na 2 S, a result diagram;
FIG. 6 shows commercially available nano silver particles for Na detection 2 S result diagram.
Detailed Description
The invention is further illustrated and described below in connection with specific embodiments. The described embodiments are merely exemplary of the present disclosure and do not limit the scope. The technical features of the embodiments of the invention can be combined correspondingly on the premise of no mutual conflict.
Example 1
Preparation of silver crystallites:
(1) Preparation of cubic silver chloride microcrystals with uniform morphology and size
2mL of 1.5M tetrapropylammonium chloride aqueous solution and 20mL of ethylene glycol are added into a 50mL round bottom flask, then 0.3mL of 1M silver nitrate aqueous solution is rapidly added, after reaction for 10min at room temperature, the obtained product is centrifuged, and the product is washed twice with absolute ethyl alcohol and deionized water, thus obtaining cubic silver chloride microcrystals with uniform size and about 3 μm.
(2) Preparation of solvent-assisted and silver chloride lattice-constrained array silver crystallites
Preparing 1mL of sodium borohydride solution containing ligand modifier under magnetic stirring, sequentially adding polyvinylpyrrolidone, sodium citrate, ascorbic acid and glutathione according to the sequence, wherein the concentration of polyvinylpyrrolidone, sodium citrate, ascorbic acid and glutathione in the final solution is 10 in sequence -4 mol/L，10 -3 mol/L，10 -5 mol/L，10 -5 mol/L, adding sodium borohydride at the end, wherein the final concentration of sodium borohydride is 5 multiplied by 10 -3 M, 0.5mg of the silver chloride cubic microcrystal prepared in the step (1) is added into 1.0mL of sodium borohydride solution containing the ligand modifier, and the mixture is stirred and reacted for 10min. Subsequently, the obtained reaction product was washed three times with deionized water to prepare silver crystallites.
Scanning electron microscope test of SERS substrate:
the scanning electron microscope image of the silver chloride cubic microcrystals with uniform morphology and size prepared in the step (1) of the embodiment is shown in figure 1, and the image can be seen by observing the image, so that the prepared silver chloride cubic microcrystals have uniform morphology and size, a cubic structure and clear edges and corners; the side length of the cubic silver chloride crystallites is about 3 μm.
The scanning electron microscope image of the solvent-assisted and silver chloride lattice-constrained array silver crystallites prepared in step (2) of this example is shown in fig. 2, and it can be seen from the image that the prepared silver crystallites still maintain a cubic outline as a whole, and the surface of the silver crystallites obtained by this preparation method is substantially uniformly covered with silver nanoparticles, the size of which is about 30nm, and the pitch is about 1 nm.
Characterization of the properties of SERS substrates
Sensitivity test
10. Mu.L, 0.1mg/mL silver crystallite SERS substrate prepared in this example was immersed to a series of concentrations of the same volume (10 -12 M to 10 -16 M) in rhodamine (R6G) aqueous solution, soaking for 30min, and taking out the substrate for SERS test. The 532nm laser is used as a light source, the acquisition time is 20s, and the detection result is shown in figure 3.
FIG. 3 shows that R6G is at 610cm -1 The characteristic peak intensity is plotted against the concentration of R6G molecules, and it can be seen from the graph that the concentration of R6G is 10 -14 M and 10 -10 Within M range, 610cm in spectrum -1 The Raman characteristic peak intensity and the corresponding R6G concentration at the position show obvious linear relation on a logarithmic scale, and the linear relation is as follows: y= 9582.64log (X) +126263, linear correlation coefficient R 2 =0.977, limit of detection 8.4×10 -14 mol/L. From this, the silver microcrystalline SERS substrate prepared in this example has good sensitivity.
Example 2
Preparation of silver crystallites:
(1) Preparation of cubic silver chloride microcrystals with uniform morphology and size
1mL of 2M tetrapropylammonium chloride aqueous solution and 20mL of ethylene glycol were added to a 50mL round bottom flask, then 0.2mL of 0.5M silver nitrate aqueous solution was rapidly added, after reacting at room temperature for 10min, the obtained product was centrifuged, and washed twice with absolute ethanol and deionized water, to obtain cubic crystallites of silver chloride of uniform size of about 3. Mu.m.
(2) Solvent-assisted and silver chloride lattice-constrained array silver crystallite preparation
Preparing 1mL of sodium borohydride solution containing ligand modifier under magnetic stirring, sequentially adding polyvinylpyrrolidone, sodium citrate, ascorbic acid and glutathione according to the sequence, wherein the concentration of polyvinylpyrrolidone, sodium citrate, ascorbic acid and glutathione in the final solution is 5×10 in sequence -4 mol/L，5×10 -3 mol/L，5×10 -5 mol/L，5×10 -5 mol/L, adding sodium borohydride at the end, wherein the final concentration of sodium borohydride is 3 multiplied by 10 -2 M, step 0.5mgThe silver chloride cubic microcrystal prepared in the step (1) is added into 1.0mL of sodium borohydride solution containing the ligand modifier, and the mixture is stirred and reacted for 10min. Subsequently, the obtained reaction product was washed three times with deionized water to prepare silver crystallites.
The characterization result of the scanning electron microscope shows that the performance stability and the sensitivity of the SERS substrate of the silver microcrystal prepared in the embodiment 2 are equal to those of the embodiment 1.
Example 3
Preparation of silver crystallites:
(1) Preparation of cubic silver chloride microcrystals with uniform morphology and size
1mL of 1M tetrapropylammonium chloride aqueous solution and 20mL of ethylene glycol were added to a 50mL round bottom flask, then 0.2mL of 0.5M silver nitrate aqueous solution was rapidly added, after reacting at room temperature for 10min, the obtained product was centrifuged, and washed twice with absolute ethanol and deionized water, to obtain cubic crystallites of silver chloride of uniform size of about 3. Mu.m.
(2) Preparation of solvent-assisted and silver chloride lattice-constrained array silver crystallites
Preparing 1mL of sodium borohydride solution containing ligand modifier under magnetic stirring, sequentially adding polyvinylpyrrolidone, sodium citrate, ascorbic acid and glutathione according to the sequence, wherein the concentration of polyvinylpyrrolidone, sodium citrate, ascorbic acid and glutathione in the final solution is 5×10 in sequence -3 mol/L，5×10 -5 mol/L，5×10 -5 mol/L，5×10 -5 mol/L, adding sodium borohydride at the end, wherein the final concentration of sodium borohydride is 5 multiplied by 10 -1 M, 0.5mg of the silver chloride cubic microcrystal prepared in the step (1) is added into 1.0mL of sodium borohydride solution containing the ligand modifier, and the mixture is stirred and reacted for 10min. Subsequently, the obtained reaction product was washed three times with deionized water to prepare silver crystallites.
The characterization result of the scanning electron microscope shows that the performance stability and the sensitivity of the SERS substrate of the silver microcrystal prepared in the embodiment 3 are equal to those of the embodiment 1.
Example 4
Unlike the very slow redox reaction to the silver nanoparticles on the surface in the presence of oxygen alone, the ion-induced covalent precipitation that occurs in the presence of both oxygen and hydrogen sulfide can achieve etching of the silver nanoparticles in a short time, expanding the nanoslit between the fixed site nanoparticles, as shown in fig. 4.
Hydrogen sulfide detection sensitivity test
10mL of 0.1mg/L silver crystallites prepared in this example 1 were mixed with an aqueous rhodamine solution containing 3mg/L oxygen, then with the same volume of a series of concentrations (10 -9 M to 10 -14 M) after 5min of mixed soaking in hydrogen sulfide, the substrate was removed for SERS testing. A532 nm laser is used as a light source, the acquisition time is 20s, and the detection result is shown in FIG. 5.
FIG. 5 shows that R6G is at 610cm -1 The characteristic peak intensity is plotted against the hydrogen sulfide concentration, and it can be seen from the graph that the hydrogen sulfide concentration is 10 -14 M and 10 -9 Within M range, 610cm in spectrum -1 Raman characteristic peak intensity at 10 -13 -10 -9 M hydrogen sulfide concentration shows obvious linear relation on logarithmic scale, and the linear relation is: i= -1103.46log (C) -8791.14, linear correlation coefficient R 2 =0.981, limit of detection 3.4x10 -13 mol/L. Therefore, the silver cubic microcrystal SERS substrate prepared by the embodiment has good sensitivity to hydrogen sulfide detection.
Comparative example 1
Common nano silver sol purchased from Nanjing Xianfeng nano materials science and technology Co., ltd, was mixed with rhodamine water solution containing 3mg/L oxygen, and then mixed with a series of concentrations (10) -9 M to 10 -14 M) after 5min of mixed soaking in hydrogen sulfide, the substrate was removed for SERS testing. A532 nm laser is used as a light source, the acquisition time is 20s, and the detection result is shown in FIG. 6.
FIG. 6 is a graph of R6G at 610cm -1 The characteristic peak intensity is plotted against the hydrogen sulfide concentration, and it can be seen from the graph that the hydrogen sulfide concentration is 10 -14 M and 10 -9 Within M range, 610cm in spectrum -1 The Raman characteristic peak intensity and the hydrogen sulfide concentration at the position completely do not show any linear relation on a logarithmic scale, and the linear correlation coefficient R 2 ＝0.06<0.765 (99% confidence).
Example 5
In order to examine the practical application of the method in saliva samples, the detection of hydrogen sulfide in saliva is examined.
mu.L of the silver cubic microcrystal SERS substrate prepared in example 1 was mixed with 1. Mu.L of 10% oxygen containing 3mg/L - 9 mixing mol/L rhodamine water solution, then mixing with saliva samples with the same volume and 5 hydrogen sulfide concentrations, and placing under a Raman spectrometer for a labeling recovery experiment. The concentration of hydrogen sulfide added to the saliva samples was 1pmol/L,10pmol/L,50pmol/L,100pmol/L, and 500pmol/L, respectively. And 532nm laser is used as a light source, and the acquisition time is 20s.
The detection result is shown in table 1, the recovery rate of the method is between 95.2 and 119 percent, and the quantitative ultrasensitive detection of hydrogen sulfide can be successfully realized in saliva samples.
TABLE 1 Hydrogen sulfide labeling recovery test results in saliva samples
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention.
Claims (6)
1. The ultra-high sensitivity SERS hydrogen sulfide detection method is characterized by comprising the following steps of:
1) Mixing silver microcrystals with a solution containing dissolved oxygen and a reporter molecule to obtain a hydrogen sulfide detection SERS substrate; the surface of the silver microcrystal is distributed with nano silver particles with uniform particle size and uniform interval; the grain diameter of the nano silver particles on the surface of the silver microcrystal ranges from 20 nm to 200nm; the interval value range of the nano silver particles on the surface of the silver microcrystal is 1-10nm; the silver crystallite size is 1-10 mu m;
2) Mixing standard samples with different concentrations and containing molecules to be detected of hydrogen sulfide with the hydrogen sulfide detection SERS substrate obtained in the step 1), placing the mixed standard samples under a Raman spectrometer for SERS detection, and establishing a quantitative curve according to the linear relation between the Raman signal intensity of the reporter molecule and the concentration of hydrogen sulfide;
3) Mixing a sample to be detected containing hydrogen sulfide with unknown concentration with the hydrogen sulfide detection SERS substrate obtained in the step 1), placing the mixture under a Raman spectrometer for SERS detection, and calculating the corresponding hydrogen sulfide concentration in the sample to be detected according to the Raman signal intensity of the reporter molecule according to the quantitative curve established in the step 2).
2. The ultra-high sensitivity SERS hydrogen sulfide detection method according to claim 1, wherein the silver crystallites in step 1) are prepared by:
a) The silver chloride cubic microcrystal is prepared by a one-pot method: mixing tetrapropylammonium chloride aqueous solution with ethylene glycol, then adding silver nitrate aqueous solution, and controlling the adding amount to ensure that the molar ratio of the silver nitrate to the tetrapropylammonium chloride is 0.05-0.2; after the reaction is finished, centrifuging the obtained product, and cleaning to obtain silver chloride cubic microcrystals;
b) Preparation of solvent-assisted and silver chloride lattice-constrained array SERS substrates: preparing a sodium borohydride solution containing a ligand modifier under magnetic stirring, wherein the ligand modifier comprises polyvinylpyrrolidone, sodium citrate, ascorbic acid and glutathione, and the concentration of the polyvinylpyrrolidone is 10 -4 -5×10 -4 M, the molar concentration ratio of each component is 10:100:1:1, a step of; the molar ratio of the sodium borohydride to the polyvinylpyrrolidone is 2 multiplied by 10 to 2 multiplied by 10 2 The method comprises the steps of carrying out a first treatment on the surface of the Adding the cubic silver chloride microcrystal prepared in the step a into the sodium borohydride solution containing the ligand modifier, and directly reducing silver chloride by sodium borohydride to generate nano silver particles with uniform particle size and uniform interval, wherein the molar ratio of the cubic silver chloride microcrystal to the sodium borohydride is 0.2-1; and stirring until the reaction is finished, and cleaning to finally obtain the silver microcrystal.
3. The method for detecting ultra-high sensitivity SERS hydrogen sulfide according to claim 2, wherein in step a), the concentration of tetrapropylammonium chloride in the aqueous tetrapropylammonium chloride solution is 0.1 to 0.2M; the volume ratio of the tetrapropylammonium chloride aqueous solution to the ethylene glycol is 0.05-0.1.
4. The method for detecting the ultrahigh-sensitivity SERS hydrogen sulfide according to claim 4, wherein the silver chloride cubic microcrystals prepared in the step a) are uniform in morphology and dimension and have a side length of 1-5 μm.
5. The method for detecting ultrahigh-sensitivity SERS hydrogen sulfide according to claim 1, wherein in the step 1), the concentration of the dissolved oxygen is 3mg/L to 8mg/L.
6. The method for detecting ultra-high sensitivity SERS hydrogen sulfide according to claim 1, wherein in the step 1), the reporter molecule is an inert molecule which does not react with metallic silver or hydrogen sulfide and has raman activity, and the concentration range is 10 -6 -10 -10 mol/L。
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