CN108444977A - A kind of surface enhanced Raman substrate material, preparation method and applications for detecting water content in organic solvent - Google Patents
A kind of surface enhanced Raman substrate material, preparation method and applications for detecting water content in organic solvent Download PDFInfo
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- CN108444977A CN108444977A CN201810460852.7A CN201810460852A CN108444977A CN 108444977 A CN108444977 A CN 108444977A CN 201810460852 A CN201810460852 A CN 201810460852A CN 108444977 A CN108444977 A CN 108444977A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910001868 water Inorganic materials 0.000 title claims abstract description 62
- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 40
- 239000003960 organic solvent Substances 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 17
- 239000000758 substrate Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical class NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011324 bead Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 229940038773 trisodium citrate Drugs 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 26
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 9
- 239000000523 sample Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000004005 microsphere Substances 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 3
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229960001051 dimercaprol Drugs 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000004451 qualitative analysis Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 2
- 238000011002 quantification Methods 0.000 abstract 1
- 238000004457 water analysis Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 230000002522 swelling effect Effects 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- 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 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 241001365789 Oenanthe crocata Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000003705 background correction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 238000009659 non-destructive testing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000005220 pharmaceutical analysis Methods 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 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 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a kind of surface enhanced Raman substrate material, preparation method and applications for detecting water content in organic solvent.Preparation method includes the following steps：(1) with 4,4 '-'-dimercaprol azobenzene of p-Mercaptoaniline derivative for probe molecule, polyvinyl alcohol gel is modified；(2) microreactor prepares the smooth PVA DMAB microballoons of uniform particle diameter and surface；(3) PVA DMAB Ag Raman substrate materials are prepared in PVA DMAB microsphere surface loading nano silvery particles by growth in situ.Preparation method of the present invention is simple, fast quantification aqueous in organic solvent and qualitative analysis may be implemented in the Raman microprobe being prepared, have the advantages that can be used repeatedly, detection sensitivity it is low, it is with important application prospects in micro or trace water analysis detection field.
Description
Technical field
The invention belongs to surface Raman detection technique fields, specifically, are related to one kind and contain for detecting in organic solvent
The surface enhanced Raman substrate material of water, preparation method and applications.
Background technology
In organic chemical reactions, water content has weight to the product of reaction, yield and the selectivity of reaction in organic solvent
It influences, while an important indicator in the products such as the characterization of water content and medicine, chemical industry, food, therefore organic solvent
The measurement of middle water content is the problem analysis most often met.Therefore it is badly in need of wanting one kind can dynamic monitoring and portable detection means
It is measured analysis.
Currently, the detection method of minor amount of water mainly has the conventional methods such as dew point method, electrolysis, Karl_Fischer method, dew point method
The influence of various disturbing factors is all highly prone to electrolysis；Karl_Fischer method be at present use common detection methods, but this
There are many side reaction of method, need to consider several factors when detecting, especially pay attention to the choosing of the cleannes, titration parameters of titration cell
It selects, the relative humidity of pseudotitration terminal phenomenon and air.Existing literature is based on fluorescent technique, is used for Water in Organic Solvents content
The relevant report of the Optochemical sensor of measurement, according to molten in organic solvent by the porous polyethylene resin of salt groups containing season
Swollen, volume is 2-5 times in water, and this swelling action causes resin reflectance spectrum in different solvent phases different.It grinds
A kind of fiber optic sensor measuring water content in acetone is made.Therefore there is still a need for a kind of optical sensors of exploitation as inspection
Survey the sensitivity of water and the means that detection line is low.
In recent years, a kind of surface-enhanced Raman (SERS) spectral technique based on noble metal substrate causes the wide of researcher
General interest.SERS technologies since it is highly sensitive, limits low advantage without destructive, detection, be widely used in detecting biomolecule,
The fields such as food additives, metal ion.Dynamic hotspot can be generated since noble metal is close to each other to generate high electricity
Magnetic, and then generate stronger Raman signal.SERS technologies detect always specific molecule, in necks such as the residual detection of agriculture, Pharmaceutical Analysis
Domain is widely used, but the detection for being directed to water never carried out research, and the substrate of one side SERS needs sol form, itself with
Water is solvent, is on the other hand required for solution when detection, to achieve the effect that detection limit is low.Therefore the spy of Raman is developed
Property be applied to the detection right and wrong of water often with there is application prospect.
Invention content
In order to overcome the shortcomings of existing method in terms of detecting hydrone, the purpose of the present invention is to provide one kind for examining
Survey the surface enhanced Raman substrate material of water content, preparation method and applications in organic solvent.The present invention develops a kind of negative
Polyvinyl alcohol microparticles (PVA-DMAB-Ag) Raman substrate material of silver-carrying nano particle, it is qualitative by Surface enhanced Raman spectroscopy
With quantitative detection water content.The spacing that the silver ion for leading to be supported on microsphere surface can be expanded after microballoon absorbs water can be increasingly
Width can make the electromagnetism of the dynamic hotspot generated reduce, to which the Raman signal generated can also reduce.Surface-enhanced Raman exists
1140cm-1Linear reduction can be presented with microballoon water swelling in the DMAB characteristic peaks of appearance.Nanometer substrate prepared by this method
Material has many advantages, such as to prepare easy, surface topography uniform, controllable, while it is brand-new for the technology of detection water now to provide one kind
Thinking, bio-sensing, environmental monitoring and analysis and surface-enhanced Raman detection etc. fields be with a wide range of applications.
Technical scheme of the present invention is specifically described as follows.
A kind of preparation method for detecting the surface enhanced Raman substrate material of water content in organic solvent, specific steps
It is as follows：
(1) PVA-DMAB microballoons are prepared
Under 55-65 DEG C of water bath condition, after PVA, p-Mercaptoaniline aqueous solution and potassium peroxydisulfate are stirred evenly, pass through
Syringe pump sample introduction enters microreactor and polymerization curing reaction occurs, and after reaction, washing, drying are prepared dried
PVA-DMAB microballoons；Wherein：A concentration of 8-12mmol/L of p-Mercaptoaniline aqueous solution；PVA, p-Mercaptoaniline aqueous solution and mistake
The mass ratio of potassium sulfate is (4~6)：2：(0.025~0.035)；
(2) PVA-DMAB-Ag microballoons are prepared
Dried PVA-DMAB microballoons are first soaked and are swollen in deionized water, are added thereto later in equal volume
5~10mmol/L AgNO3The trisodium citrate aqueous solution of aqueous solution and 10~20mmol/L, reductase 12 0-30h, reacts at room temperature
After, the PVA-DMAB beads for having loaded Nano silver grain are taken out, 15-25min is dried in 120-125 DEG C of baking oven, prepares
Go out PVA-DMAB-Ag microballoons to get to the surface enhanced Raman substrate material for detecting water content in organic solvent.
In the present invention, in step (1), n-butyl acetate and ethyl acetate is used to wash successively when washing.
In the present invention, in step (1), drying temperature is 55-65 DEG C, and drying time is 6-10 hours.
In the present invention, in step (1), when sample introduction, flow velocity 1-3mL/min, sample injection time 8-12min, retention time
For 2.5-3.5h.
In the present invention, in step (2), PVA-DMAB microballoons and AgNO3The mass volume ratio of aqueous solution is 1:1~1:10g/
mL。
The present invention also provides the surface increasings for detecting water content in organic solvent made from a kind of above-mentioned preparation method
Hale graceful base material.
The present invention further provides a kind of above-mentioned surface enhanced Raman substrates for detecting water content in organic solvent
The application of material.The organic solvent is selected from one or more of ethyl alcohol, acetone, acetonitrile or dichloromethane.
Compared with existing analysis method, the device have the advantages that being：
1, the present invention designs the microballoon of the PVA-DMAB of the load Nano silver grain with Raman trait, has and prepares letter
The advantages that singly and capable of reusing.
2, the present invention using in situ synthesis in microsphere surface silver nanoparticles loaded, have surface topography uniform, controllable,
The advantages that Raman active is high；
3, the present invention uses Raman spectrum analysis method to carry out qualitative and quantitative detection to water content for the first time, when water contains in ethyl alcohol
For amount in 0.5-4vol%, water content and Raman signal have that responsiveness is fast, detection sensitivity is high at good linear relationship,
The advantages that non-destructive testing.
Description of the drawings
Fig. 1 is the scanning electron microscope diagram of the drying PVA-DMAB-Ag microballoons prepared in embodiment 1.
Fig. 2 is the microscope figure of PVA-DMAB-Ag microballoons in embodiment 1.
Fig. 3 is the Raman spectrogram of bead in the presence of the drying of embodiment 1 and water.
Fig. 4 is the Raman quantitative spectra figure of water in dry PVA-DMAB-Ag microballoons detection ethyl alcohol in application examples 1.
Fig. 5 is the linear relationship chart of water in dry PVA-DMAB-Ag microballoons detection ethyl alcohol in application examples 1.
Fig. 6 is the Raman spectrogram that dry PVA-DMAB-Ag microballoons detection different solvents water content is 2% in application examples 2.
Specific implementation mode
Technical scheme of the present invention is described in detail with reference to the accompanying drawings and examples.
Embodiment 1
(1) PVA-DMAB microballoons are prepared
It weighs 5g PVA and is dissolved in 60 DEG C of water-baths, oscillation shakes up, and adds the p-Mercaptoaniline aqueous solution of 2g 10mM, magnetic force
It stirs evenly, is slowly added to 30mg potassium peroxydisulfates, on the one hand crosslinking agent carries out the polymerization of PVA, while being catalyzed p-Mercaptoaniline
4,4 '-'-dimercaprol azobenzene DMAB are turned to, ultrasound removes bubble removing, prepares the sample introduction of syringe pump.By microreactor, flow velocity is set
2mL/min, sample injection time 10min, retention time 3h prepare PVA-DMAB microballoons by polymerizing curable.Successively just with acetic acid
Butyl ester, ethyl acetate washing, are put into 60 DEG C of oven drying 8h.
(2) PVA-DMAB-Ag microballoons are prepared
Dried PVA-DMAB beads are first immersed and are swollen in deionized water, take out the bead being swollen later
It is put into clean vial.Then 5mM AgNO are prepared3With 10mM citric acid three sodium solutions, 8.5mgAgNO is taken3With 29.4g lemons
Lemon acid trisodium is dissolved in respectively in 10mL deionized waters, takes the AgNO of equal volume3It is added to citric acid three sodium solution above-mentioned
Vial in, reductase 12 4h at room temperature.Silver nano-grain is prepared using reduction of sodium citrate method, is passing through primary reconstruction, profit
Bridging is carried out with the sulfydryl of DMAB and silver nano-grain, prepares PVA-DMAB-Ag microballoons, it is aobvious to preparing microballoon Scanning Electron
Micro mirror analyzes the upgrowth situation (Fig. 1) of Ag nano particles, it is seen that is uniformly distributed, has good Raman active.
(3) dried pellet is prepared
The PVA-DMAB beads for having loaded Nano silver grain taking-up is placed on drying and dehydrating in 120 DEG C of baking ovens, is taken after 20min
Go out, at room temperature kept dry.Obtained dried pellet can measure the characteristic peak of probe molecule by surface-enhanced Raman, for
Water absorption and swelling carries out the analysis of water content, the PVA-DMAB-Ag microballoons under the lower microscope of the macroscopic view as prepared by Fig. 2.
(4) the Raman qualitative detection of water
Investigate absorption swelling effect of the PVA-DMAB-Ag microballoons for water, aggregation for surface silver nano-grain and its
The dispersibility of hot spot carries out qualitative detection.It is measured using the Portable Raman spectrometer of 785nm excitation wavelengths, setting integral
Time 10000s.It takes a PVA-DMAB-Ag microballoon to put on the silicon die, acquires six points and measure SERS signal, as parallel
Experiment, reaches initial spectrum.Then a drop water is added dropwise on bead, after microballoon water absorption and swelling, acquires six points and measures SERS
Signal.Simultaneously using background correction, linear multi fitting correction baseline, such as Fig. 3 is added dropwise before water, and Raman shift is in 1140cm-1
There is apparent characteristic peak, is added dropwise after water, 1140cm-1Characteristic peak disappear, it was demonstrated that microspheres swell leads to Nano silver grain
Distance increases, the reduction of hot spot, and the characteristic peak of probe molecule disappears, this has important meaning for qualitative analysis detection water content
Justice.
Application examples 1
Water content in ethanol solution is detected using PVA-DMAB-Ag microballoons of the present invention, concrete operations are as follows
It is shown：
Two PVA-DMAB-Ag dried pellets that respectively prepared by embodiment 1 first are put on the silicon die, are acquired six points and are surveyed
Measure SERS signal.The ethyl alcohol of different moisture content is prepared, volume ratio is 0~20%, and microballoon is immersed in different concentration ethanol solution
In.After abundant water absorption and swelling, takes out bead and put on the silicon die, acquire six points and measure SERS signal, such as Fig. 4 can be seen
Go out swelling effect of the different moisture content to microballoon, Raman signal weakens as water content increases.In 1140cm-1Raman signal,
With gradually increasing for water content 0-10vol%, signal linear decrease is drawn in the case that water content is more than 10%
Graceful signal is preferably minimized, it was demonstrated that microballoon water absorption and swelling is saturated, and reaches hot spot minimum.As illustrated in fig. 5, when water content in ethyl alcohol
In 0.5-4vol%, water content is with Raman signal at good linear relationship, and by the fitting of straight line, linear equation is
I1140=-9.8 [H2O]+54.8, therefore the raman scattering intensity under ethyl alcohol difference water content can be become by measuring PVA-DMAB-Ag
Change, obtains true water content in solution.
Application examples 2
In order to verify response of the PVA-DMAB-Ag microballoons to water content, the Raman spectrum of the water content of different solvents is measured,
The organic reagent of selection is that analysis is pure, and ethyl alcohol, dichloromethane, acetone, acetonitrile and its mixing respectively is investigated as different solvents
The property of PVA-DMAB-Ag microballoons.2% solution of water content is prepared respectively, microballoon is placed in one, and acquires raman spectral signal,
As shown in fig. 6, the microballoon Raman spectrogram of acetone, ethyl alcohol, acetonitrile, dichloromethane and its four kinds of mixed solutions, the results show that
Under the same terms, the raman scattering intensity of microballoon will not change, and show different organic solvents to feature in PVA-DMAB-Ag microballoons
Peak not will produce interference, be adapted to the water content detection of all kinds of organic solvents.Novel surface prepared by this results show increases
Strong Raman spectrum base material can detect by Raman spectra qualitative and quantitatively water content, and the technology to detect water provides one kind
Brand-new thinking is of great significance in fields such as bio-sensing, environmental monitoring and analysis and surface-enhanced Raman detections.
Claims (7)
1. a kind of preparation method for detecting the surface enhanced Raman substrate material of water content in organic solvent, feature exists
In being as follows：
(1) PVA-DMAB microballoons are prepared
Under 55-65 DEG C of water bath condition, after PVA, p-Mercaptoaniline aqueous solution and potassium peroxydisulfate are stirred evenly, pass through injection
Pump sample introduction enters microreactor and polymerization curing reaction occurs, and after reaction, dried PVA- is prepared in washing, drying
DMAB microballoons；Wherein：A concentration of 8-12mmol/L of p-Mercaptoaniline aqueous solution；PVA, p-Mercaptoaniline aqueous solution and persulfuric acid
The mass ratio of potassium is (4~6)：2：(0.025~0.035)；
(2) PVA-DMAB-Ag microballoons are prepared
Dried PVA-DMAB microballoons are first soaked and are swollen in deionized water, it is added isometric 5 thereto later~
10mmol/L AgNO3The trisodium citrate aqueous solution of aqueous solution and 10~20mmol/L, at room temperature reductase 12 0-30h, reaction are tied
Shu Hou takes out the PVA-DMAB beads for having loaded Nano silver grain, dries 15-25min in 120-125 DEG C of baking oven, prepare
PVA-DMAB-Ag microballoons are to get to the surface enhanced Raman substrate material for detecting water content in organic solvent.
2. preparation method according to claim 1, which is characterized in that in step (1), use acetic acid positive fourth when washing successively
Ester and ethyl acetate washing.
3. preparation method according to claim 1, which is characterized in that in step (1), drying temperature is 55-65 DEG C, dry
Time is 6-10 hours.
4. preparation method according to claim 1, which is characterized in that in step (1), when sample introduction, flow velocity 1-3mL/
Min, sample injection time 8-12min, retention time 2.5-3.5h.
5. preparation method according to claim 1, which is characterized in that in step (2), PVA-DMAB microballoons and AgNO3It is water-soluble
The mass volume ratio of liquid is 1:1~1:10g/mL.
6. the table made from a kind of preparation method according to one of claim 1-5 for detecting water content in organic solvent
Face enhances Raman substrate material.
7. a kind of according to claim 6 for detecting the surface enhanced Raman substrate material of water content in organic solvent
Using.
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| CN110208242A (en) * | 2019-06-10 | 2019-09-06 | 上海应用技术大学 | A kind of gel rubber material and its preparation method and application quickly detected for pesticide |
| CN111948086A (en) * | 2019-05-17 | 2020-11-17 | 张洁风 | Method for directly and rapidly determining water content of industrial anhydrous methylamine product with unknown absorbed dose |
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| CN103868908A (en) * | 2014-02-26 | 2014-06-18 | 江南大学 | Surface enhanced Raman substrate based on sepharose gel as well as preparation method of substrate |
| CN107084968A (en) * | 2017-04-07 | 2017-08-22 | 吉林大学 | A kind of method that utilization molecular template Contrast agent lifts SERS substrate detection sensitivities |
| CN107365254A (en) * | 2016-05-12 | 2017-11-21 | 北京大学 | A kind of application of polymer microballoon in Raman detection |
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| AU2003304525A8 (en) * | 2002-08-28 | 2005-05-19 | Ut Battelle Llc | Sers diagnostic platforms, methods and systems including microarrays, biosensors and biochips |
| WO2010116345A1 (en) * | 2009-04-08 | 2010-10-14 | National University Of Ireland, Galway | Silver nanoplates |
| CN103868908A (en) * | 2014-02-26 | 2014-06-18 | 江南大学 | Surface enhanced Raman substrate based on sepharose gel as well as preparation method of substrate |
| CN107365254A (en) * | 2016-05-12 | 2017-11-21 | 北京大学 | A kind of application of polymer microballoon in Raman detection |
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| CN111948086A (en) * | 2019-05-17 | 2020-11-17 | 张洁风 | Method for directly and rapidly determining water content of industrial anhydrous methylamine product with unknown absorbed dose |
| CN111948086B (en) * | 2019-05-17 | 2022-05-06 | 张洁风 | Method for directly and rapidly determining water content of industrial anhydrous methylamine product with unknown absorbed dose |
| CN110208242A (en) * | 2019-06-10 | 2019-09-06 | 上海应用技术大学 | A kind of gel rubber material and its preparation method and application quickly detected for pesticide |
| CN110208242B (en) * | 2019-06-10 | 2021-09-28 | 上海应用技术大学 | Gel material for rapid detection of pesticide and preparation method and application thereof |
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| CN108444977B (en) | 2020-10-02 |
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