CN105021590B - A kind of quick determination method of water body Malachite Green - Google Patents
A kind of quick determination method of water body Malachite Green Download PDFInfo
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- CN105021590B CN105021590B CN201510412433.2A CN201510412433A CN105021590B CN 105021590 B CN105021590 B CN 105021590B CN 201510412433 A CN201510412433 A CN 201510412433A CN 105021590 B CN105021590 B CN 105021590B
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Abstract
The invention discloses a kind of quick determination method of water body Malachite Green.Comprise the following steps：1) a series of malachite green standard sample of concentration is wrapped up in into nanometer magnetic bead with silver respectively to mix, adsorbs thereon malachite green, and silver is collected using magnetic field and wrap up in nanometer magnetic bead；2) to step 1) the middle silver collected wraps up in nanometer magnetic bead and carries out SERS measure, and draw the standard curve between malachite green concentration and Raman signal intensity；3) take testing sample successively by step 1) and step 2) handled, predict the Raman signal intensity of testing sample, then substitute into step 2) standard curve in, learn testing sample Malachite Green concentration.Wrapping up in nanometer magnetic bead as SERS using silver strengthens substrate, realizes the quantitative analysis of trace malachite green in water body.Easy to operate, test limit is very low, accurate and quick, and can be directly used for the detection of actual water sample Malachite Green.
Description
Technical field
The invention belongs to composition detection field, and in particular to a kind of quick determination method of water body Malachite Green.
Background technology
Malachite green (Malachite green, MG) is a kind of one kind for being widely used in the industries such as printing and dyeing, weaving, papermaking
The green colouring material of triphenylmenthane type, while because it has good bactericidal effect and cheap and easy to get, aquaculture is used for for a long time
The antifungal of industry, bactericidal, the medicine of antiparasitic.Due to its potential carcinogenic, teratogenesis, mutagenic toxic action, by
Multiple countries forbid using in aquaculture, are the pollutants of key monitoring in water pollution and Safety of Aquatic Products.Current peacock
The method that predominantly detects of malachite green includes high performance liquid chromatography (HPLC) and high performance liquid chromatography tandem mass spectrum method (LC-MS) etc.,
Although these methods have the features such as sensitivity is high, accuracy is good, there is detection time length, pretreatment is complicated, detect into
This height is, it is necessary to the deficiency such as professional's operation, it is difficult to meet food or the real-time of environmental sample, quick detection requirement.Therefore, grind
Study carefully and develop it is easy to operate, fast and accurately malachite green vestigial new detecting method there is very important economic value and society
Value.
One kind that Raman spectrum belongs in light scattering phenomenon, its frequency, peak position change, peak width, peak intensity and polarization are with being tested
The molecular composition of material and molecular structure are relevant.SERS (Surface enhanced Raman
Scattering, SERS) at interface and Surface Science, material analysis, biology, medical science, food security, environmental monitoring and state
The fields such as family's safety are widely applied.SERS technologies are not only able to provide the structural information of more rich chemical molecular, can
Real-time, in-situ investigation is realized, and sensitivity is high, data processing is simple, accuracy rate is high, is a kind of strong trace detection work
Tool.Due to its without sample pretreatment, easy to operate, detection speed is fast, accuracy rate is high, instrument is portable the features such as, SERS detection
Positive effect is served in food security quick detection.The preparation of SERS nano materials is always that SERS technologies are most crucial
Key factor, and played an important role for the research range and application field for expanding SERS.
The content of the invention
It is an object of the invention to provide a kind of quick determination method of water body Malachite Green, the detection method is wrapped up in silver to be received
Rice magnetic bead strengthens trace malachite green in substrate, energy Quantitative detection water body as SERS (SERS).
Detection method provided by the present invention, comprises the following steps：
1) a series of malachite green standard sample of concentration is wrapped up in into nanometer magnetic bead with silver respectively to mix, passes through malachite green
Dimethylamino on non-phenyl ring is adsorbed in silver and wrapped up on the argent on nanometer magnetic bead surface, and wraps up in nano magnetic using magnetic field collection silver
Pearl, leaves and takes stand-by；
2) to step 1) the middle silver collected wraps up in nanometer magnetic bead and carries out SERS measure, and draw malachite green
Standard curve between concentration and Raman signal intensity；
3) testing sample is taken successively by step 1) and step 2) handled, the Raman signal intensity of testing sample is predicted,
Substitute into step 2 again) standard curve in, learn testing sample Malachite Green concentration.
In above-mentioned detection method, step 1) in, a series of concentration range of the malachite green standard sample of concentration is
10-3Mol/L~10-14Mol/L, wherein, big concentration is 10 times of small concentration in the malachite green standard sample of two adjacent concentration.
It is the presence in the form of silver wraps up in nanometer magnetic bead aqueous suspension that the silver, which wraps up in nanometer magnetic bead, wherein, the silver, which is wrapped up in, to be received
The concentration that silver wraps up in nanometer magnetic bead in rice magnetic bead aqueous suspension is 1-3mg/mL, concretely 2mg/mL.
The volume ratio that the malachite green standard sample and the silver wrap up in nanometer magnetic bead aqueous suspension is 1：(1-3), tool
Body can be 1:2.
The temperature of the mixing is 20-30 DEG C, and concretely 25 DEG C, the time is 20-40min, concretely 30min.
The utilization magnetic field collection silver wraps up in nanometer magnetic bead, specifically can be as follows：Silver, which is collected, using magnet wraps up in nano magnetic
Pearl is enriched in container bottom, removes supernatant, you can obtains silver and wraps up in nanometer magnetic bead.
, can will be collected in addition, in order to ensure silver wraps up in the malachite green molecule of all absorption in nanometer magnetic bead surface
Silver is wrapped up in nanometer magnetic bead and is scattered in deionized water, sonic oscillation 1-2min (concretely 1min), enters the malachite green of residual
Enter in deionized water, then, repeat the step of collection silver wraps up in nanometer magnetic bead-remove supernatant-addition deionized water at least 3
It is secondary.
In above-mentioned detection method, step 1) in, in addition to the silver being collected into is wrapped up in into nanometer magnetic bead be scattered in deionized water
The step of, the silver being collected into is wrapped up in nanometer magnetic bead and uniform suspended state is presented, the silver being collected into wraps up in nanometer magnetic bead
Suspension, wherein, the silver being collected into wraps up in silver in nanometer magnetic bead suspension and wraps up in the concentration of nanometer magnetic bead for 0.5-1.5 μ g/ μ L,
Specially 1 μ g/ μ L.
The silver wraps up in nanometer magnetic bead concretely Fe3O4@SiO2@Ag nanometer magnetic beads, the particle diameter that the silver wraps up in nanometer magnetic bead is
360~600nm.
The silver is wrapped up in nanometer magnetic bead and can specifically prepared by following correlation methods.
In above-mentioned detection method, step 2) in, the condition that the SERS is determined is as follows：Optical maser wavelength
633nm, time for exposure 10-20s, integral number of times 1-5 times, laser intensity 0.5-5mW.
Nanometer magnetic bead and preparation method thereof is wrapped up in it is also another object of the present invention to provide silver.
Silver provided by the present invention wraps up in nanometer magnetic bead for Fe3O4@SiO2@Ag nanometer magnetic beads, the silver wraps up in the grain of nanometer magnetic bead
Footpath is 360~600nm, the Fe3O4@SiO2@Ag nanometer magnetic beads are followed successively by Fe from the inside to the outside3O4、SiO2And Ag, wherein, SiO2
Connected between Ag by PAH (PAH).
The PAH (PAH) carries amino, and self-organizing is in Fe3O4@SiO2Microsphere surface, passes through amino
It is coupled with Nano Silver.
Fe provided by the present invention3O4@SiO2The preparation method of@Ag nanometer magnetic beads, comprises the following steps：
A) by nanogold and Fe3O4@SiO2Nanoparticle is mediated by high molecular polymer PAH, prepares Fe3O4@
SiO2- Au nano particles (Fe3O4@SiO2-Au NPs)；
B) by Fe3O4@SiO2- Au nano particles are scattered in the silver nitrate aqueous solution containing PVP, add the water of formaldehyde
The aqueous solution of solution and ammonia, ultrasonic vibration obtains Fe3O4@SiO2@Ag microballoons.
In above-mentioned preparation method, in step a), the Fe3O4@SiO2Nanoparticle can be specifically prepared via a method which
Arrive：I) solvent structure Fe is passed through3O4Nanometer magnetic bead；Ii) by silylating reagent to Fe3O4Nanometer magnetic bead carries out silanization
Processing, obtains Fe3O4@SiO2Nanoparticle.
Wherein, the solvent structure Fe3O4The method of nanometer magnetic bead is specific as follows：By FeCl3·6H2O, NaAc and
PEG6000 reacts 10-12h (concretely 12h) under 150-250 DEG C (concretely 200 DEG C), obtained in ethylene glycol
Fe3O4Nanometer magnetic bead, wherein, FeCl3·6H2O, NaAc and PEG6000 mass ratio are (1.30-1.40)：(2.5-2.7)：1,
Concretely 1.35：2.7：1.
The step of silanization treatment, is as follows：By the Fe3O4Nanometer magnetic bead and tetraethoxysilane in deionized water-
In the mixed solution of ammonia-ethanol, 40-50min (concretely 45min) is reacted under 20-30 DEG C (concretely 25 DEG C), its
In, the volume ratio of deionized water, ammonia and ethanol is 1 in the mixed solution of the deionization water-ammonia-ethanol：(0.6.-0.9)：
(15-20), concretely 1:0.8:18.
In above-mentioned preparation method, in step a), the Fe3O4@SiO2- Au nano particles can specifically be prepared as follows：
By high molecular polymer PAH and Fe3O4@SiO2Ultrasonically treated 15-30min is (concretely in deionized water for nanoparticle
20min), high molecular polymer PAH self-organizings are made in Fe3O4@SiO2On nanoparticle, make amino in its surface modification；Again will be through
The Fe of PAH modifications3O4@SiO2The nanogold of nanoparticle and colloidal state mixes ultrasonically treated 0.5-1h (concretely 1h), its
In, high molecular polymer PAH and Fe3O4@SiO2The mass ratio of nanoparticle is (2-3)：1, concretely 2.5:1, colloidal state
Nanogold can be prepared by method of the prior art.
In above-mentioned preparation method, in step b), the molar concentration of silver nitrate is in the silver nitrate aqueous solution containing PVP
0.2-0.4mM (concretely 0.25mM), PVP mass fraction are 0.15-0.30% (concretely 0.2%).
The volume fraction of the aqueous solution of the formaldehyde is 30-45% (concretely 37%).
The volume fraction of the aqueous solution of the ammonia is 20-30% (concretely 25%).
The temperature of the ultrasonic vibration is 25-40 DEG C, and concretely 30 DEG C, the time is 1-5min, concretely 2min.
Pass through Fe described in step a)3O4@SiO2Nanogold in-Au nano particles makes the nitre in step b) as seed
The Nano Silver of sour silver reduction generation grows in nanogold, so as to form one layer of silver for being rolled in magnetic bead surfaces.
In addition, Fe of the present invention3O4@SiO2@Ag nanometer magnetic beads strengthen as SERS (SERS)
Application in substrate falls within protection scope of the present invention.
The present invention wraps up in nanometer magnetic bead as SERS by the use of prepared silver strengthens substrate, is successfully realized trace hole in water body
The quantitative analysis of sparrow malachite green.This method is easy to operate, and test limit is very low, accurate and quick, and can be directly used in actual water sample
The detection of malachite green.
Brief description of the drawings
Silver of the Fig. 1 obtained by embodiment 1 wraps up in the TEM schematic diagrames of nanometer magnetic bead.
Fig. 2 wraps up in Fe during nanometer magnetic bead to prepare silver in embodiment 13O4Microballoon, Fe3O4@SiO2- Au NPs and silver, which are wrapped up in, to be received
The corresponding XRD of rice magnetic bead.
Fig. 3 be embodiment 2 in utilize silver wrap up in nanometer magnetic bead detect malachite green process schematic.
Fig. 4 is the SERS examination criteria curves of the middle and high concentration malachite green of embodiment 2.
Fig. 5 is the SERS examination criteria curves of low concentration malachite green in embodiment 2.
Embodiment
The method of the present invention is illustrated below by specific embodiment, but the invention is not limited in this.
Experimental method described in following embodiments, is conventional method unless otherwise specified；The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1, prepare silver and wrap up in nanometer magnetic bead：
1) with solvent structure Fe3O4Nanometer magnetic bead：By 1.35g FeCl3·6H2O is added in 40mL ethylene glycol,
Magnetic stirs 30min, it is dissolved in ethylene glycol；And then, 2.7g NaAc and 1g PEG6000 are added, are stirred continuously straight
To being completely dissolved；Finally, mixed solution is transferred in 50mL Teflon-lined autoclaves, and in heating at 200 DEG C
12h, is washed three times respectively with deionized water and ethanol, and prepared 400nm Fe are collected with magnet3O4Microballoon, in 60 DEG C of vacuum
Lower dry 5h, leaves and takes stand-by；
2)Fe3O4@SiO2The preparation of microballoon：Take the above-mentioned Fe of 0.1g3O4Microballoon is scattered in the mixing of deionization water-ammonia-ethanol
(three's volume ratio is 1 in solution:0.8:18, concretely 10mL/8mL/180mL), the ultrasonic vibration 15min at 25 DEG C, and
During ultrasonic vibration, 100 μ L tetraethoxysilane (TEOS) is added slowly thereto, whole reaction system is in room temperature
45min is kept under (25 DEG C)；Finally, after deionized water and ethanol are cleaned several times, prepared product is collected with magnet, and
In drying 5h under 60 DEG C of vacuum, leave and take stand-by；
3) silver of high molecular polymer PAH (PAH) mediation wraps up in the preparation of nanometer magnetic bead：By macromolecule
Polymer is coupled to Fe by way of self-organizing3O4@SiO2Microsphere surface, specifically first can be dissolved into deionization by 0.25g PAH
In water, then the freshly prepd Fe of 0.1g are added thereto3O4@SiO2Nanoparticle, ultrasonic 20min, PAH self-organizings are in nanoparticle
Surface so that the upper amino of microsphere surface modification；
Prepare 3nm nanogold particle：At room temperature, 200mL is contained into 0.25mM HAuCl4With 0.25mM citric acids
The aqueous solution of trisodium strong stirring in conical flask；Afterwards, by the 6mL 0.1mol/L just prepared NaBH4Solution is rapidly joined
Into above-mentioned solution, solution can be made to immediately become pink, show the formation of nanogold；Then, by by PAH modifications
Fe3O4@SiO2Microballoon mixes ultrasonically treated 1h with the 3nm nanogold of colloidal state, generates Fe3O4@SiO2-Au NPs；Finally, lead to
Magneticaction is crossed by Fe3O4@SiO2- Au NPs are separated from superfluous colloidal solution, and are flushed three times with deionized water；
4) monodispersed Fe is prepared3O4@SiO2@Ag microballoons：By 10mg Fe3O4@SiO2- Au NPs are scattered in 100mL
In the 0.25mM silver nitrate aqueous solution containing 0.2wt%PVP, excessive volume fraction is then sequentially added for 37% formalin
Solution (150 μ L) and 25% ammonia solution (300 μ L)；By the Fe of acquisition3O4@SiO2@Ag microballoons are in ultrasonic vibration at 30 DEG C
2min；Final products remove unnecessary PVP by magnetic separation, and with deionized water rinsing 5 times, that is, obtain being used for malachite
The silver of green detection wraps up in nanometer magnetic bead, its average grain diameter be 530nm, its corresponding TEM and XRD as depicted in figs. 1 and 2, from Fig. 1
Learn：Magnetic bead surfaces one layer of Nano Silver of formation, learns from Fig. 2：For nanometer Fe3O4, its 30 °, 37.1 °, 43 °, 53.4 °,
56.9 ° and 62.5 ° of diffraction maximum corresponds to (112), (202), (220), (024), (303) and (224) respectively；When coupled to Nano gold
Afterwards, from XRD spectrum as can be seen that its diffraction maximum that gold crystals by adopting is occurred in that at 38.2 °, 44.3 ° and 64.5 °, corresponding to (111),
And (220) (200)；After Nano Silver is wrapped, occur silver typical diffractive peak, correspond respectively to (111), (200), (220) and
(311)。
Embodiment 2, based on SERS principles, use silver to wrap up in the standard curve that nanometer magnetic bead determines malachite green：
1) malachite green detection process is as shown in figure 3, first by 50 μ L various concentrations malachite green and 100 μ L 2mg/mL
Nano Silver, which is wrapped up in nanometer magnetic bead aqueous suspension and is added in 0.5mL EP pipes, to be mixed, and absorption is mixed on blending instrument
30min, prevents silver from wrapping up in nanometer magnetic bead deposition and causing absorption incomplete, in the process, malachite green molecule can pass through non-benzene
Dimethylamino absorption on ring is on the argent that silver wraps up in nanometer magnetic bead surface；
2) mix after absorption, EP pipes are taken out, being positioned over bottom has on the magnetic frame of magnet, will by the attraction of magnet
Silver wraps up in nanometer magnetic bead and is enriched in bottom of the tube.Supernatant is suctioned out with liquid-transfering gun afterwards, the silver for retaining ttom of pipe wraps up in nanometer magnetic bead, Xiang Guan
150 μ L of interior addition ultra-pure water, then vibrates 1min in numerical control ultrasonic cleaning machine, the malachite green of residual is entered in water,
Then repeat silver and wrap up in nanometer magnetic bead enrichment-Aspirate supernatant-addition ultra-pure water step 3 time, it is ensured that silver wraps up in nanometer magnetic bead
The malachite green molecule of all absorption in surface；Then plus 50 μ L ultra-pure water, Nano Silver is wrapped up in nanometer magnetic bead and be presented uniform
Suspended state；
3) 2 μ L of absorption Nano Silver wraps up in nanometer magnetic bead and drops in the gold nano-plates surface being fixed on double faced adhesive tape on slide,
Determined after after its natural air drying, proceeding by SERS.Wherein condition determination is：Optical maser wavelength 633nm, center wave number 1500cm-1,
Time for exposure 10s, integral number of times 1 time, laser intensity 1mW；
4) according to the relation of its corresponding Raman signal intensity of concentration of malachite green, standard curve is drawn, such as Fig. 4 institutes
Show.As a result show, the condition determination is for 10-10More than mol/L concentration linear relationship very well, and does not have then to low concentration
Preferable linear relationship.Therefore need to carry out certain condition optimizing to reduce detection limit；
5) it is the malachite green solution of detection low concentration, while keeping other condition determinations constant, by integral number of times
Bring up to 5 times, again to 10-10Mol/L~10-14Mol/L malachite green solution carries out SERS measure, may be significantly
Linear relationship between malachite green concentration and Raman signal intensity, as shown in Figure 5.
Embodiment 3, wrap up in Nano Silver the running water mark-on sample that nanometer magnetic bead determines malachite green：
1) malachite green detection process be the same as Example 2, first by 50 μ L running water mark-on sample and 100 μ L 2mg/mL
Silver is wrapped up in be mixed in the EP pipes for be added in nanometer magnetic bead aqueous suspension 0.5mL, and absorption 30min is mixed on blending instrument.
In the process, malachite green molecule can be by the absorption of the dimethylamino on non-phenyl ring on the argent of magnetic bead surfaces；
2) mix after absorption, EP pipes are taken out, being positioned over bottom has on the magnetic frame of magnet, will by the attraction of magnet
Silver wraps up in nanometer magnetic bead and is enriched in bottom of the tube；Supernatant is suctioned out with liquid-transfering gun afterwards, the silver for retaining ttom of pipe wraps up in nanometer magnetic bead, Xiang Guan
150 μ L of interior addition ultra-pure water, then vibrates 1min in numerical control ultrasonic cleaning machine, the malachite green of residual is entered in water,
Then repeat silver and wrap up in nanometer magnetic bead enrichment-Aspirate supernatant-addition ultra-pure water step 3 time, it is ensured that magnetic bead surfaces are whole
It is the malachite green molecule in absorption；Plus 50 μ L ultra-pure water wraps up in nanometer magnetic bead by Nano Silver uniform suspension is presented then
State；
3) 2 μ L of absorption Nano Silver wraps up in nanometer magnetic bead and drops in the gold nano-plates surface being fixed on double faced adhesive tape on slide,
Determined after after its natural air drying, proceeding by SERS.Wherein condition determination is：Optical maser wavelength 633nm, center wave number 1500cm-1,
Time for exposure 10s, integral number of times 5 times, laser intensity 1mW；
4) standard curve in embodiment 2, conversion obtains the detectable concentration of malachite green, and is carried out with spiked levels
Compare, obtain the rate of recovery of malachite green.As known from Table 1, the recovery of standard addition of running water Malachite Green is 90%~110%
Between, meet detection and require.
Embodiment 4, wrap up in Nano Silver the secondary clarifier effluent mark-on sample that nanometer magnetic bead determines malachite green：
1) malachite green detection process leads to embodiment 2, first by 50 μ L secondary clarifier effluent mark-on sample and 100 μ L 2mg/
ML silver, which is wrapped up in nanometer magnetic bead aqueous suspension and is added in 0.5mL EP pipes, to be mixed, and absorption is mixed on blending instrument
30min.In the process, malachite green molecule can be adsorbed by the dimethylamino on non-phenyl ring and wrap up in nanometer magnetic bead surface in silver
On argent；
2) mix after absorption, EP pipes are taken out, being positioned over bottom has on the magnetic frame of magnet, will by the attraction of magnet
Silver wraps up in nanometer magnetic bead and is enriched in bottom of the tube.Supernatant is suctioned out with liquid-transfering gun afterwards, the silver for retaining ttom of pipe wraps up in nanometer magnetic bead, Xiang Guan
150 μ L of interior addition ultra-pure water, then vibrates 1min in numerical control ultrasonic cleaning machine, the malachite green of residual is entered in water,
Then repeat silver and wrap up in nanometer magnetic bead enrichment-Aspirate supernatant-addition ultra-pure water step 3 time, it is ensured that silver wraps up in nanometer magnetic bead
Surface is entirely the malachite green molecule in absorption.Plus 50 μ L ultra-pure water wraps up in nanometer magnetic bead by Nano Silver and is presented uniform then
Suspended state；
3) 2 μ L of absorption Nano Silver wraps up in nanometer magnetic bead and drops in the gold nano-plates surface being fixed on double faced adhesive tape on slide,
Determined after after its natural air drying, proceeding by SERS.Wherein condition determination is：Optical maser wavelength 633nm, center wave number 1500cm-1,
Time for exposure 10s, integral number of times 5 times, laser intensity 1mW.
4) standard curve in embodiment 2, conversion obtains the detectable concentration of malachite green, and is carried out with spiked levels
Compare, obtain the rate of recovery of malachite green.As known from Table 1, the recovery of standard addition of running water Malachite Green is 95%~110%
Between, meet detection and require.
Table 1, wrap up in using Nano Silver nanometer magnetic bead detection running water and secondary clarifier effluent malachite green mark-on experimental result
Claims (7)
1. a kind of silver wraps up in the preparation method of nanometer magnetic bead, it is characterised in that：
The silver wraps up in nanometer magnetic bead for Fe3O4@SiO2@Ag nanometer magnetic beads, are followed successively by Fe from the inside to the outside3O4、SiO2And Ag, wherein,
SiO2Connected between Ag by PAH, the particle diameter that the silver wraps up in nanometer magnetic bead is 360 ~ 600nm；
Comprise the following steps：a）By nanogold and Fe3O4@SiO2Nanoparticle is mediated by high molecular polymer PAH, is prepared into
To Fe3O4@SiO2- Au nano particles；The Fe3O4@SiO2Nanoparticle is prepared via a method which to obtain：i）Pass through solvent heat
Method synthesizes Fe3O4Nanometer magnetic bead；ii）By silylating reagent to Fe3O4Nanometer magnetic bead carries out silanization treatment, obtains Fe3O4@
SiO2Nanoparticle；
Wherein, the solvent structure Fe3O4The method of nanometer magnetic bead is as follows：By FeCl3·6H2O, NaAc and PEG6000 in
In ethylene glycol, 10-12h is reacted at 150-250 DEG C, Fe is obtained3O4Nanometer magnetic bead, FeCl3·6H2O, NaAc and PEG6000
Mass ratio be（1.30-1.40）：（2.5-2.7）：1；
The step of silanization treatment, is as follows：By the Fe3O4Nanometer magnetic bead and tetraethoxysilane are in deionization water-ammonia-second
In the mixed solution of alcohol, 40-50 min are reacted at 20-30 DEG C, wherein, in the mixed solution of the deionization water-ammonia-ethanol
The volume ratio of deionized water, ammonia and ethanol is 1：（0.6.-0.9）：（15-20）；
b）By Fe3O4@SiO2- Au nano particles are scattered in the silver nitrate aqueous solution containing PVP, add the aqueous solution of formaldehyde
With the aqueous solution of ammonia, ultrasonic vibration obtains Fe3O4@SiO2@Ag microballoons.
2. preparation method according to claim 1, it is characterised in that：Step a）In, the Fe3O4@SiO2- Au nanometers
Grain is prepared as follows：By high molecular polymer PAH and Fe3O4@SiO2Nanoparticle ultrasonically treated 15- in deionized water
30 min；The Fe that will be modified again through PAH3O4@SiO2The nanogold of nanoparticle and colloidal state mixes ultrasonically treated 0.5-1h,
Wherein, high molecular polymer PAH and Fe3O4@SiO2The mass ratio of nanoparticle is（2-3）：1.
3. preparation method according to claim 1 or 2, it is characterised in that：Step b）In, the silver nitrate containing PVP
The molar concentration of silver nitrate is 0.2-0.4mM in the aqueous solution, and PVP mass fraction is 0.15-0.30%；
The volume fraction of the aqueous solution of the formaldehyde is 30-45%；The volume fraction of the aqueous solution of the ammonia is 20-30%；
The temperature of the ultrasonic vibration is 25-40 DEG C, and the time is 1-5min.
4. a kind of quick determination method of water body Malachite Green, comprises the following steps：
1）A series of malachite green standard sample of concentration is wrapped up in into nanometer magnetic bead with silver respectively to mix, malachite green is adsorbed in silver
On the argent for wrapping up in nanometer magnetic bead surface, and nanometer magnetic bead is wrapped up in using magnetic field collection silver；
The silver wraps up in nanometer magnetic bead for Fe3O4@SiO2@Ag nanometer magnetic beads, the particle diameter that the silver wraps up in nanometer magnetic bead is 360 ~ 600nm；
The silver is wrapped up in nanometer magnetic bead and obtained according to the preparation method any one of claim 1-3；
It is described to collect silver using magnetic field and wrap up in nanometer magnetic bead and carry out as follows：Silver is wrapped up in into nanometer magnetic bead using magnet and is enriched in appearance
Device bottom, removes supernatant, you can obtains silver and wraps up in nanometer magnetic bead；
2）To step 1）The silver of middle collection wraps up in nanometer magnetic bead and carries out SERS measure, and draws malachite green concentration
Standard curve between Raman signal intensity；
3）Take testing sample successively by step 1）With step 2）Handled, predict the Raman signal intensity of testing sample, then generation
Enter step 2）Standard curve in, learn testing sample Malachite Green concentration.
5. detection method according to claim 4, it is characterised in that：Step 1）In, a series of malachite of concentration
The concentration range of green standard sample is 10-3mol/L~10-14Mol/L, wherein, in the malachite green standard sample of two adjacent concentration
Big concentration is 10 times of small concentration；
It is the presence in the form of silver wraps up in nanometer magnetic bead aqueous suspension that the silver, which wraps up in nanometer magnetic bead, wherein, the silver wraps up in nano magnetic
The concentration that silver wraps up in nanometer magnetic bead in pearl aqueous suspension is 1-3 mg/mL；
The volume ratio that the malachite green standard sample and the silver wrap up in nanometer magnetic bead aqueous suspension is 1：（1-3）；
The temperature of the mixing is 20-30 DEG C, and the time is 20-40 min.
6. the detection method according to claim 4 or 5, it is characterised in that：Step 1）In, in addition to the silver being collected into wrapped up in
Nanometer magnetic bead is scattered in deionized water, sonic oscillation 1-2min, the malachite green of residual is entered in deionized water, then,
Repeat the step of collection silver wraps up in nanometer magnetic bead-remove supernatant-addition deionized water at least 3 times；
Step 1）In, in addition to the silver being collected into wrapped up in into the step that nanometer magnetic bead is scattered in deionized water, make described be collected into
Silver wrap up in nanometer magnetic bead uniform suspended state be presented, obtain silver and wrap up in nanometer magnetic bead suspension, wherein, the silver wraps up in nanometer magnetic bead
The concentration that silver wraps up in nanometer magnetic bead in suspension is 0.5-1.5 μ g/ μ L.
7. the detection method according to claim 4 or 5, it is characterised in that：Step 2）In, the SERS
The condition of measure is as follows：Optical maser wavelength 633nm, time for exposure 10-20s, integral number of times 1-5 times, laser intensity 0.5-5mW.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510412433.2A CN105021590B (en) | 2015-07-14 | 2015-07-14 | A kind of quick determination method of water body Malachite Green |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510412433.2A CN105021590B (en) | 2015-07-14 | 2015-07-14 | A kind of quick determination method of water body Malachite Green |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105021590A CN105021590A (en) | 2015-11-04 |
| CN105021590B true CN105021590B (en) | 2017-09-26 |
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| CN101294904A (en) * | 2008-06-05 | 2008-10-29 | 华东理工大学 | Production method of surface reinforced Raman scattering substrate |
| CN102128908A (en) * | 2010-01-19 | 2011-07-20 | 华东理工大学 | On-site quick detection method for organic pollutants in water |
| CN104122135A (en) * | 2014-07-31 | 2014-10-29 | 中国科学院生态环境研究中心 | Method for separating and enriching malachite green through cloud point extraction and Raman detection method |
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| CN101294904A (en) * | 2008-06-05 | 2008-10-29 | 华东理工大学 | Production method of surface reinforced Raman scattering substrate |
| CN102128908A (en) * | 2010-01-19 | 2011-07-20 | 华东理工大学 | On-site quick detection method for organic pollutants in water |
| CN104122135A (en) * | 2014-07-31 | 2014-10-29 | 中国科学院生态环境研究中心 | Method for separating and enriching malachite green through cloud point extraction and Raman detection method |
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| Multifunctional Silver-Embedded Magnetic Nanoparticles as SERS Nanoprobes and Their Applications;Bong-Hyun Jun et al.;《Small》;20100131;第6卷(第1期);第119-125页、流程图1 * |
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