CN105223183A - A kind of substrate that can be used for zwitterion pigment selective enumeration method - Google Patents
A kind of substrate that can be used for zwitterion pigment selective enumeration method Download PDFInfo
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- CN105223183A CN105223183A CN201510600538.0A CN201510600538A CN105223183A CN 105223183 A CN105223183 A CN 105223183A CN 201510600538 A CN201510600538 A CN 201510600538A CN 105223183 A CN105223183 A CN 105223183A
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Abstract
The present invention has synthesized Fe
3o
4/ SiO
2/ Au magnetic-particle, utilize the method at magnetic-particle finishing cationic polyelectrolyte and anionic polyelectrolyte, make negative ion pigment sunset yellow and kation pigment malachite green selective enrichment on the surface of magnetic basement, and be observed the raman characteristic peak of zwitterion pigment by Portable Raman spectrometer respectively.By series of experiments prove the sample preparation methods that the present invention adopts and object analytical approach easy and simple to handle, the selective enumeration method of pigment can be realized.
Description
Technical field
The present invention relates to the method utilizing magnetic basement selective enumeration method zwitterion pigment, especially utilize the Fe that polyelectrolyte is modified
3o
4/ SiO
2the method of/Au magnetic basement selective enumeration method negative ion pigment sunset yellow and kation pigment malachite green.
Technical background
Nineteen twenty-eight India physicist Raman has found Raman scattering effect, and Raman spectrum (RS) technology set up based on this has a wide range of applications in the field such as molecular structure and analytical chemistry.Fleischmann in 1974 etc. observe the Surface enhanced raman spectroscopy (SurfaceEnhancedRamanScattering) of pyridine for the first time in coarse silver electrode, be called for short SERS phenomenon, Single Molecule Detection is achieved to SERS effect in 1997, subsequently due to the develop rapidly of nanometer technology, certain achievement is also achieved to the research of SERS.As a kind of high detection sensitivity, high resolving power, to water inertia, can quench fluorescence, good stability technology, SERS is widely used in the direction such as adsorbate interface orientation and configuration, conformation research and structure analysis.
The preparation of substrate is the key realizing excellent SERS signal, is also one of the study hotspot in SERS field.Current, prepare the satisfactory SERS substrate with nanostructured surface and remain a challenge experimentally.The sharpest edges of nano surface structure are: (1) can obtain pattern and the substantially controlled nanoscale particle of particle diameter; (2) carry out quantitative examination SERS by various ordered nano-structure simulation " rough surface " and strengthen mechanism; (3) be convenient to optimize and obtain the experiment condition of strong SERS effect.The noble metal nano particles such as gold, silver are SERS active-substrate the most frequently used in current Surface enhanced raman spectroscopy, can obtain the particle that diameter pattern within the scope of 20nm ~ 100nm is homogeneous, and stable in properties, applied widely.
The safety problem of food is owing to being related to human health and social progress and being subject to people's attention.Sunset yellow is a kind of Prof. Du Yucang colorant, the effect of the food appearance color that changes, if the food of long term consumer or disposable a large amount of edible sunset yellow content overproof, the symptom such as allergy, diarrhoea may be caused, when intake is excessive, when exceeding liver load, can accumulate in vivo, certain injury is produced to kidney, liver.Malachite green is a kind of triphenylmethane chemical dyestuff, is widely used in prevention and the treatment saprolegniasis of all kinds of aquatic livestock and the control to protozoon.But malachite green, because of spinoffs such as potential teratogenesis, carcinogenic, mutagenesis, becomes one of forbidden drugs of much national aquaculture.Pigment detection method conventional at present has high performance liquid chromatography, vapor-phase chromatography and GC-MS analytical method, and these method instruments are expensive, and requires higher to sample pre-treatments.Therefore, explore easy economy, food colour detection method rapidly and efficiently become one of the important research direction in current environmental analysis field.Theoretically, monitoring analysis SERS active-substrate being used for food colour is feasible, but the subject matter limiting its application is complex matrices in actual food product system can interfere with detecting of SERS signal.Therefore prepare cheap, stable in properties, the New type of S ERS substrate that can be applicable to food colour selective enumeration method possesses significance to environmental analysis field.
Summary of the invention
The present invention has synthesized a kind of Fe
3o
4/ SiO
2/ Au magnetic nanoparticle, utilizes negative and positive polyelectrolyte to modify magnetic-particle surface.Magnetic nanoparticle after modification is used for the enrichment of pigment, and is observed the raman characteristic peak of pigment by Portable Raman spectrometer.By series of experiments prove the sample preparation methods that the present invention adopts and target contaminant analytical approach easy and simple to handle, not only can realize the selective enumeration method of single pigment, the detection of polychrom mixed solution can also be used for.
First the present invention has synthesized Fe
3o
4/ SiO
2magnetic-particle, utilizes polyelectrolyte to modify Fe
3o
4/ SiO
2behind surface, disperseed, in Au colloidal sol, to prepare the Fe that Au is coated
3o
4/ SiO
2magnetic nanoparticle, this particle has Fe concurrently
3o
4magnetic and the Raman-enhancing energy of nanogold particle.By the Fe prepared
3o
4/ SiO
2after/Au magnetic-particle is distributed to finite concentration cationic polyelectrolyte solution, because electrostatic attraction effect has made the coated rapidly polyelectrolyte of one deck positively charged in electronegative magnetic-particle surface, the pigment of the electronegative negative ion of this magnetic basement alternative absorption.By the positive electricity Fe prepared
3o
4/ SiO
2after/Au magnetic-particle is distributed to finite concentration anionic polyelectrolyte solution, due to the electrostatic attraction effect electronegative polyelectrolyte of one deck that made the magnetic-particle surface of positively charged coated rapidly, the kation pigment of this magnetic basement alternative absorption positively charged.After now collecting the magnetic-particle adsorbing pigment with externally-applied magnetic field, utilize Portable Raman spectrometer the raman characteristic peak of pigment can be detected in 5s.
Particular content of the present invention is illustrated by description below:
(1) Fe is obtained with high-temperature decomposition
3o
4particle: by 2.7gFeCl
36H
2o and 7.2g sodium acetate mixes with 100mL ethylene glycol and magnetic agitation 1h, and put into polytetrafluoro reactor 200 DEG C reaction 12h, be cooled to room temperature ethanol purge 3 times, washed with de-ionized water 3 times after heating terminates, vacuum drying chamber 50 DEG C of dry 2h obtain Fe
3o
4magnetic nanoparticle.
(2) core-shell type Fe
3o
4/ SiO
2the preparation of magnetic-particle: the nanometer Fe of getting preparation in 0.2g step (1)
3o
4be scattered in salpeter solution, ultrasonic 10min, by washed with de-ionized water 6 times, be scattered in the mixed liquor of 20mL ethanol and 4mL deionized water, ultrasonic 10min, pours in three mouthfuls of round-bottomed flasks, drips 1mL ammoniacal liquor and 0.8mL tetraethyl orthosilicate (TEOS) wherein continuously under mechanical stirring, after 3h is carried out in reaction, the sediment of generation is obtained Fe in vacuum 60 DEG C of dry 1h
3o
4/ SiO
2nano particle.
(3) polyelectrolyte modifies Fe
3o
4/ SiO
2the preparation of magnetic-particle: diallyl dimethyl ammoniumchloride (PDDA) solution of preparation 100mL2%, magnetic agitation 0.5h, transfers to solution in three mouthfuls of round-bottomed flasks, adds the Fe of preparation in 0.1g step (2) under mechanical stirring
3o
4/ SiO
2magnetic-particle, after 3h is carried out in reaction, by the sediment washed with de-ionized water 6 times generated, obtains the Fe that polyelectrolyte is modified
3o
4/ SiO
2magnetic-particle.
(4) with high temperature reduction method synthesis Au nano particle: by the HAuCl of 2mL2%
4solution joins in 46mL deionized water, heating said solution under churned mechanically condition in oil bath pan, when temperature rises to 100 DEG C, the aqueous solution of 2mL containing 114mg sodium citrate is added in above-mentioned solution, reaction 20min stops heating, product is continued stirring and is cooled to room temperature, obtain Au nano particle.
(5) Fe that Au is coated
3o
4/ SiO
2the preparation of magnetic-particle: the Fe that 0.02g step (3) is obtained
3o
4/ SiO
2magnetic-particle is scattered in the obtained Au colloidal sol of 40mL step (4), puts into shaking table, with 150 revs/min of reaction 20min at 30 DEG C, by product washed with de-ionized water 6 times, obtains the Fe that Au is coated
3o
4/ SiO
2magnetic-particle.
(6) preparation of the SERS substrate of positive polyelectrolyte modification: the Fe that Au 0.02g step (5) obtained is coated
3o
4/ SiO
2magnetic-particle is scattered in the PDDA solution of 10mL2%, reacts 20min at putting into shaking table 30 DEG C with 150 revs/min, by the positive magnetic SERS substrate PDDA-Fe that product washed with de-ionized water obtains PDDA afterwards and modifies for 6 times
3o
4/ SiO
2/ Au (FSPAP).
(7) preparation of the SERS substrate of negative polyelectrolyte modification: the FSPAP magnetic-particle that 0.01g step (6) obtains is scattered in kayexalate (PSS) solution of 10mL3%, reacts 20min with 150 revs/min at putting into shaking table 30 DEG C.By the negative magnetic SERS substrate PSS-Fe that product washed with de-ionized water obtains PSS afterwards and modifies for 6 times
3o
4/ SiO
2/ Au (FSPAPP).
(8) enrichment of pigment and detection: the magnetic SERS substrate that 0.2mg step (7) obtains is scattered in pigment solution after mixing certain hour and with externally-applied magnetic field, magnetic-particle is collected, use Raman spectrometer to carry out signals collecting, obtain the SERS spectrogram of pigment.
Accompanying drawing explanation
Below by marginal data principal character of the present invention.
The transmission electron microscope photo of the selectivity substrate that accompanying drawing 1 is prepared for the present invention, Fig. 1 experimental result shows the Fe prepared
3o
4/ SiO
2/ Au even particle size, the Au nano particle of substrate surface is evenly coated.
Accompanying drawing 2 is obtain the Raman spectrogram of kation magnetic basement FSPAP to the Congo red selective enumeration method of anionic dye in the present invention.Testing result absolutely proves that the positive FSPAP that the present invention obtains only has Raman response to feminine gender is Congo red, the negative dyestuff of alternative detection.
Accompanying drawing 3 is obtain the Raman spectrogram of FSPAPP at the bottom of anion base to Degradation of Cationic Dye Crystal Violet selective enumeration method in the present invention, and testing result absolutely proves that the negative substrate alternative that the present invention obtains detects positive dyestuff.
Accompanying drawing 4 is Raman spectrograms that FSPAP at the bottom of positive group detects negative pigment sunset yellow, and result shows, can detect that concentration is 5x10
-8the negative sunset yellow of mol/L.
Accompanying drawing 5 is Raman spectrograms that negative substrate FSPAPP detects positive pigment malachite green, and result shows, can detect that concentration is 5x10
-8the positive malachite green of mol/L.
Accompanying drawing 6 is general figure of Raman that FSPAP and FSPAPP detects hybrid pigment (sunset yellow+malachite green).Result shows, positive FSPAP only can detect negative malachite green, and negative FSPAPP only can detect positive malachite green, and experimental result fully demonstrates the feasibility of detection method, illustrates that this method possesses the potentiality being applied to food colour selective enumeration method.
Inventive embodiments
The present invention is set forth below further by embodiment.
Embodiment 1Fe
3o
4the preparation of nano particle: by 2.7gFeCl
36H
2o and 7.2g sodium acetate mixes with 100mL ethylene glycol and magnetic agitation 1h, and high temperature 200 DEG C reaction 12h, by product 50 DEG C of vacuum drying 2h, collects and obtain Fe
3o
4magnetic nanoparticle; Fe
3o
4/ SiO
2the preparation of magnetic-particle: the nanometer Fe of getting preparation in 0.2g step (1)
3o
4be scattered in (0.1mol/L) in 20mL salpeter solution, ultrasonic 10min, by washed with de-ionized water 6 times, be scattered in (20mL ethanol+4mL deionized water) in mixed liquor, ultrasonic 10min, pours in three mouthfuls of round-bottomed flasks, drips 1mL ammoniacal liquor and 0.8mLTEOS wherein continuously under mechanical stirring, after 3h is carried out in reaction, the sediment of generation is obtained Fe in vacuum 60 DEG C of dry 1h
3o
4/ SiO
2nano particle.Get 0.1mgFe
3o
4/ SiO
2magnetic-particle is distributed to (10mL20%PDDA+90mL deionized water+88.2mg sodium chloride+11.5mg sodium citrate) in the PDDA solution of 100mL2%, after mechanical raking 3h, by the sediment washed with de-ionized water 6 times generated, obtain the Fe that polyelectrolyte is modified
3o
4/ SiO
2magnetic-particle; The Fe that Au is coated
3o
4/ SiO
2the preparation of magnetic-particle: by the HAuCl of 2mL2%
4solution joins in 46mL deionized water, heating said solution under churned mechanically condition in oil bath pan, when temperature rises to 100 DEG C, adds the aqueous solution of 2mL containing 114mg sodium citrate in above-mentioned solution.Reaction 20min, stops heating, product is continued stirring and is cooled to room temperature, obtain Au nano particle.By the Fe that the PDDA of 0.02g modifies
3o
4/ SiO
2the preparation of magnetic-particle is scattered in 40mLAu colloidal sol, shaking table (30 DEG C, 150 revs/min) reaction 20min.By product washed with de-ionized water 6 times, obtain Fe
3o
4/ SiO
2/ Au magnetic-particle; The preparation of the SERS substrate that positive polyelectrolyte is modified: by 0.02gFe
3o
4/ SiO
2/ Au is scattered in (the PDDA+9mL deionized water+8.82mg sodium chloride+1.15mg sodium citrate of 1mL20%) in the PDDA solution of 10mL2%, puts into shaking table (30 DEG C, 150 revs/min) reaction 20min.By the positive magnetic SERS substrate FSPAP that product washed with de-ionized water obtains PDDA afterwards and modifies for 6 times; The preparation of the SERS substrate that negative polyelectrolyte is modified: 0.01gFSPAP magnetic-particle is scattered in (the PSS solution+9mLDI+3mgNaCl of 1mL30%) in the PSS solution of 10mL3%, put into shaking table (30 DEG C, 150 revs/min) reaction 20min.By the negative magnetic SERS substrate FSPAPP that product washed with de-ionized water obtains PSS afterwards and modifies for 6 times; The enrichment of pigment and detection: 0.2mg magnetic SERS substrate is scattered in 1mL pigment solution, with externally-applied magnetic field, magnetic-particle is collected after mixing 1h, the magnetic-particle being enriched pigment is placed on silicon chip, ENWAVE Portable Raman spectrometer is used to carry out signals collecting, INSTRUMENT MODEL is EZRaman-ISeries, the place of production U.S., optical maser wavelength 785nm, sweep time, 5s, obtained the SERS spectrogram of pigment.
Embodiment 2 gathers the preparation method of the selective enumeration method SERS substrate of electrolysis modifying with embodiment 1.The enrichment of pigment mixed solution and detection: be scattered in by the magnetic nanoparticle that 0.2mg polyelectrolyte is modified in 1mL pigment mixed solution, two kinds of pigments separately concentration are 1x10
-4mol/L.Collect magnetic-particle with externally-applied magnetic field after 1h, be placed on silicon chip by the magnetic-particle being enriched pigment, use Portable Raman spectrometer to carry out signals collecting, sweep time is 5s, obtains the SERS spectrogram of colorant mixture.
Claims (10)
1. can be used for a substrate for zwitterion pigment selective enumeration method, its synthesis step is as follows:
(1) Fe is obtained with high-temperature decomposition
3o
4particle: by 2.7gFeCl
36H
2o and 7.2g sodium acetate mixes with 100mL ethylene glycol and magnetic agitation 1h, and put into polytetrafluoro reactor 200 DEG C reaction 12h, be cooled to room temperature ethanol purge 3 times, washed with de-ionized water 3 times after heating terminates, vacuum drying chamber 50 DEG C of dry 2h obtain Fe
3o
4magnetic nanoparticle;
(2) core-shell type Fe
3o
4/ SiO
2the preparation of magnetic-particle: the nanometer Fe of getting preparation in 0.2g step (1)
3o
4be scattered in salpeter solution, ultrasonic 10min, by washed with de-ionized water 6 times, be scattered in the mixed liquor of 20mL ethanol and 4mL deionized water, ultrasonic 10min, pours in three mouthfuls of round-bottomed flasks, drips 1mL ammoniacal liquor and 0.8mL tetraethyl orthosilicate (TEOS) wherein continuously under mechanical stirring, after 3h is carried out in reaction, the sediment of generation is obtained Fe in vacuum 60 DEG C of dry 1h
3o
4/ SiO
2nano particle;
(3) polyelectrolyte modifies Fe
3o
4/ SiO
2the preparation of magnetic-particle: diallyl dimethyl ammoniumchloride (PDDA) solution of preparation 100mL2%, magnetic agitation 0.5h, transfers to solution in three mouthfuls of round-bottomed flasks, adds the Fe of preparation in 0.1g step (2) under mechanical stirring
3o
4/ SiO
2magnetic-particle, after 3h is carried out in reaction, by the sediment washed with de-ionized water 6 times generated, obtains the Fe that polyelectrolyte is modified
3o
4/ SiO
2magnetic-particle;
(4) with high temperature reduction method synthesis Au nano particle: by the HAuCl of 2mL2%
4solution joins in 46mL deionized water, heating said solution under churned mechanically condition in oil bath pan, when temperature rises to 100 DEG C, the aqueous solution of 2mL containing 114mg sodium citrate is added in above-mentioned solution, reaction 20min stops heating, product is continued stirring and is cooled to room temperature, obtain Au nano particle;
(5) Fe that Au is coated
3o
4/ SiO
2the preparation of magnetic-particle: the Fe that 0.02g step (3) is obtained
3o
4/ SiO
2magnetic-particle is scattered in the obtained Au colloidal sol of 40mL step (4), puts into shaking table, with 150 revs/min of reaction 20min at 30 DEG C, by product washed with de-ionized water 6 times, obtains the Fe that Au is coated
3o
4/ SiO
2magnetic-particle;
(6) preparation of surface-enhanced Raman (SERS) substrate of positive polyelectrolyte modification: the Fe that Au 0.02g step (5) obtained is coated
3o
4/ SiO
2magnetic-particle is scattered in the PDDA solution of 10mL2%, reacts 20min at putting into shaking table 30 DEG C with 150 revs/min, by the positive magnetic SERS substrate PDDA-Fe that product washed with de-ionized water obtains PDDA afterwards and modifies for 6 times
3o
4/ SiO
2/ Au (FSPAP);
(7) preparation of the SERS substrate of negative polyelectrolyte modification: the FSPAP magnetic-particle that 0.01g step (6) obtains is scattered in 10mL kayexalate (PSS) solution, 20min are reacted with 150 revs/min, by the negative magnetic SERS substrate PSS-Fe that product washed with de-ionized water obtains PSS afterwards and modifies for 6 times at putting into shaking table 30 DEG C
3o
4/ SiO
2/ Au (FSPAPP);
(8) enrichment of pigment and detection: the magnetic SERS substrate that 0.2mg step (7) obtains is scattered in pigment solution after mixing certain hour and with externally-applied magnetic field, magnetic-particle is collected, use Raman spectrometer to carry out signals collecting, obtain the SERS spectrogram of pigment.
2. a kind of substrate that can be used for zwitterion pigment selective enumeration method as claimed in claim 1, in step (2), concentration of nitric acid 0.1mol/L, consumption is 20mL.
3. a kind of substrate that can be used for zwitterion pigment selective enumeration method as claimed in claim 1, in step (3), PDDA solution preparation method is: in the PDDA solution of 10mL20%, add 90mL deionized water, 88.2mg sodium citrate, 11.5mg sodium chloride.
4. a kind of substrate that can be used for zwitterion pigment selective enumeration method as claimed in claim 1, in step (6), PDDA solution preparation method is: in the PDDA solution of 1mL20%, add 9mL deionized water, 8.82mg sodium citrate, 1.15mg sodium chloride.
5. a kind of substrate that can be used for zwitterion pigment selective enumeration method as claimed in claim 1, in step (7), kayexalate (PSS) solution preparation method is: in the PSS solution of 1mL30%, add 9mL deionized water, 3mg sodium chloride.
6. a kind of substrate that can be used for zwitterion pigment selective enumeration method as claimed in claim 1, the kation pigment detected in step (8) is crystal violet and malachite green, and negative ion pigment is Congo red and sunset yellow.
7. a kind of substrate that can be used for zwitterion pigment selective enumeration method as claimed in claim 1, in step (8), the enrichment method of negative ion pigment is as follows: be placed in 1.5mL centrifuge tube by FSPAP at the bottom of 0.2mg cation radical, add 1mL negative ion pigment, mixing 1h, reclaims the magnetic-particle being enriched negative ion pigment with externally-applied magnetic field.
8. a kind of substrate that can be used for zwitterion pigment selective enumeration method as claimed in claim 1, the enrichment method of step (8) cationic pigment is as follows: be placed in 1.5mL centrifuge tube by FSPAPP at the bottom of 0.2mg anion base, add 1mL kation pigment, incorporation time 1h, reclaims the magnetic-particle being enriched kation pigment with externally-applied magnetic field.
9. a kind of substrate that can be used for zwitterion pigment selective enumeration method as claimed in claim 1, in step (8), the enrichment method of hybrid pigment solution is as follows: be placed in 1.5mL centrifuge tube respectively by FSPAPP at the bottom of FSPAP and 0.2mg anion base at the bottom of 0.2mg anion base, respectively add 1mL hybrid pigment, incorporation time 1h, reclaims the magnetic-particle being enriched pigment with externally-applied magnetic field.
10. a kind of substrate that can be used for zwitterion pigment selective enumeration method as claimed in claim 1, in step (8), the detection method of pigment is as follows: be placed on silicon chip by the magnetic-particle being enriched pigment, Portable Raman spectrometer is utilized to carry out signals collecting, optical maser wavelength 785nm, sweep time 5s.
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Cited By (10)
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CN105738341A (en) * | 2016-02-22 | 2016-07-06 | 中国科学院生态环境研究中心 | Heavy metal mercury ion detection method |
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CN106053427A (en) * | 2016-05-23 | 2016-10-26 | 中国科学院生态环境研究中心 | Heavy metal hexavalent chromium detection method |
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CN108827929A (en) * | 2018-04-17 | 2018-11-16 | 华东理工大学 | A kind of SERS probe and preparation method thereof based on MOFs |
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CN111484843A (en) * | 2020-02-21 | 2020-08-04 | 南京理工大学 | Composite nano-particle for enhancing full-spectrum absorption characteristic of sunlight |
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CN105738341A (en) * | 2016-02-22 | 2016-07-06 | 中国科学院生态环境研究中心 | Heavy metal mercury ion detection method |
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CN106770159A (en) * | 2016-12-02 | 2017-05-31 | 中国计量大学 | High sensitivity food color detection method |
CN107064105A (en) * | 2017-04-10 | 2017-08-18 | 上海应用技术大学 | It is a kind of at the same detect aquatic products in sunset yellow and malachite green method |
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