CN105910881B - A kind of micromation heat auxiliary sample pretreatment device and application detected for Surface enhanced Raman spectroscopy - Google Patents
A kind of micromation heat auxiliary sample pretreatment device and application detected for Surface enhanced Raman spectroscopy Download PDFInfo
- Publication number
- CN105910881B CN105910881B CN201610234944.4A CN201610234944A CN105910881B CN 105910881 B CN105910881 B CN 105910881B CN 201610234944 A CN201610234944 A CN 201610234944A CN 105910881 B CN105910881 B CN 105910881B
- Authority
- CN
- China
- Prior art keywords
- sample
- gasification
- substance
- surface enhanced
- analyzed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 48
- 238000002309 gasification Methods 0.000 claims abstract description 79
- 238000010438 heat treatment Methods 0.000 claims abstract description 52
- 238000001514 detection method Methods 0.000 claims abstract description 48
- 239000000126 substance Substances 0.000 claims abstract description 45
- 239000012159 carrier gas Substances 0.000 claims abstract description 17
- 238000001212 derivatisation Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 15
- 238000002347 injection Methods 0.000 claims abstract description 12
- 239000007924 injection Substances 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 10
- 238000002203 pretreatment Methods 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 238000001069 Raman spectroscopy Methods 0.000 claims description 50
- 239000007788 liquid Substances 0.000 claims description 23
- 230000002708 enhancing effect Effects 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000005259 measurement Methods 0.000 claims description 7
- 239000012491 analyte Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006073 displacement reaction Methods 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 9
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 238000009835 boiling Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 82
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 41
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 29
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 27
- 238000001237 Raman spectrum Methods 0.000 description 12
- 239000010865 sewage Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 235000013312 flour Nutrition 0.000 description 7
- 238000004611 spectroscopical analysis Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000010842 industrial wastewater Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- -1 3- methyl-benzothiazole hydrazone Chemical class 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- AHIBWURJLGCHAY-UHFFFAOYSA-N [S].C1=CC=CC=C1 Chemical class [S].C1=CC=CC=C1 AHIBWURJLGCHAY-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003891 environmental analysis Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004853 microextraction Methods 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- 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
- G01N1/44—Sample treatment involving radiation, e.g. heat
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (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 for the micromation heat auxiliary sample pretreatment device of Surface enhanced Raman spectroscopy detection and application, and described device includes carrier gas system, heating chamber, gasification pond and reception pipe；Gasification pond is set in heating chamber, and for placing sample, heating chamber is a cavity, and both ends are provided with air inlet and air outlet, and position corresponding with gasification pond is provided with injection port above cavity；Carrier gas system is connected by air inlet with heating chamber；Reception pipe is connected by gas outlet with heating chamber, and reception pipe is built-in with the solution for absorbing gasification sample.The device of the invention is analysed to gasification substance, being kept completely separate for object and matrix is realized using the boiling point difference of substance to be analyzed and matrix, and it can be according to the property of the substance to be analyzed in sample, using direct volatilization mode, derivatization mode, turn volatilization mode and catalysis mode progress sample pre-treatments, improves the sensitivity and accuracy of Surface enhanced Raman spectroscopy detection.
Description
Technical field
The present invention relates to analytical chemistry sample pre-treatments and analysis detection fields, more particularly to a kind of surface enhanced that is used for draw
Graceful micromation heat auxiliary sample pretreatment device and application, it is weak to be suitable for volatile, non-volatile or surface-enhanced Raman signals
Object real-time quick analysis.
Background technique
Surface enhanced Raman spectroscopy (SERS) is the new detection technique developed in recent years, has detection speed fast, sensitive
The features such as degree is high, and instrument is portable, is answered in environmental analysis, food safety, pesticide residue and public safety health field
With.However, there are still many urgent problems to be solved, such as enhancing particle in the analytic process for being applied to complex system by SERS
Stability, sample substrate interference elimination and instrument stability.Wherein, sample substrate interference is main problem, former
Cause is that SERS enhancing particle is easy to reunite in complicated matrix environment or other physicochemical changes occur, and leads to SERS spirit
Sensitivity and accuracy are greatly reduced.In order to solve this problem, the method that scientific research personnel uses sample pre-treatments, by sample with base
Matter separates as far as possible, so as to improve the sensitivity and accuracy of SERS.
Current Sample Pretreatment Technique mainly has molecular engram, Solid Phase Extraction, liquid-liquid micro-extraction and magnetic material function
Change etc..The development and application of these pretreatment technologies improve the accuracy of SERS detection.However these pretreatment process are opposite
Complicated, time-consuming, some needs use a large amount of poisonous and hazardous organic reagents.In addition, device body needed for these pre-treating methods
Product is huge, not readily portable to combine SERS progress scene to test and analyze real-time, quickly to scene.
Summary of the invention
It is an object of the invention to overcome shortcoming and defect in the prior art, provide a kind of for surface-enhanced Raman light
The micromation heat of spectrum detection assists sample pretreatment device, and the apparatus structure is simple, progress easy to carry to live small in size is real
When detect.
The present invention is achieved by the following technical solutions: a kind of micromation heat for Surface enhanced Raman spectroscopy detection
Assist sample pretreatment device, including carrier gas system, heating chamber, gasification pond and reception pipe；The gasification pond is set to heating chamber
Interior, for placing sample, the heating chamber is a cavity, and both ends are provided with air inlet and air outlet, above cavity with gas
Change the corresponding position in pond and is provided with injection port；The carrier gas system is connected by air inlet with heating chamber；The reception pipe passes through
Gas outlet is connected with heating chamber, and the reception pipe is built-in with the solution for absorbing gasification sample.
Compared with the existing technology, before the micromation heat auxiliary sample for Surface enhanced Raman spectroscopy detection of the invention
Device is managed, gasification substance is analysed to, realizes the complete of object and matrix using the boiling point difference of substance to be analyzed and matrix
Separation, to achieve the purpose that eliminate Matrix effects.Also, described device structure is simple, it is small in size it is easy to carry to live into
Row real-time detection.
Further, the pretreating device further includes power supply unit, the gasification bottom of pond portion be provided with heating sheet slot and
Jack, heating sheet is provided in the heating sheet slot, and the conducting wire of the heating sheet is electrically connected by jack with power supply unit.
Further, cavity side position corresponding with gasification pond is provided with gasification pond inlet and outlet, the gasification pond
It is placed in heating chamber by gasification pond inlet and outlet or is taken out out of heating chamber.It is easy to clean or more after processing before every time
Ventilationization pond.
Further, the gasification pond is the aluminium material through anodic oxidation, and the heating sheet is miniature ceramic heating flake.
Further, the injection port and gasification pond inlet and outlet end are provided with silica gel piece.
Meanwhile the present invention also provides the micromation heat detected for Surface enhanced Raman spectroscopy auxiliary sample pre-treatments dresses
The application set, comprising the following steps:
(1) sample pretreatment: taking sample to be tested, configures a series of titer of the substance to be analyzed of various concentrations；
(2) sample and titer gasification process: sample and titer are used by pretreating device directly volatilize respectively
Mode, derivatization mode turn volatilization mode or are catalyzed mode treatment, and the liquid that is absorbed in reception pipe is to be measured；
(3) drafting of standard curve: respectively to the absorbing liquid through a series of step (2) treated various concentration titers
The middle same amount of enhancing particle of addition is detected with Raman after mixing, is read at substance Characteristic Raman displacement to be analyzed
Peak area draws the peak area-substance content standard curve to be analyzed at Characteristic Raman displacement；
(4) measurement of sample concentration: measuring the absorbing liquid with the sample to be tested of same volume in step (3), is added identical
The enhancing particle of amount is detected with Raman after mixing, and testing conditions are identical as step (3), reads material property to be analyzed
Peak area at Raman shift, the peak area-substance content standard curve to be analyzed at compare feature Raman shift, obtains to be measured
The content of substance to be analyzed in sample.
Compared with the existing technology, the application of device of the present invention can use at least four detection patterns, directly wave
Hair mode, derivatization mode turn volatilization mode and catalysis mode, carry out in combination with the property of the substance to be analyzed in sample to be tested
The detection of a variety of volatile materials or derivatization means, and pre-treatment separates sample to be tested as far as possible with matrix, improves
The sensitivity and accuracy of Surface enhanced Raman spectroscopy detection.
Further, when substance to be analyzed is volatile and has Surface enhanced Raman spectroscopy response, using the mould that directly volatilizees
The titer of sample to be tested or substance to be analyzed is directly added into gasification pond, is absorbed after gasification by solution in reception pipe by formula
After detected.
Further, when substance to be analyzed is volatile but does not have Surface enhanced Raman spectroscopy response, using derivatization mould
The titer of sample to be tested or substance to be analyzed is directly added into gasification pond, is absorbed after gasification by solution in reception pipe by formula
After derivatization reagent is added, detected after making substance to be analyzed that derivative reaction occur.
Further, when substance to be analyzed is not easy to volatilize and do not have Surface enhanced Raman spectroscopy response, using a turn volatilization
Mode adds in gasification pond to being added after reactant in the titer of sample to be tested or substance to be analyzed, by connecing after gasification
Derivatization reagent is added after absorbing in solution in closed tube, is detected after making substance to be analyzed that derivative reaction occur.
Further, there is surface when test analyte matter does not have Surface enhanced Raman spectroscopy response and is difficult to derivative chemical conversion
Enhance Raman spectrum response substance when, using catalysis mode, gasification pond in be added catalyst after, to gasification pond in be added to
The titer of sample or substance to be analyzed gasifies, and is detected after absorbing cooling by solution in reception pipe.
In order to better understand and implement, the invention will now be described in detail with reference to the accompanying drawings.
Detailed description of the invention
Fig. 1 is the knot of the micromation heat auxiliary sample pretreatment device for Surface enhanced Raman spectroscopy detection of the invention
Structure schematic diagram.
Fig. 2 is benzene in the micromation heat auxiliary sample pretreatment device analytical industry waste water of Surface enhanced Raman spectroscopy detection
The Raman spectrum and standard curve of thiophenol content.
Fig. 3 is that formaldehyde contains in the micromation heat auxiliary sample pretreatment device analysis flour of Surface enhanced Raman spectroscopy detection
The Raman spectrum and standard curve of amount.
Fig. 4 is sulphion in the micromation heat auxiliary sample pretreatment device analysis sewage of Surface enhanced Raman spectroscopy detection
The Raman spectrum and standard curve of content.
Fig. 5 is first in the micromation heat auxiliary sample pretreatment device analytical industry alcohol of Surface enhanced Raman spectroscopy detection
The Raman spectrum and standard curve of alcohol content.
Specific embodiment
It is of the invention to reach the technological means and its technical effect that predetermined goal of the invention is taken further to illustrate, with
Under in conjunction with the embodiments and attached drawing, sample is assisted to a kind of micromation heat for Surface enhanced Raman spectroscopy detection proposed by the present invention
The step of structure of product pretreating device, feature, method and its specific embodiment are illustrated, and detailed description are as follows.
Referring to Fig. 1, it is before the micromation heat for Surface enhanced Raman spectroscopy detection of the invention assists sample
Manage the structural schematic diagram of device comprising carrier gas system 1, heating chamber 2, gasification pond 3 and reception pipe 4.The air inlet of the heating chamber 2
End and outlet side are connected to carrier gas system 1 and reception pipe 4.The gasification pond 3 is set in heating chamber 2.
The heating chamber 2 is a cavity, and both ends are provided with air inlet 21 and gas outlet 22.The cavity be additionally provided with into
Sample mouth 23 and gasification pond inlet and outlet 24.The injection port 23 is set to position corresponding with gasification pond 3 above cavity.The gasification
Pond inlet and outlet 24 are set to 2 side of heating chamber position corresponding with gasification pond 3.24 ends are imported and exported in the injection port 23 and gasification pond
Portion is provided with silica gel piece, for sealing.The heating chamber 2 is glass material.
The carrier gas system 1 is controllable velocity air pump or miniature nitrogen gas tank.The carrier gas system 1 by air inlet 21 with
Heating chamber 2 is connected.
The gasification pond 3 is placed in heating chamber 2 by gasification pond inlet and outlet 24 or is taken out out of heating chamber 2.The gas
Change pond 3 for placing sample.3 bottom of gasification pond is provided with heating sheet slot and jack.2 bottom of gasification pond is provided with
Heating sheet is set in the heating sheet slot of gasification 2 bottom of pond.The conducting wire of the heating sheet passes through jack and power supply unit electricity
Connection is heated for gasification pond 3, makes the sample gasification being placed in gasification pond 3.In the present embodiment, the gasification pond 3 is through anode
The aluminium material of oxidation, the heating sheet are miniature ceramic heating flake, but not limited to this, other lists that can be heated for gasification pond 3
Member.
The reception pipe 4 is connected by gas outlet 22 with heating chamber 2.The reception pipe 4, which is built-in with, absorbs gasification sample
Solution.
Compared with the existing technology, before the micromation heat auxiliary sample of Surface enhanced Raman spectroscopy detection of the present invention
It is simple, small in size to manage apparatus structure, field quick detection can be carried out, and sample is separated with matrix, to improve table
Face enhances the sensitivity and accuracy of Raman spectrum detection.There are four types of detection patterns for device tool of the present invention, directly volatilize
Mode, derivatization mode turn volatilization mode and catalysis mode, in combination with the property of test substance carry out a variety of volatile materials or
The detection of derivatization means, and pre-treatment separates sample to be tested as far as possible with matrix, improves Surface enhanced Raman spectroscopy
The sensitivity and accuracy of detection.
Embodiment 1
In order to further illustrate the present invention, the micromation using Surface enhanced Raman spectroscopy detection is described in detail in the present embodiment
Heat auxiliary sample pretreatment device detects the benzenethiol in industrial wastewater under direct volatilization mode.Wherein, sample to be tested is work
Industry waste water, substance to be analyzed are benzenethiol.The direct volatilization mode can be used for volatile and have using not limited to this
The detection of the test analyte of Surface enhanced Raman spectroscopy response.In the present embodiment, the reception pipe 4 is built-in with 5mL's
10% (v/v) ethanol water.Specifically, including the following steps:
(1) sample pretreatment: industrial wastewater sample is taken；Configure a series of benzenethiol titer of various concentrations.
(2) sample and titer gasification process: carrier gas system 1 is opened, measures 100 μ L industrial wastewater samples and 100 μ respectively
A series of benzenethiol titer of various concentrations of L passes through in the injection gasification of injection port 23 pond 3.Power supply unit power supply is opened, makes to add
Backing heats gasification pond 3, and then so that trade effluent sample and titer is gasified, and gasifying gas is blown by carrier gas system 1
Into reception pipe 4.After sample and titer volatilization gasification completely, stop heating.Then by the absorbing liquid constant volume in reception pipe 4
It is to be measured to 10mL.
(3) drafting of standard curve: a series of benzene sulphur of various concentrations through step (2) processing of 200 μ L is measured respectively
In Raman pipe, the enhancing particle CP-1 for being separately added into 100 μ L after mixing, is examined the absorbing liquid of phenol titer with Raman
It surveys, and reads 1024cm-1Peak area at Raman shift draws 1024cm-1Peak area-benzenethiol content at Raman shift
Standard curve.Wherein, the CP-1 is the Au nanoparticle of diameter about 55nm, and concentration is 2.94 × 10-4The enhancing grain of mol/L
Son.The Raman is DeltaNu Raman, excitation wavelength 785nm, sweep time 1s.
(4) measurement of sample concentration: measuring the absorbing liquid of sample in 200 μ L steps (2), and the enhancing particle of 100 μ L is added
CP-1 after mixing, is detected with Raman, and testing conditions are identical as step (3), reads 1024cm-1Peak face at Raman shift
Product compares 1024cm-1Peak area-benzenethiol content standard curve at Raman shift, obtains benzenethiol in industrial wastewater sample
Content.
Referring to Fig. 2, it is the micromation heat auxiliary sample pretreatment device analysis work of Surface enhanced Raman spectroscopy detection
The Raman spectrum and standard curve of benzenethiol content in industry waste water.It can be calculated from figure, benzenethiol in industrial wastewater sample
Content be 0.30 μ g/mL, the content of benzenethiol is 0.68 μ g/mL, recovery of standard addition 95.0% after mark-on.
Embodiment 2
In order to further illustrate the present invention, the micromation using Surface enhanced Raman spectroscopy detection is described in detail in the present embodiment
Heat auxiliary sample pretreatment device detects the formaldehyde in flour under derivatization mode, wherein the sample to be tested is flour, institute
Stating substance to be analyzed is formaldehyde.The straight derivatization mode can be used for volatile but not have surface using not limited to this
Enhance the detection of the test analyte of Raman spectrum response.In the present embodiment, it is 200 that the reception pipe 4, which is built-in with 5mL concentration,
The 3- methyl-benzothiazole hydrazone aqueous solution of μ g/mL.Specifically, including the following steps:
(1) sample pretreatment: weighing 0.1g flour, and 10mL water ultrasonic mixing 5min is added, and 10000r/min is centrifuged 5min,
Take supernatant to be measured；Configure a series of methanol titer of various concentrations.
(2) measurement of sample and standard curve: opening carrier gas system 1, measure 100 μ L respectively treated flour sample and
A series of methanol titer of 100 various concentrations of μ L passes through in the injection gasification of injection port 23 pond 3.Power supply unit power supply is opened, is made
Heating sheet heats gasification pond 3, and then sample liquid and titer is made to gasify, and gasifying gas is blown to by carrier gas system 1 and is connect
In closed tube 4.After sample and titer volatilization gasification completely, stop heating.It is added and derives into the absorbing liquid of reception pipe 4 respectively
1% ammonium ferric sulfate solution (HCl of 0.1mol/L is solvent) for changing 300 μ L of reagent, makes methanol that derivative reaction, reaction occur
10mL is settled to after 15min, it is to be measured.
(3) drafting of standard curve: a series of methanol of various concentrations through step (2) processing of 200 μ L is measured respectively
In Raman pipe, the enhancing particle CP-2 for being separately added into 100 μ L after mixing, is detected the absorbing liquid of titer with Raman,
And read 1275cm-1Peak area at Raman shift draws 1275cm-1Peak area-content of formaldehyde standard at Raman shift is bent
Line.Wherein, the CP-2 is the Au/SiO that diameter is about 55nm2Colloidal sol, SiO2Cladding with a thickness of 1-2nm, concentration is 2.94 ×
10-4mol/L.The Raman is DeltaNu Raman, excitation wavelength 785nm, sweep time 1s.
(4) measurement of sample concentration: measuring the absorbing liquid of sample in 200 μ L steps (2), and the enhancing particle of 100 μ L is added
CP-2 after mixing, is detected with Raman, and testing conditions are identical as step (3), reads 1275cm-1Peak face at Raman shift
Product compares 1275cm-1Peak area-content of formaldehyde standard curve at Raman shift, obtains the content of formaldehyde in flour.
Referring to Fig. 3, it is the micromation heat auxiliary sample pretreatment device analysis face of Surface enhanced Raman spectroscopy detection
The Raman spectrum and standard curve of content of formaldehyde in powder.It being calculated from figure, the content of formaldehyde in flour is 72.5mg/kg,
The content of formaldehyde is 155.6mg/kg, recovery of standard addition 83.1% after mark-on.
Embodiment 3
In order to further illustrate the present invention, the micromation using Surface enhanced Raman spectroscopy detection is described in detail in the present embodiment
Heat auxiliary sample pretreatment device detects the sulphion in sewage in the case where turning volatilization mode, wherein and the sample to be tested is sewage,
The substance to be analyzed is sulphion.Described turn of volatilization mode can be used for not volatile and not have using not limited to this
The detection of the test analyte of Surface enhanced Raman spectroscopy response.In the present embodiment, the reception pipe 4 is built-in with the dense of 5mL
Degree is 2g/L zinc acetate aqueous solution.Specifically, including the following steps:
(1) sample pretreatment: sewage sample is taken；Configure a series of sulphion titer of various concentrations.
(2) sample and titer gasification process: opening carrier gas system 1, a series of not to 100 μ L sewage samples and 100 μ L
With reactant 10 μ L 50% (v/v) phosphate aqueous solution is separately added into the sulphion titer of concentration, then pass through sample introduction respectively
In 23 injection gasification ponds 3 of mouth.Power supply unit power supply is opened, heats heating sheet to gasification pond 3, and then make sewage sample and standard
Liquid gasification, and gasifying gas is blown in reception pipe 4 by carrier gas system 1.After sample and titer volatilization gasification completely, stop
Only heat.The N of the 2mg/mL of derivatization reagent 1mL is sequentially added into the absorbing liquid of reception pipe 4 respectively, N- dimethyl is to benzene two
The 5mol/L aqueous sulfuric acid of 1mL and the 4.9mg/mL ferric chloride solution of 300 μ L is added (containing 0.1mol/L in amine aqueous solution
HCl), it is settled to 10mL with secondary water after reaction 10min, it is to be measured.
(3) drafting of standard curve: measure respectively a series of different sulphur of concentration through step (2) processing of 200 μ L from
In Raman pipe, the enhancing particle CP-2 for being separately added into 100 μ L after mixing, is examined the absorbing liquid of substandard liquid with Raman
It surveys, and reads 452cm-1Peak area at Raman shift draws 452cm-1Peak area-sulfite ion concentration mark at Raman shift
Directrix curve.Wherein, the CP-2 is the Au/SiO that diameter is about 55nm2Colloidal sol, SiO2Cladding is with a thickness of 1-2nm, concentration 2.94
×10-4mol/L.The Raman is DeltaNu Raman, excitation wavelength 785nm, sweep time 1s.
(4) measurement of sample concentration: measuring the absorbing liquid of sample in 200 μ L steps (2), and the enhancing particle of 100 μ L is added
CP-2 after mixing, is detected with Raman, and testing conditions are identical as step (3), reads 452cm-1Peak face at Raman shift
Product compares 452cm-1Peak area-sulfite ion concentration standard curve at Raman shift, obtains the content of sulphion in sewage.
Referring to Fig. 4, it is that the micromation heat auxiliary sample pretreatment device analysis of Surface enhanced Raman spectroscopy detection is dirty
The Raman spectrum and standard curve of sulfite ion concentration in water.It is calculated from figure, the sulfite ion concentration in sewage is 79.0mg/
L, the content of sulphion is 125.4mg/L, recovery of standard addition 95.4% after mark-on.
Embodiment 4
In order to further illustrate the present invention, the micromation using Surface enhanced Raman spectroscopy detection is described in detail in the present embodiment
Heat auxiliary sample pretreatment device detects the methanol in industrial alcohol under catalysis mode, wherein the sample to be tested is industry
Alcohol, the substance to be analyzed are that methanol exists.The catalysis mode can be used for not having surface enhanced using not limited to this
Raman spectrum responds and is difficult to the detection that derivative chemical conversion has the test analyte of Surface enhanced Raman spectroscopy response.The present embodiment
In, the reception pipe 4 is built-in with 0.25% (v/v) the acetylacetone,2,4-pentanedione solution of the pH=6.0 of 5mL (by the ammonium acetate of 50mg/mL
Buffer is adjusted to pH=6.0).Specifically, including the following steps:
(1) it sample pretreatment: takes industrial alcohol sample and dilutes 10 times；Configure a series of methanol standard of various concentrations
Liquid.
(2) sample and titer gasification process: gasification pond 3 is added in 0.1g copper powder catalyst, carrier gas system 1 is opened, beats
Power supply unit power supply is opened, heats heating sheet to gasification pond 3, by the sample and 500 μ L after the dilution of 500 μ L after copper powder blackening
A series of methanol titer of various concentrations is added dropwise in gasification pond 3.After addition, by the absorbing liquid of reception pipe 4 70
DEG C heating water bath 3min with secondary water is settled to 10mL after cooling, to be measured.
(3) drafting of standard curve: a series of different methanol of concentration through step (2) processing of 100 μ L is measured respectively
In Raman pipe, the enhancing particle CP-1 for being separately added into 200 μ L after mixing, is detected the absorbing liquid of titer with Raman,
And read 1540cm-1Peak area at Raman shift draws 1540cm-1Peak area-methanol content standard at Raman shift is bent
Line.Wherein, the CP-1 is the Au nanoparticle of diameter about 55nm, and concentration is 2.94 × 10-4The enhancing particle of mol/L.It is described
Raman is DeltaNu Raman, excitation wavelength 785nm, sweep time 3s.
(4) measurement of sample concentration: measuring the absorbing liquid of sample in 100 μ L steps (2), and the enhancing particle of 200 μ L is added
CP-1 after mixing, is detected with Raman, and testing conditions are identical as step (3), reads 1540cm-1Peak face at Raman shift
Product compares 1540cm-1Peak area-methanol content standard curve at Raman shift, obtains the content of methanol in sewage.
Referring to Fig. 5, it is the micromation heat auxiliary sample pretreatment device analysis work of Surface enhanced Raman spectroscopy detection
The Raman spectrum and standard curve of methanol content in industry alcohol.It can be calculated from figure, the methanol content of industrial alcohol is
72.2mg/mL, the content of methanol is 92.2mg/mL, recovery of standard addition 86.1% after mark-on.
The invention is not limited to above embodiment, if not departing from the present invention to various changes or deformation of the invention
Spirit and scope, if these changes and deformation belong within the scope of claim and equivalent technologies of the invention, then this hair
It is bright to be also intended to encompass these changes and deformation.
Claims (9)
1. the application of the micromation heat auxiliary sample pretreatment device for Surface enhanced Raman spectroscopy detection, it is characterised in that:
Micromation heat auxiliary sample pretreatment device for Surface enhanced Raman spectroscopy detection includes carrier gas system, heating chamber, gasification
Pond and reception pipe；The gasification pond is set in heating chamber, and for placing sample, the heating chamber is a cavity, and both ends are set
Air inlet and air outlet are equipped with, position corresponding with gasification pond is provided with injection port above cavity；The carrier gas system passes through
Air inlet is connected with heating chamber；The reception pipe is connected by gas outlet with heating chamber, and the reception pipe is built-in with absorption gasification
The solution of sample；Its application method the following steps are included:
(1) sample pretreatment: taking sample to be tested, configures a series of titer of the substance to be analyzed of various concentrations；
(2) sample and titer gasification process: respectively by sample and titer by pretreating device using directly volatilization mode,
Derivatization mode turns volatilization mode or is catalyzed mode treatment, and the liquid that is absorbed in reception pipe is to be measured；
(3) drafting of standard curve: respectively into the absorbing liquid through a series of step (2) treated various concentration titers plus
Enter same amount of enhancing particle to be detected with Raman after mixing, reads the peak face at substance Characteristic Raman displacement to be analyzed
Product draws the peak area-substance content standard curve to be analyzed at Characteristic Raman displacement；
(4) measurement of sample concentration: measuring the absorbing liquid with the sample to be tested of same volume in step (3), is added same amount of
Enhancing particle is detected with Raman after mixing, and testing conditions are identical as step (3), read substance Characteristic Raman to be analyzed
Peak area at displacement, the peak area-substance content standard curve to be analyzed at compare feature Raman shift, obtains sample to be tested
In substance to be analyzed content.
2. the micromation heat according to claim 1 for Surface enhanced Raman spectroscopy detection assists sample pretreatment device
Application, it is characterised in that: the pretreating device further includes power supply unit, and the gasification bottom of pond portion is provided with heating sheet slot
And jack, heating sheet is provided in the heating sheet slot, the conducting wire of the heating sheet is electrically connected by jack with power supply unit.
3. the micromation heat according to claim 1 or 2 for Surface enhanced Raman spectroscopy detection assists sample pre-treatments
The application of device, it is characterised in that: cavity side position corresponding with gasification pond is provided with gasification pond inlet and outlet, described
Gasification pond is placed in heating chamber by gasification pond inlet and outlet or is taken out out of heating chamber.
4. the micromation heat according to claim 2 for Surface enhanced Raman spectroscopy detection assists sample pretreatment device
Application, it is characterised in that: the gasification pond be the aluminium material through anodic oxidation, heating sheet be miniature ceramic heating flake.
5. the micromation heat according to claim 3 for Surface enhanced Raman spectroscopy detection assists sample pretreatment device
Application, it is characterised in that: the injection port and gasification pond inlet and outlet end be provided with silica gel piece.
6. the micromation heat according to claim 1 for Surface enhanced Raman spectroscopy detection assists sample pretreatment device
Application, it is characterised in that: when substance to be analyzed is volatile and have Surface enhanced Raman spectroscopy response when, using directly volatilization
The titer of sample to be tested or substance to be analyzed is directly added into gasification pond, is inhaled after gasification by solution in reception pipe by mode
It is detected after receipts.
7. the micromation heat according to claim 1 for Surface enhanced Raman spectroscopy detection assists sample pretreatment device
Application, it is characterised in that: when substance to be analyzed is volatile but do not have Surface enhanced Raman spectroscopy response when, using derivatization
The titer of sample to be tested or substance to be analyzed is directly added into gasification pond, is inhaled after gasification by solution in reception pipe by mode
Derivatization reagent is added after receipts, is detected after making substance to be analyzed that derivative reaction occur.
8. the micromation heat according to claim 1 for Surface enhanced Raman spectroscopy detection assists sample pretreatment device
Application, it is characterised in that: when substance to be analyzed be not easy volatilize and do not have Surface enhanced Raman spectroscopy response when, using turn wave
Hair mode adds in gasification pond to being added after reactant in the titer of sample to be tested or substance to be analyzed, passes through after gasification
Derivatization reagent is added after absorbing in solution in reception pipe, is detected after making substance to be analyzed that derivative reaction occur.
9. the micromation heat according to claim 1 for Surface enhanced Raman spectroscopy detection assists sample pretreatment device
Application, it is characterised in that: have when test analyte matter does not have Surface enhanced Raman spectroscopy and responds and be difficult to derivative chemical conversion
When the substance of Surface enhanced Raman spectroscopy response, using catalysis mode, after catalyst is added in gasification pond, to gasification Chi Zhongjia
The titer for entering sample to be tested or substance to be analyzed gasifies, and is detected after absorbing cooling by solution in reception pipe.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610234944.4A CN105910881B (en) | 2016-04-14 | 2016-04-14 | A kind of micromation heat auxiliary sample pretreatment device and application detected for Surface enhanced Raman spectroscopy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610234944.4A CN105910881B (en) | 2016-04-14 | 2016-04-14 | A kind of micromation heat auxiliary sample pretreatment device and application detected for Surface enhanced Raman spectroscopy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105910881A CN105910881A (en) | 2016-08-31 |
| CN105910881B true CN105910881B (en) | 2018-12-28 |
Family
ID=56746176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610234944.4A Active CN105910881B (en) | 2016-04-14 | 2016-04-14 | A kind of micromation heat auxiliary sample pretreatment device and application detected for Surface enhanced Raman spectroscopy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105910881B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108333034A (en) * | 2018-05-14 | 2018-07-27 | 中山大学 | A kind of air film for Surface enhanced Raman spectroscopy detection detaches sample pretreatment device |
| CN109239048A (en) * | 2018-08-30 | 2019-01-18 | 江苏师范大学 | A method of detecting the measuring of benzenethiol from soil |
| CN109932354B (en) * | 2019-05-06 | 2021-10-08 | 中山大学 | In-situ separation and enrichment device for surface enhanced Raman spectroscopy trace analysis and application |
| CN115184103A (en) * | 2021-04-07 | 2022-10-14 | 江苏师范大学 | Rapid separation, enrichment and detection method for formaldehyde in milk and milk products |
| CN114166824B (en) * | 2021-12-08 | 2024-01-23 | 桂林医学院 | Method for analyzing drug content in health care product by tracing auxiliary agent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101270295A (en) * | 2008-04-29 | 2008-09-24 | 中国科学院广州地球化学研究所 | Accurate temperature control thermal decomposition apparatus for open type hydrocarbon producing kinetics research |
| CN102565236A (en) * | 2011-12-31 | 2012-07-11 | 聚光科技(杭州)股份有限公司 | Substance testing method |
| CN103926232A (en) * | 2014-01-27 | 2014-07-16 | 中山大学 | Method for rapidly detecting formaldehyde through surface-enhanced Raman scattering, and its application |
| CN104181152A (en) * | 2014-08-06 | 2014-12-03 | 中山大学 | Device and method for online detecting residue of dithio carbamate bactericide |
| CN104833551A (en) * | 2015-04-27 | 2015-08-12 | 中山大学 | Method utilizing surface-enhanced Raman scattering (SERS) to measure ethylene in atmosphere around vegetables and fruits |
-
2016
- 2016-04-14 CN CN201610234944.4A patent/CN105910881B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101270295A (en) * | 2008-04-29 | 2008-09-24 | 中国科学院广州地球化学研究所 | Accurate temperature control thermal decomposition apparatus for open type hydrocarbon producing kinetics research |
| CN102565236A (en) * | 2011-12-31 | 2012-07-11 | 聚光科技(杭州)股份有限公司 | Substance testing method |
| CN103926232A (en) * | 2014-01-27 | 2014-07-16 | 中山大学 | Method for rapidly detecting formaldehyde through surface-enhanced Raman scattering, and its application |
| CN104181152A (en) * | 2014-08-06 | 2014-12-03 | 中山大学 | Device and method for online detecting residue of dithio carbamate bactericide |
| CN104833551A (en) * | 2015-04-27 | 2015-08-12 | 中山大学 | Method utilizing surface-enhanced Raman scattering (SERS) to measure ethylene in atmosphere around vegetables and fruits |
Non-Patent Citations (1)
| Title |
|---|
| 《Rapid analysis of trace volatile formaldehyde in aquatic products by derivatization reaction-based surface enhanced Raman spectroscopy》;Zhuomin Zhang et al.;《Analyst》;20141231;第139卷;第3614-3621页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105910881A (en) | 2016-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105910881B (en) | A kind of micromation heat auxiliary sample pretreatment device and application detected for Surface enhanced Raman spectroscopy | |
| Le et al. | Decomposition of organoarsenic compounds by using a microwave oven and subsequent determination by flow injection‐hydride generation‐atomic absorption spectrometry | |
| CN100498287C (en) | Nano argentum spectrophotometry for detecting hydroxy free radical | |
| WO2023159532A1 (en) | Method for detecting organophosphorus pesticides by using microfluidic chip based on fluorescent sensing film | |
| de Quadros et al. | Mercury speciation by high-performance liquid chromatography atomic fluorescence spectrometry using an integrated microwave/UV interface. Optimization of a single step procedure for the simultaneous photo-oxidation of mercury species and photo-generation of Hg0 | |
| CN108760715A (en) | Detect Polychlorinated biphenyls Surface enhanced Raman scattering aptamer Sensors & Application | |
| CN108088889B (en) | The device and method of negative ion mode ion mobility spectrometry on-line checking formaldehyde | |
| CN108982465B (en) | High-flux SERS (surface enhanced Raman Scattering) online detection method for sulfur dioxide in wine | |
| CN105044049A (en) | Method and device for measuring volatile compounds | |
| CN113138185B (en) | Method for detecting sodium thiocyanate in milk by using SERS (surface enhanced Raman Scattering) technology based on MOF (metal-organic framework) | |
| CN104535555A (en) | Automatic classification detecting method for multiple analytes based on surface enhancement Raman scattering technology | |
| CN112697770A (en) | Method for measuring glutaraldehyde in water based on metal organic framework material composite substrate surface enhanced Raman spectroscopy | |
| Su et al. | Determination of trace mercury in geological samples by direct slurry sampling cold vapor generation atomic absorption spectrometry | |
| Fan et al. | A new cataluminescence-based gas sensor for simultaneously discriminating benzene and ammonia | |
| CN102863379A (en) | Analytical reagent for measuring heavy metal and method for preparing same | |
| CN108333034A (en) | A kind of air film for Surface enhanced Raman spectroscopy detection detaches sample pretreatment device | |
| CN101201318A (en) | Detection of trace amount gold nanometer particle by HAuCl4 spectrophotometric method | |
| CN101419205B (en) | Method for measuring residual organic solvent in pectins | |
| CN101319991A (en) | Flame atomic absorption spectrometry for trace amount of hydrogen peroxide | |
| CN115144477B (en) | In-situ mass spectrometry method for rapidly detecting aromatic amine released by forbidden azo dye | |
| CN104897622B (en) | It is a kind of to be used for the method for the sampling device of iodine and the concentration for testing iodine in environmental water sample | |
| CN109781829B (en) | Trace bismuth analysis method based on metal organic framework material Fe-BTC | |
| Khvostikov et al. | Determination of mercury by nondispersive atomic fluorescence spectrometry | |
| CN211014004U (en) | Sampling device for directly measuring trace elements in solid sample | |
| CN109900769A (en) | The method and device of ammonia nitrogen in a kind of ion mobility spectrometry quantitative measurment water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |