CN110064360A - Superparamagnetism Fe3O4@SiO2The preparation method of@Ag nanocomposite - Google Patents

Superparamagnetism Fe3O4@SiO2The preparation method of@Ag nanocomposite Download PDF

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CN110064360A
CN110064360A CN201910401109.9A CN201910401109A CN110064360A CN 110064360 A CN110064360 A CN 110064360A CN 201910401109 A CN201910401109 A CN 201910401109A CN 110064360 A CN110064360 A CN 110064360A
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冯军
程昊
黄文艺
李利军
孔红星
李彦青
徐亚娟
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Guangxi University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0233—Compounds of Cu, Ag, Au
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties

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Abstract

The present invention relates to a kind of superparamagnetism Fe3O4@SiO2The preparation method of@Ag nanocomposite provides a kind of simple, effective seed mediating growth method, i.e. crystal seed method.High-performance Ag coating Fe is prepared by seed mediating growth method3O4@SiO2 NPs, the isotropic growth of all Ag seeds and the static stabilization of polyvinylpyrrolidone (PVP) form Ag shell completely.Occurred using mechanical stirring and sonication techniques come abundant stimulate the reaction simultaneously and further avoid assembling, preparation method is simple and quick, the Fe of preparation3O4@SiO2@AgNPs has good magnetic property, can quickly separate from sample solution, is enriched with target molecule, shortens detection time, and hot spot between also can produce particle abundant is assembled by Magnetic guidance.Substrate Fe prepared by the present invention3O4@SiO2@Ag nuclear shell structure nano compound has certain application value in the quick context of detection of food, drug.

Description

Superparamagnetism Fe3O4@SiO2The preparation method of@Ag nanocomposite
Technical field
The present invention relates to a kind of preparation method of superparamagnetic nano composite material, in particular to a kind of superparamagnetism Fe3O4@SiO2The preparation method of@Ag nanocomposite.
Background technique
1977, Jeanmaire and Van Duyne increased extremely in coarse Ag electrode surface discovery Raman signal intensity By force, up to million times.Further study show that a small amount of precious metal element such as Au, Ag and Cu free electron metalloid material surface, it can Show apparent Raman enhancement effect, i.e. surface-enhanced Raman (SERS).And since Ag nanoparticle is easy to be produced, and with The other materials such as Au, Cu are compared, and be can get and are higher by nearly 100 times of reinforcing effect, thus become the most common research pair in SERS As.In recent years, since semiconductor nano material can collectively constitute semiconductor composite-SERS with noble metals such as Au, Ag and Cu Active substrate, to realize the corresponding function of semiconductor nano material, to obtain extensive concern.
Fe3O4Magnetic nano-particle (MNP) has superparamagnetism, has the function such as enrichment well, separation in complicated substrate Can, therefore it is widely used in the fields such as biomedicine, imaging, bio-separation, catalysis.But naked Fe3O4Nanoparticle be easy to aoxidize or Aggregation, is soluble in acid solution, and active group is insufficient, limits Fe3O4Application of the nanoparticle in every field.Therefore, Numerous materials such as SiO2, polymer etc. be used to cladding Fe3O4The surface of NPs forms core-shell magnetic nanostructure, on improving State disadvantage.It has been reported that Fe3O4@SiO2Nano-complex can shield dipolar magnetic interaction, avoid particle agglomeration, prevent Only Fe3O4Ion is oxidized, and improves its stability.Therefore, SERS active-substrate is had been widely used for, with-Ag nanometers of object Particle is built into Fe3O4@SiO2Object-Ag sandwich structure, to be used for quickly detecting to object.But this detection side Formula is cumbersome, and since the Ag nanoparticle of dispersion will appear irregular agglomeration, detects poor repeatability.Meanwhile Ag nanometers Particle is few between each other generated " hot spot ", and SERS activity is lower, and sensitivity is not high.Therefore, Hu et al. has prepared Fe3O4@ SiO2@AgNPs compound is studied as SERS substrate, and to its performance, but its preparation process is cumbersome, time-consuming, and is detected Effect is not satisfactory.
At present in open source literature, " Ag/Fe3O4@ SiO2The preparation of magnetic nanometer adsorbent and its deep desulfurization of gasoline Can " disclose a kind of Ag/Fe3O4@ SiO2The preparation method of magnetic Nano material uses thermal decomposition method deposition silver, there is consumption When, the disadvantages of preparation process is cumbersome, and reaction condition requires high (need to calcine 2 hours in 500 DEG C of conditions), and it is prepared Ag/Fe3O4@ SiO2Magnetic Nano material is used as adsorbent, is not used for the substrate of surface-enhanced Raman.
Summary of the invention
The technical problem to be solved by the present invention is providing a kind of superparamagnetism Fe3O4@SiO2The system of@Ag nanocomposite Preparation Method, this method is with Fe3O4For core, SiO2Fe is constructed for shell3O4@SiO2Core-shell structure, and utilize the isotropism of Ag kind The stabilization of growth and polyvinylpyrrolidone (PVP) form Ag nanoparticle and are deposited on core-shell structure, obtain dispersing good It gets well, magnetic response is good, high sensitivity, integrated Fe3O4@SiO2@Ag core-shell structure.
The technical solution for solving above-mentioned technical problem is: a kind of superparamagnetism Fe3O4@SiO2The system of@Ag nanocomposite Preparation Method, comprising the following steps:
(1) Fe3O4Preparation: by FeCl3·6H2O is dissolved in ethylene glycol, FeCl3·6H2The mass volume ratio of O and ethylene glycol are as follows: 1g: 25~35mL stirs 25~35 min；Then, FeCl is added in acquired solution3·6H21.9~2.1 times of NaAc of O mass And FeCl3·6H20.7~0.8 times of PEG 4000 of O mass, stirring to reactant are completely dissolved；Later, which is transferred to In autoclave, it is put into 205~215 DEG C of high temperature oven 5~7 h of reaction；It is cooled to room temperature, the Fe of preparation3O4Nanoparticle is used Magnet is collected, and with deionized water and ethanol washing, is put into vacuum oven dry 5~7 h at 55~65 DEG C, for use；
(2) Fe3O4@SiO2The preparation of nanoparticle: the Fe of step (1) preparation is weighed3O4Solid is distributed in ethanol water, Fe3O4With the mass volume ratio of ethanol water are as follows: 1g: 140~150mL, ethanol water are by dehydrated alcohol and water by volume Than mixing for 4~6: 1, after being ultrasonically treated 15~25min, 23~27% ammonium hydroxide of mass concentration is added dropwise, ammonium hydroxide dripping quantity presses 1g Fe3O45~6mL of ammonium hydroxide meter is added dropwise；Then TEOS is added dropwise under mechanical stirring, control rate of addition is 95~105 μ L/ Min, TEOS dripping quantity press 1g Fe3O43.5~4.5mL of TEOS meter is added dropwise；Completion of dropwise addition afterpulse ultrasonic reaction 230~ 250min collects gained particle with magnet and is washed respectively with ethyl alcohol and deionized water；It is put into 55~65 DEG C of vacuum ovens and does Dry 11~13 h, obtains Fe3O4@SiO2Nanoparticle is stand-by；
(3) Fe3O4@SiO2The preparation of@Ag nanoparticle: silver nitrate is dissolved in water, and the mass volume ratio of silver nitrate and water is 1g: 18~22mL, then be added mass concentration 23~27% ammonium hydroxide, ammonium hydroxide additional amount by 0.2g silver nitrate be added ammonium hydroxide 380~ 420 μ L meter, is ultrasonically treated 5~15min；Fe prepared by step (2)3O4@SiO2Nanoparticle is scattered in the solution, Fe3O4@ SiO2The mass ratio of nanoparticle and silver nitrate is 28~32: 0.2；Then it is 0.01~0.03g/ mL polyethylene that concentration, which is added, Pyrrolidones ethanol solution, Fe3O4@SiO2The mass ratio of nanoparticle and polyvinylpyrrolidone is 28~32: 500, at ultrasound 15~25 min are managed, reactant is transferred to autoclave, is placed in 115~125 DEG C of baking ovens, react 3.5~4.5 h； After reaction, the particle obtained by magnetite absorptive collection, is washed with water and dehydrated alcohol, is subsequently placed in vacuum oven 55 Dry 4~6 h, obtain Fe at~65 DEG C3O4@SiO2@Ag nanoparticle.
The present invention and " Ag/Fe3O4@ SiO2The preparation and its deep desulfurization of gasoline performance of magnetic nanometer adsorbent " it compares, Prepare Fe3O4@SiO2 During@AgNPs, in Fe3O4@SiO2 There are significant differences for the method for NPs deposition nano Ag particles.This Invention is using crystal seed method first in Fe3O4@SiO2 Silver-colored crystal seed is connected on NPs compound, is then received using chemical reduction method preparation Rice silver particles.And " Ag/Fe3O4@SiO2The preparation and its deep desulfurization of gasoline performance of magnetic nanometer adsorbent " it is using thermal decomposition The technical solution of method deposition silver.
The invention proposes a kind of simple, effective seed mediating growth methods, i.e. crystal seed method.Pass through seed mediating growth Method prepares high-performance Ag coating Fe3O4@SiO2 NPs, the isotropic growth and polyvinylpyrrolidone of all Ag seeds (PVP) static stabilization forms Ag shell completely.It is sent out simultaneously using mechanical stirring and sonication techniques come abundant stimulate the reaction It gives birth to and further avoids assembling, preparation method is simple and quick, the Fe of preparation3O4@SiO2@AgNPs has good magnetic property, can It is quickly separated from sample solution, is enriched with target molecule, shorten detection time, also can produce by Magnetic guidance aggregation abundant Hot spot between particle.
Fe prepared by the present invention3O4@SiO2When@AgNPs is as SERS active-substrate, there is good superparamagnetism energy, surely Qualitative good, uniform deposition of the Ag nanoparticle on core-shell structure improves detection repeatability.Fe3O4@SiO2@AgNPs SERS Active substrate can be quickly enriched with from sample solution, separate object, improved sensitivity, reproducibility, shortened detection time.Not only In this way, Fe3O4@SiO2@AgNPs structure can also be assembled by Magnetic guidance also can produce between Ag nanoparticle abundant " heat Point " significantly improves SERS activity, further increases sensitivity.
Detailed description of the invention
Fig. 1 is respectively Fe3O4 NPs、Fe3O4@SiO2、Fe3O4@SiO2SEM figure, TEM figure and the EDS figure of@AgNPs.Wherein, (a)(b)Fe3O4；(c)(d)Fe3O4@SiO2；(e)(f)Fe3O4@SiO2@Ag。
Fig. 2 is Fe3O4；Fe3O4@SiO2；Fe3O4@SiO2The XRD spectra of@Ag.
Fig. 3 is respectively Fe3O4、Fe3O4@SiO2、Fe3O4@SiO2Infrared spectroscopy (IR) figure of@Ag.
Fig. 4 is the Raman spectrogram of different base.Wherein, (a) Fe3O4；(b)Fe3O4@SiO2；(c)Fe3O4@SiO2@Ag； (d) oxacillin standard items；(e) Ag- oxacillin (10-3Mol/L);(f)Fe3O4@SiO2@Ag- oxacillin (10-3mol/ L).
Fig. 5 is the oxacillin of various concentration in Fe3O4@SiO2SERS spectrogram in@Ag substrate.
Fig. 6 is six groups of oxacillin (10-9 Mol/L SERS spectra and six parts of oxacillin (10)-9 Mol/L) solution exists 1028 cm−1The Raman peak figure at place.Wherein, (a) is six groups of oxacillin (10-9 Mol/L SERS spectra)；It (b) is six parts of benzene Azoles XiLin (10-9 Mol/L) solution is in 1028 cm−1The Raman peaks at place, error bars indicate the standard deviation of measured value three times.
Fig. 7 is the oxacillin of different dosage forms in Fe3O4@SiO2SERS spectrogram and Raman peaks in@Ag substrate are located at 1028 cm-1The error analysis figure at place.Wherein, (a) standard items；(b) capsule；(c) tablet；(d) powder-injection.
Specific embodiment
A kind of embodiment 1: superparamagnetism Fe3O4@SiO2The preparation method of@Ag nanocomposite, comprising the following steps:
(1) Fe3O4Preparation: Fe has been synthesized using Modiization solvent thermal reaction3O4NPs, i.e., by 1.35 g FeCl3·6H2O is molten In 40 mL ethylene glycol, 30 min of magnetic agitation.Then, 2.7 g NaAc and 1.0 g PEG are added in acquired solution 4000, stirring to reactant is completely dissolved.Later, which is transferred in autoclave, is put into 210 DEG C of high temperature oven React 6 h.It is cooled to room temperature, the Fe of preparation3O4Nanoparticle is collected with magnet, and deionized water and ethyl alcohol are respectively washed three times, is put into true Empty drying box dry 6 h at 60 DEG C, for use.
(2) Fe3O4@SiO2The preparation of nanoparticle: the Fe of above-mentioned preparation is weighed3O40.5 g of solid, be distributed to 60 mL without In the mixed solution of water-ethanol and 12 mL water after 20 min of ultrasound, 25% ammonium hydroxide, 2.8 mL is added dropwise.Then 5 under mechanical stirring by It is added dropwise to 2 mL of TEOS, control rate of addition is 100 μ L/min.240 min of completion of dropwise addition afterpulse ultrasonic reaction, uses magnet Gained particle is collected respectively to be washed 3 times with ethyl alcohol and deionized water respectively.Dry 12 h are put into 60 DEG C of vacuum ovens, for use.
(3) Fe3O4@SiO2The preparation of@Ag nanoparticle: 0.2 g silver nitrate is dissolved in the water of 4 mL, is then added 25% 400 μ L of ammonium hydroxide, 10 min of ultrasound.By 30 mg Fe3O4@SiO2It is scattered in the solution.Then it is added and is dissolved in anhydrous second Reactant is transferred to autoclave, juxtaposition by polyvinylpyrrolidone (0.5 g) solution of alcohol (26 mL), 20 min of ultrasound 120 DEG C in baking oven, 4 h are reacted.After reaction, each 3 times are alternately washed with water and dehydrated alcohol under magnetite absorption, so Postposition 60 DEG C of 5 h of drying in a vacuum drying oven, obtain Fe3O4@SiO2@Ag nanoparticle.
Fe manufactured in the present embodiment3O4@SiO2@Ag nanoparticle by SEM, the phenetic analysis such as TEM, EDC means to its into Row performance characterization.
1, SEM, TEM and EDS are characterized
Fig. 1 is Fe3O4 NPs、Fe3O4@SiO2、Fe3O4@SiO2@AgNPs scanning, transmission electron microscope picture (upper right) and energy spectrum diagram. By (Fig. 1 a) it is found that Fe3O4NPs(200 nm) size is uniform, good dispersion, surface are smooth, and only goes out in power spectrum (Fig. 1 b) Existing Fe, O element spectral peak, illustrates Fe3O4There is no other impurities on surface.With silica to Fe3O4After NPs is coated, Fe3O4NPs forms apparent nucleocapsid structure, and outer layer is transparent silicon shell (20 nm), and internal layer is darker Fe3O4Core (Fig. 1 c Upper right), and occur the spectral peak of Si element in power spectrum (Fig. 1 d), this shows that silica successfully coats Fe3O4Nanoparticle Son.By Fe3O4@SiO2SEM(Fig. 1 e of@AgNPs) and TEM(Fig. 1 e upper right) figure can see, Ag uniform particle is interspersed Fe3O4@SiO2Biggish Ag particle is seldom observed on surface, forms the continuous shell with nanoscale rough degree, and in energy There is the spectral peak of Ag element in spectrum (Fig. 1 f), further proves Fe3O4@SiO2@AgNPs is successfully prepared.
2, XRD characterization
The present invention is using X-ray diffractometer (XRD) respectively to Fe3O4、Fe3O4@SiO2And Fe3O4@SiO2The knot of@AgNPs sample Brilliant degree and crystalline structure are characterized, and are such as schemed shown in (2).Fe3O4Magnetic particle (2a) and Fe3O4@SiO2(2b) core-shell particles 2 There is diffraction maximum in 18.4 °, 30.1 °, 35.5 °, 37.2 °, 43.1 °, 53.6 °, 57.0 °, 62.6 °, 74.1 ° in θ.With standard PDF card (PDF01-1111) compares it is found that these peaks are respectively belonging to Fe3O4(111) of cube structure, (220), (311), (222), (400), (422), (211), (440) and (533) crystal face.This explanation is in SiO2Coat Fe3O4During, There is no destroy Fe3O4The crystalline structure of magnetic particle.Fe3O4@SiO2@Ag(Fig. 3 c) and Fe3O4XRD spectra comparison, the former It is respectively to occur new diffraction maximum at 38.2 °, 44.3 °, 64.5 ° and 77.4 ° in 2 θ.It is right with standard card (COD 9011607) It is found than after, these diffraction maximums respectively correspond (111), (200), (220) and (311) crystal face of silver, and without destroying nucleocapsid Inside configuration Fe3O4Crystalline structure.This shows Fe3O4@SiO2@AgNPs is successfully prepared, with aforementioned SEM, TEM, EDS characterization point Analysis result is consistent.
3, FT-IR is characterized
Comparison diagram (3a), (3c) are it can be found that Fe3O4Surface coated Si O2Afterwards in 1056 cm-1There is apparent characteristic peak in place, The absorption peak is as caused by Si-O key stretching vibration.(Fig. 3 b) has found that the absorption peak strength of Si-O key has after further depositing Ag Weakened, this is because Fe3O4@SiO2Surface deposition Ag particle it is thicker and covering uniformly caused by, this also with Fe3O4@SiO2@ It is consistent observed by the SEM and TEM of Ag.
Fe manufactured in the present embodiment3O4@SiO2@Ag nanoparticle is for the detection to drug oxacillin.
1, the preparation of sample solution
The preparation of standard solution: 4 mg oxacillin standard items accurately are weighed, with aqueous hydrochloric acid solution (pH 3.0) constant volume in 10 mL In volumetric flask, and it is stand-by that above-mentioned solution is diluted to required concentration.
The preparation of sample solution: firstly, oxacillin capsule (removing its shell), tablet are ground, then, claim respectively The oxacillin sample for taking 4 mg, tri- kinds of dosage forms, it is stand-by in 10 mL volumetric flasks with aqueous hydrochloric acid solution (pH 3.0) constant volume.
2, the preparation of sample and Raman spectrum acquisition parameter
It takes 500 μ L of sample to be tested and Fe prepared by 10 mg is added3O4@SiO2After@Ag nanocomposite mixes 1 h of ultrasound, Mixed solution drop is dried in the quartz glass on piece of externally-applied magnetic field, each sample acquires 3 Raman spectrums.The parameter of spectrum Are as follows: wavelength is 638 nm, and the time of integration is 5 s, and average time is 1 time.
3、Fe3O4@SiO2Detection of the@Ag SERS substrate to drug oxacillin
Fig. 4 is the SERS spectra figure of different base, from Fig. 4 (a), (b), (c) it can be seen that Fe3O4、Fe3O4@SiO2、Fe3O4@ SiO2Tri- kinds of blank substrates of@Ag illustrate that this three groups of substrates do not interfere with oxacillin SERS signal there is no SERS signal.Figure (d) oxacillin standard items are in 683 cm-1、1036 cm-1、1196 cm-1、1501 cm-1、1636 cm-1Drawing occurs in place Graceful spectral peak, and in 1028 cm in figure (f)-1(carboxyl C-O key stretching vibration causes), 1621 cm-1(phenyl ring C-C key slip key Vibration causes) at Raman peaks significantly increase, after comparison, it was found that, that slight red shift has occurred is (big at peak at two for this with standard items (Fig. 4 d) About 10 cm-1).May be as caused by the influence of substrate, but have no effect on the substrate (Fe3O4@SiO2@Ag) to oxacillin Detection.
Fig. 5 is the oxacillin of various concentration in Fe3O4@SiO2SERS spectrogram in@Ag substrate, as can be seen from the figure With the reduction of oxacillin concentration, 1028 cm-1The feature peak intensity at place is gradually lowered, in terms of S/N >=3, oxacillin Detection be limited to 10-11 mol/L.And as can be seen that Fe from Fig. 4 (e-f)3O4@SiO2The SERS signal of@Ag substrate is significantly high In silver sol be substrate SERS signal, this be primarily due to Fe3O4Enrichment, not only increase SERS " hot spot ", also It is enriched with the oxacillin molecule for being adsorbed on the surface Ag, enhances the purer Ag nanoparticle of sensitivity greatly.Together When to oxacillin peak SERS intensity (1028 cm-1Place) and concentration (10-4-10-11 Mol/L) logarithm in range carries out linear Fitting, discovery have preferable linear relationship between the two, and linear equation is y=294.03x+3651.7, and r 0.996 illustrates this Substrate may be implemented to the quick analysis detection of the oxacillin of low concentration, the calculation formula of Raman enhancement factor EF are as follows:
WhereinIt absorbs in Fe3O4@SiO2The characteristic peak of oxacillin molecule in@Ag substrate；
The normal Raman intensity of oxacillin molecule；
-Fe3O4@SiO2The oxacillin molecular number that laser irradiation arrives in@Ag substrate；
The molecular number that oxacillin molecule is irradiated with a laser.
The present invention is with 1028cm-1The Raman peak intensity conduct at placeIValue,With 103It substitutes into formula and calculates Fe3O4@SiO2@ Ag substrate is 2.5 × 10 to the enhancement factor of oxacillin5。
Spectrum reproducibility is an important factor for influencing this method validity and practicability, and the benzene azoles prepared in parallel to six parts is western Woods solution (10-9 Mol/L Raman detection (Fig. 6 (a))) has been carried out, the spectrum reproducibility of oxacillin on this substrate has been investigated, It was found that it is in 1028 cm-1The RSD for locating Raman signal intensity is 7.2%(Fig. 6 (b)), illustrate that this method reproducibility is good.
4, the SERS detection of different dosage forms oxacillin
The present invention detects oxacillin powder needle, capsule, tablet respectively.Fig. 7 is that the oxacillin of different dosage forms exists Fe3O4@SiO2SERS spectrogram and Raman peaks in@Ag substrate are located at 1028 cm-1The error analysis figure at place, can from figure Out, the oxacillin of different dosage forms and standard items compare, in 1028 cm-1、1621 cm-1There are preferable Raman absorption, and glue The Raman absorption of capsule is relatively strong, followed by tablet, and powder-injection is most weak, this may be due in capsule oxacillin content compared with Height, and tablet and content in powder-injection are less.Some researches show that have with sulfydryl, amino, the molecule of benzene ring structure and the surface Ag There is very strong chemical affinity.Why base material prepared by us can show excellent anti-interference ability, attribution After the substrate is in conjunction with the amino of object, phenyl ring, Fe is utilized3O4Superparamagnetism, can from complex sample solution quickly Separation, enrichment oxacillin molecule, to exclude the interference of auxiliary material in preparation.
The present invention uses LBL self-assembly method, is prepared for superparamagnetism, high SERS active-substrate Fe3O4@SiO2@Ag core Shell structural nano compound, and its pattern is characterized with structure.The material is well dispersed, magnetic response is good, high sensitivity, collection Cheng Hua effectively can be enriched with and be separated to target sample to be measured, significantly improve detection sensitivity and anti-interference ability.At this On SERS active-substrate, oxacillin detection is limited up to 1 × 10-11 Mol/L, in concentration (10-4-10-11 Mol/L) range interior lines Sexual intercourse is good, r 0.996.Substrate Fe prepared by the present invention3O4@SiO2@Ag nuclear shell structure nano compound is in food, drug Quick context of detection have certain application value.

Claims (1)

1. a kind of superparamagnetism Fe3O4@SiO2The preparation method of@Ag nanocomposite, it is characterised in that: the following steps are included:
(1) Fe3O4Preparation: by FeCl3·6H2O is dissolved in ethylene glycol, FeCl3·6H2The mass volume ratio of O and ethylene glycol are as follows: 1g: 25~35mL stirs 25~35 min；Then, FeCl is added in acquired solution3·6H21.9~2.1 times of NaAc of O mass And FeCl3·6H20.7~0.8 times of PEG 4000 of O mass, stirring to reactant are completely dissolved；Later, which is transferred to In autoclave, it is put into 205~215 DEG C of high temperature oven 5~7 h of reaction；It is cooled to room temperature, the Fe of preparation3O4Nanoparticle is used Magnet is collected, and with deionized water and ethanol washing, is put into vacuum oven dry 5~7 h at 55~65 DEG C, for use；
(2) Fe3O4@SiO2The preparation of nanoparticle: the Fe of step (1) preparation is weighed3O4Solid is distributed in ethanol water, Fe3O4With the mass volume ratio of ethanol water are as follows: 1g: 140~150mL, ethanol water are by dehydrated alcohol and water by volume Than mixing for 4~6: 1, after being ultrasonically treated 15~25min, 23~27% ammonium hydroxide of mass concentration is added dropwise, ammonium hydroxide dripping quantity presses 1g Fe3O45~6mL of ammonium hydroxide meter is added dropwise；Then TEOS is added dropwise under mechanical stirring, control rate of addition is 95~105 μ L/ Min, TEOS dripping quantity press 1g Fe3O43.5~4.5mL of TEOS meter is added dropwise；Completion of dropwise addition afterpulse ultrasonic reaction 230~ 250min collects gained particle with magnet and is washed respectively with ethyl alcohol and deionized water；It is put into 55~65 DEG C of vacuum ovens and does Dry 11~13 h, obtains Fe3O4@SiO2Nanoparticle is stand-by；
(3) Fe3O4@SiO2The preparation of@Ag nanoparticle: silver nitrate is dissolved in water, and the mass volume ratio of silver nitrate and water is 1g: 18~22mL, then be added mass concentration 23~27% ammonium hydroxide, ammonium hydroxide additional amount by 0.2g silver nitrate be added ammonium hydroxide 380~ 420 μ L meter, is ultrasonically treated 5~15min；Fe prepared by step (2)3O4@SiO2Nanoparticle is scattered in the solution, Fe3O4@ SiO2The mass ratio of nanoparticle and silver nitrate is 28~32: 0.2；Then it is 0.01~0.03g/ mL polyethylene that concentration, which is added, Pyrrolidones ethanol solution, Fe3O4@SiO2The mass ratio of nanoparticle and polyvinylpyrrolidone is 28~32: 500, at ultrasound 15~25 min are managed, reactant is transferred to autoclave, is placed in 115~125 DEG C of baking ovens, react 3.5~4.5 h； After reaction, the particle obtained by magnetite absorptive collection, is washed with water and dehydrated alcohol, is subsequently placed in vacuum oven 55 Dry 4~6 h, obtain Fe at~65 DEG C3O4@SiO2@Ag nanoparticle.
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