CN104209106B - The Fe of 5-sulphosalicylic acid functionalization 3o 4magnetic nano-particle and synthetic method thereof and application - Google Patents

The Fe of 5-sulphosalicylic acid functionalization 3o 4magnetic nano-particle and synthetic method thereof and application Download PDF

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CN104209106B
CN104209106B CN201410438856.7A CN201410438856A CN104209106B CN 104209106 B CN104209106 B CN 104209106B CN 201410438856 A CN201410438856 A CN 201410438856A CN 104209106 B CN104209106 B CN 104209106B
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邓必阳
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Guangxi Normal University
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Abstract

The invention discloses a kind of Fe of 5-sulphosalicylic acid functionalization 3o 4magnetic nano-particle and synthetic method thereof and application.The Fe of described 5-sulphosalicylic acid functionalization 3o 4magnetic nano-particle by ethyl orthosilicate to Fe 3o 4magnetic nano-particle carries out coated, gained Fe 3o 4/ SiO 2magnetic nano-particle obtains with 5-sulfosalisylic acyl chloride reaction again.The synthetic method of particle of the present invention is simple, and synthesize the particle obtained spherical in shape, size uniform, good dispersion, has good suction-operated to Se form, for the Determination of Trace Selenium form in research environment water sample provides feasibility foundation.

Description

The Fe of 5-sulphosalicylic acid functionalization 3o 4magnetic nano-particle and synthetic method thereof and application
Technical field
The present invention relates to a kind of Fe of 5-sulphosalicylic acid functionalization 3o 4magnetic nano-particle and synthetic method thereof and application, belong to technical field of nano material.
Background technology
Magnetic-particle (MPs) usually by magnetic element as iron, nickel, cobalt and oxide thereof form.SPIO nano particle (Fe 3o 4, γ-Fe 2o 3), as the novel solid phase extraction adsorbents of one, cause extensive concern in atomic spectroscopic analysis field.Magnetic nano-particle has the following advantages: surface easily modification, analyze thing selective absorption, have bio-compatibility.Exposed Fe 3o 4be easy to assemble, and do not have selective to the matrix absorption in complex sample, adopt SiO 2coated Fe 3o 4nano particle is avoided particle surface oxidized and changes magnetic, provides possibility for further chemistry functional simultaneously.
In prior art, the conventional active function groups that magnetic nano particle sub-surface is modified is comprised: carboxyl (-COOH), amino (-NH 2), hydroxyl (-OH), sulfydryl (-SH) etc., in addition, conjugated structure (as polyaniline etc.), large surface area (as C18 etc.) and micella performance can be utilized to carry out suction-operated.Also there is not yet the research report modified magnetic nano-particle with 5-sulphosalicylic acid at present, the magnetic nano-particle that also there is not yet after 5-sulphosalicylic acid is modified has adsorbing report to plasma selenium.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of Fe of 5-sulphosalicylic acid functionalization 3o 4magnetic nano-particle and synthetic method thereof and application.The Fe of the 5-sulphosalicylic acid functionalization obtained is synthesized by the method for the invention 3o 4magnetic nano-particle is spherical in shape, size uniform, good dispersion, has good suction-operated to Se form.
The Fe of 5-sulphosalicylic acid functionalization of the present invention 3o 4magnetic nano-particle, its structural formula is as follows:
Wherein, represent Fe 3o 4magnetic nano-particle.
The Fe of 5-sulphosalicylic acid functionalization of the present invention 3o 4the synthetic method of magnetic nano-particle is: first adopt coprecipitation to prepare Fe 3o 4magnetic nano-particle, then with ethyl orthosilicate to Fe 3o 4magnetic nano-particle carries out coated, obtains Fe 3o 4/ SiO 2magnetic nano-particle, gained Fe 3o 4/ SiO 2magnetic nano-particle again with 5-sulfosalisylic acyl chloride reaction, namely obtain the Fe of 5-sulphosalicylic acid functionalization 3o 4magnetic nano-particle; Described 5-sulfosalisylic acyl chlorides reacts obtained by two hydration 5-sulphosalicylic acids and excessive thionyl chloride under catalyst formamide existent condition.
The more specifically Fe of 5-sulphosalicylic acid functionalization 3o 4the synthetic method of magnetic nano-particle, specifically comprises the following steps:
1) Fe 3o 4the preparation of magnetic nano-particle
Coprecipitation is adopted to prepare Fe 3o 4magnetic nano-particle;
2) Fe 3o 4/ SiO 2the preparation of magnetic nano-particle
Get Fe 3o 4magnetic nano-particle is placed in alcohol/aqueous solution; ethyl orthosilicate is added wherein after ultrasonic disperse; under protective atmosphere; regulate pH=4 ~ 5 or pH=9 ~ 10 of solution; and under 70 ~ 90 DEG C of conditions stirring reaction 1 ~ 16h, reactant mixture use external magnetic field be separated, washing; drying, obtains Fe 3o 4/ SiO 2magnetic nano-particle;
3) Fe 3o 4/ SiO 2the sulfo group functionalization of magnetic nano-particle
3.1) get two hydration 5-sulphosalicylic acids and add excessive thionyl chloride, then add catalyst formamide, in 100 ~ 120 DEG C of reaction 5 ~ 12h, steam except excessive thionyl chloride after reactant cooling, obtain 5-sulfosalisylic acyl chlorides;
3.2) Fe is got 3o 4/ SiO 2magnetic nano-particle and excessive 5-sulfosalisylic acyl chlorides are placed in reaction vessel, add catalyst pyridine, and in 0 ~ 10 DEG C of stirring reaction 12 ~ 24h, reactant mixture uses external magnetic field to be separated, and washing is dry, obtains the Fe of 5-sulphosalicylic acid functionalization 3o 4magnetic nano-particle.
The step 1 of above-mentioned synthetic method) in, adopt coprecipitation to prepare Fe 3o 4the step of magnetic nano-particle is identical with existing routine techniques, preferably includes following steps: by Fe 3+: Fe 2+the ratio of the amount of substance of=1.3 ~ 2:1 takes FeCl 36H 2o and FeCl 24H 2o is placed in reaction vessel, adds deoxygenated water and makes it dissolve, and under protective atmosphere, is warming up to 60 ~ 90 DEG C, adds ammoniacal liquor and regulates pH=9 ~ 10, insulation reaction 30 ~ 120min, and reactant mixture uses external magnetic field to be separated, and washing is dry, obtains Fe 3o 4magnetic nano-particle.The consumption of above-mentioned deoxygenated water calculates with 50 ~ 150mL deoxygenated water by every 0.01mol molysite (comprising divalent iron salt and trivalent iron salt) usually.
The step 2 of above-mentioned synthetic method) in, the alcohol in described alcohol/aqueous solution is glycerine or ethanol, and the volume ratio of alcohol and water is preferably 0.6 ~ 1.5:1, and the consumption of alcohol/aqueous solution presses 1gFe usually 3o 4magnetic nano-particle 50 ~ 100mL alcohol/aqueous solution calculates.In this step, the time of ultrasonic disperse is same as the prior art, is generally 10 ~ 50min; After ultrasonic disperse, the addition of ethyl orthosilicate is same as the prior art, preferably control Fe 3o 4the mass volume ratio of magnetic nano-particle and ethyl orthosilicate is: 1g:2 ~ 5ml.After adding ethyl orthosilicate, pH=4 ~ 5 of solution or pH=9 ~ 10 are regulated to carry out reacting all can obtaining Fe again 3o 4/ SiO 2magnetic nano-particle, and regulate pH=4 ~ 5 of solution or pH=9 ~ 10 to carry out again reacting the Fe obtained 3o 4/ SiO 2magnetic nano-particle does not almost have difference in proterties and performance; Generally, with pH=4 ~ 5 of weak acid-conditioning solution, as glacial acetic acid or formic acid etc.; PH=9 ~ 10 of solution are regulated, as ammoniacal liquor or sodium acid carbonate etc. with weak base.
The step 3.1 of above-mentioned synthetic method) in, under normal circumstances, the mol ratio of two hydration 5-sulphosalicylic acids and thionyl chloride is generally 1:25 ~ 72.The consumption of described catalyst formamide is generally 20 ~ 55% of two hydration 5-sulphosalicylic acid moles.Reaction is carried out usually under oil bath condition, produces bumping phenomenon, preferably in reaction system, add several zeolites in order to avoid during reaction.
The step 3.2 of above-mentioned synthetic method) in, Fe 3o 4/ SiO 2the mass ratio of magnetic nano-particle and 5-sulfosalisylic acyl chlorides is generally 1:3 ~ 6.Described catalyst pyridine is anhydrous pyridine, specifically pyridine is pressed existing conventional method removing moisture content wherein; The consumption of described anhydrous pyridine is generally Fe 3o 4/ SiO 25 ~ 10% of magnetic nano particle protonatomic mass.Reaction is carried out usually under condition of ice bath.
In synthetic method of the present invention, used water can be not for reaction system brings the water of other impurity into, as sub-boiling water, distilled water, deionized water, pure water etc.; Described protective atmosphere can be specifically other protective atmospheres such as nitrogen, argon gas, helium; The alternately washing of water (as previously mentioned, can be sub-boiling water, distilled water, deionized water, pure water etc.) and absolute ethyl alcohol is normally used in described washing; Described drying adopts vacuum drying usually.
The Fe of the 5-sulphosalicylic acid functionalization obtained is synthesized by said method 3o 4the particle diameter of magnetic nano-particle is at 10 ~ 15nm, spherical in shape, size uniform, good dispersion.
The present invention also comprises the Fe of above-mentioned sulfo group functionalization 3o 4the application of magnetic nano-particle in adsorbing separation Se form, specifically to Se (VI), Se (IV), SeMet (selenomethionine) and SeCys 2the adsorption effect of (selenocystine) four kinds of Se form is better, wherein with best to the absorption of Se (IV).When adsorbing, regulating pH=1 ~ 5 (preferred pH=3 ~ 5, more preferably pH=4) containing plasma selenium or the fluid sample containing selenizing conjunction, then adding the Fe of sulfo group functionalization 3o 4magnetic nano-particle adsorbs, absorption time>=4min time absorption can reach good effect, preferably control as 5min.Total concentration≤the 20ngmL of plasma selenium in containing plasma selenium or the fluid sample that closes containing selenizing -1time, under these conditions (pH=4 of testing liquid sample, adsorption time are 5min), the Fe of sulfo group functionalization 3o 4when the addition of magnetic nano-particle is 10mg, can to the plasma selenium absorption in above-mentioned sample completely.If need to resolve with the mensuration to Selenium In Some Selenium-rich Biological Samples ion concentration to the plasma selenium of absorption, specifically when resolving, the Fe of plasma selenium sulfo group functionalization will be adsorbed 3o 4magnetic nano-particle is placed in container, adds Na 2cO 3solution carries out ultrasonic wash-out, ultrasonic time>=3min, be preferably 4min, then collect the detection that supernatant carries out Se content; Described Na 2cO 3the concentration of solution is preferably 0.1 ~ 2.0mol/L.
Further, the invention provides the Fe of sulfo group functionalization 3o 4application during magnetic nano-particle Se form analysis and Determination of Trace Selenium in fluid sample detect.In described fluid sample, the detection of Determination of Trace Selenium is limited to 0.17 ~ 0.54ng/mL.
Compared with prior art, the invention provides a kind of Fe of the sulfo group functionalization through the modification of 5-sulfosalisylic acyl chlorides 3o 4magnetic nano-particle, the synthetic method of described particle is simple, and synthesize the particle obtained spherical in shape, size uniform, good dispersion, has good suction-operated to Se form.
Accompanying drawing explanation
Fig. 1 is the IR Characterization spectrogram of MNPs, SMNPs and SSA-SMNPs magnetic nano-particle that the embodiment of the present invention 1 obtains, wherein, a is the infrared spectrum of MNPs magnetic nano-particle, and b is the infrared spectrum of SMNPs magnetic nano-particle, and c is the infrared spectrum of SSA-SMNPs magnetic nano-particle;
Fig. 2 is the XRD figure of the SSA-SMNPs magnetic nano-particle that the embodiment of the present invention 1 obtains;
Fig. 3 is the TEM figure of the SSA-SMNPs magnetic nano-particle that the embodiment of the present invention 1 obtains;
Fig. 4 is the hysteresis curve of the SSA-SMNPs magnetic nano-particle that the embodiment of the present invention 1 obtains;
Fig. 5 is the obtained SSA-SMNPs magnetic nano-particle of the embodiment of the present invention 1 without magnetic field with there is state under magnetic field condition, wherein a figure represents that SSA-SMNPs magnetic nanometer is without the state under magnetic field condition, and b figure expression SSA-SMNPs magnetic nanometer is having the state under magnetic field condition;
Fig. 6 ~ 9 are respectively mixed standard solution (Se (VI), Se (IV) SeMet and SeCys 2concentration be 5ngmL -1) in Se (VI), Se (IV), SeMet and SeCys 2working curve;
Figure 10 is the electrophoretogram that CE-ETAAS measures Se form in mixed standard solution and fermented bean curd liquid and fermented bean curd wastewater sample, and wherein A is that concentration is 5ngmL -1se (VI), Se (IV) SeMet and SeCys 2the electrophoretogram of mixed standard solution; B is the electrophoretogram of fermented bean curd wastewater sample; C is 4ngmL -1se (VI), 3ngmL -1se (IV), 2ngmL -1seMet, 2ngmL -1seCys 2with the electrophoretogram of the mixed liquor of fermented bean curd wastewater sample; D is the electrophoretogram of fermented bean curd liquid; E is 6n gmL -1se (VI), 4ngmL -1se (IV), 3ngmL -1seMet, 4ngmL -1seCys 2with the electrophoretogram of the mixed liquor of rotten samples of latex.
Detailed description of the invention
With specific embodiment, the invention will be further described below, but the present invention is not limited to these embodiments.
In following embodiment, described MNPs represents Fe 3o 4magnetic nano-particle, described SMNPs represents Fe 3o 4/ SiO 2magnetic nano-particle, described SSA-SMNPs represents the Fe of 5-sulphosalicylic acid functionalization 3o 4magnetic nano-particle.
Embodiment 1
1) Fe 3o 4the preparation of magnetic nano-particle (MNPs)
Accurately take 4.7300gFeCl 36H 2o and 1.9881gFeCl 24H 2o (Fe 3+: Fe 2+=1.75:1; n/n); dissolve in 200mL deoxygenated water (the sub-boiling water of deoxygenation); ultrasonic 10min; then proceed in 500mL three-neck flask, 85 DEG C are stirred 30min with 800rpm under nitrogen protection, add rapidly the ammoniacal liquor that 20mL concentration is 25% ~ 28%; solution colour blackening immediately (now the pH of solution is 9.5), slaking 30min.Reactant mixture is cooled to room temperature, is separated by external magnetic field, uses sub-boiling water and absolute ethyl alcohol to replace washing 3 times, vacuum 70 DEG C of dryings, and cooling, obtains MNPs.
2) Fe 3o 4/ SiO 2the preparation of magnetic nano-particle (SMNPs)
Above-mentioned obtained MNPs2g is dissolved in 200mL glycerine and sub-boiling water (1:1; v/v) ultrasonic disperse 30min in; add 10mLTEOS (ethyl orthosilicate; the addition of TEOS adds 5mLTEOS by 1gMNPs and calculates); proceed in 500mL three-neck flask; nitrogen protection; pH to 4.5 is adjusted with glacial acetic acid; with 800rpm stirring reaction 2h under 90 DEG C of conditions, reactant mixture is cooled to room temperature, and external magnetic field is separated; sub-boiling water and absolute ethyl alcohol is used to replace washing 3 times; vacuum 70 DEG C of dryings, cooling, obtains SMNPs.
3) Fe of 5-sulphosalicylic acid functionalization 3o 4the preparation of magnetic nano-particle (SSA-SMNPs)
3.1) take 2.5gSSA (two hydration 5-sulphosalicylic acids) in 100mL three-neck flask, put into 3 zeolites, add 40mLSOCl 2with the formamide accounting for SSA mole dosage 24%, at oil bath 110 DEG C reaction 7h, after reactant is cooled to room temperature, steam except excessive SOCl with Rotary Evaporators 55 DEG C 2, obtain light brown grease, be 5-sulfosalisylic acyl chlorides.Characterize through result, determine that the structural formula of 5-sulfosalisylic acyl chlorides is as follows:
3.2) above-mentioned obtained SMNPs is got and excessive 5-sulfosalisylic acyl chlorides (mass ratio of SMNPs and 5-sulfosalisylic acyl chlorides is 1:3) is placed in and reacts molten container, add the anhydrous pyridine being equivalent to SMNPs5% quality, stirring reaction 24h under the condition of 5 ~ 10 DEG C, then be separated by external magnetic field, washing is replaced 3 times with sub-boiling water and absolute ethyl alcohol, vacuum 70 DEG C of dryings, cooling, obtains SSA-SMNPs.The synthetic route of described SSA-SMNPs is as follows:
Above-mentioned obtained SSA-SMNPs is characterized:
1, FT-IR spectrum
Adopt FT-IR spectrum to characterize SSA-SMNPs, determine that silicone hydroxyl and sulfo group are bonded to Fe 3o 4magnetic nano particle sub-surface.To the IR Characterization figure of MNPs, SMNPs and SSA-SMNPs as shown in Figure 1.In MNPs, 586cm -1the peak at place is the characteristic absorption peak of Fe-O.Fe 3o 4-the OH of particle surface can with SiO 2carry out bonding, prevent Fe 3o 4oxidized and provide a platform for next step meets functional group.In SMNPs, 1080.12cm -1the peak at place is the stretching vibration of Si-O, and SiO is described 2successfully be bonded to Fe 3o 4surface.In SSA-SMNPs, 1670cm -1place is C=O stretching vibration, and carbonyl and phenyl ring conjugation, absorb and shift to low frequency.1431.54cm -1place is phenyl ring skeletal vibration [27], the existence of phenyl ring is described.1160cm -1peak, place is-SO 3h stretching vibration absworption peak.Illustrate that SSA is successfully bonded to SMNPs magnetic nano particle sub-surface.
2, elementary analysis
Elementary analysis is the element that exists in authenticating compound and containing quantitative analysis.Carbon in measured matter, hydrogen, nitrogen, sulphur are separately converted to carbon dioxide, steam, nitrogen, sulfur dioxide after catalytic oxidization-reduction.Oxygen in measured matter obtains carbon monoxide through Pintsch process.Under the promotion of carrier gas, this mist is efficiently separated after chromatographic column, and each component is by elemental analyser TCD detector sequentially determining.Carry out elementary analysis to the C in SSA-SMNPs particle, S, H element in experiment, to obtain C content be 6.86%, S content is 2.618%.Being 7:1 by calculating the mol ratio of C and S, illustrating that sulfosalicylic acid is successfully grafted to SiO 2on coated MNPs, synthesize the SSA-SMNPs magnetic nano-particle of sulfo group functionalization.
3, XRD analysis
X-ray diffraction (XRD) is the effective ways of research crystalline solid and some AMAT microstructure.The XRD figure of the SSA-SMNPs magnetic nano-particle that above-described embodiment obtains as shown in Figure 2.As we know from the figure, SSA-SMNPs is 30.38 ° at 2 θ, 35.70 °, 43.28 °, 53.86 °, and diffraction maximum appears in 57.36 ° and 62.86 ° of places, respectively corresponding Emission in Cubic Fe 3o 4(220), (311), (400), (422), (511) and (440) crystal face.With standard Fe 3o 4crystal data consistent (JCPDSNo.65-3107).The peak position of each diffraction maximum does not change substantially, and Surface coating SiO is described 2fe is not changed with in sulfonic functional process 3o 4the spinel structure of nano particle.Analyze SSA-SMNPs magnetic nanometer collection of illustrative plates by software Jade5.0, estimation SSA-SMNPs average grain diameter is 10.9nm.
4, tem analysis
Transmission electron microscope (TEM) directly can obtain size and the form of particle.The TEM figure of the SSA-SMNPs magnetic nano-particle that above-described embodiment obtains as shown in Figure 3.As seen from the figure, SSA-SMNPs average grain diameter obtained by this method is about 10.9nm, size uniform, for spherical, and good dispersion.By coated Si O 2with sulfo group functionalization, the reunion between magnetic nanometer is improved, improves the dispersiveness of magnetic nanometer, enhance the chemical stability of magnetic nanometer.
5, VSM analyzes
Hysteresis curve has reacted the responding ability of magnetic material to changes of magnetic field, is the important curve characterizing magnetic material properties.The SSA-SMNPs magnetic property utilizing vibrating specimen magnetometer (VSM) obtained to above-described embodiment is studied, and its hysteresis curve as shown in Figure 4.Be the hysteresis curve measured at 300k of SSA-SMNPs in figure, the saturation magnetization of SSA-SMNPs is 69.4emug -1.In magnetic history, the SSA-SMNPs intensity of magnetization increases sharply along with the increase of external magnetic field strength, reach capacity fast, when external magnetic field strength weakens, the intensity of magnetization of SSA-SMNPs returns along former magnetic path, presents reversible " S " type, without any B-H loop, show that SSA-SMNPs does not have remanent magnetism phenomenon and coercivity at 300k, there is good superparamagnetism.Fig. 5 is the SSA-SMNPs magnetic nano-particle that obtains of above-described embodiment without magnetic field with there is state under magnetic field condition, wherein a figure represents that SSA-SMNPs magnetic nanometer is without the state under magnetic field condition, and b figure expression SSA-SMNPs magnetic nanometer is having the state under magnetic field condition.Under the effect having external magnetic field, SSA-SMNPs is adsorbed on a bottle side, wall magnetic field, also illustrates that SSA-SMNPs has good magnetic.
Embodiment 2
1) preparation of MNPs
By Fe 3+: Fe 2+the ratio of the amount of substance of=2:1 accurately takes FeCl 36H 2o and FeCl 24H 2o; (deoxygenated water is the sub-boiling water of deoxygenation to add deoxygenated water; the consumption of deoxygenated water calculates by every 0.01mol molysite (comprising divalent iron salt and trivalent iron salt) 100mL deoxygenated water); ultrasonic 5min; then proceed in 500mL three-neck flask; 70 DEG C are stirred 10min with 1000rpm under nitrogen protection, add rapidly ammoniacal liquor (concentration is 25%) and regulate the pH of solution to be 10, slaking 60min.Reactant mixture is cooled to room temperature, is separated by external magnetic field, uses sub-boiling water and absolute ethyl alcohol to replace washing 3 times, vacuum 60 DEG C of dryings, and cooling, obtains MNPs;
2) preparation of SMNPs
Above-mentioned obtained MNPs2g is dissolved in 200mL ethanol and sub-boiling water (0.6:1, v/v) ultrasonic disperse 10min in, add TEOS (addition of TEOS adds 2mLTEOS by 1gMNPs and calculates), proceed in 500mL three-neck flask, nitrogen protection, pH to 5 is adjusted with glacial acetic acid, with 800rpm stirring reaction 10h under 80 DEG C of conditions, reactant mixture is cooled to room temperature, external magnetic field is separated, and uses sub-boiling water and absolute ethyl alcohol to replace washing 3 times, vacuum 70 DEG C of dryings, cooling, obtains SMNPs;
3) preparation of SSA-SMNPs
3.1) take 2.5gSSA (two hydration 5-sulphosalicylic acids) in 100mL three-neck flask, put into 2 zeolites, add 50mLSOCl 2with the formamide accounting for SSA mole dosage 40%, at oil bath 110 DEG C reaction 10h, after reactant is cooled to room temperature, steam except excessive SOCl with Rotary Evaporators 70 DEG C 2, obtain 5-sulfosalisylic acyl chlorides;
3.2) above-mentioned obtained SMNPs is got and excessive 5-sulfosalisylic acyl chlorides (mass ratio of SMNPs and 5-sulfosalisylic acyl chlorides is 1:5) is placed in and reacts molten container, add the anhydrous pyridine being equivalent to SMNPs10% quality, stirring reaction 18h under the condition of 0 ~ 4 DEG C, then be separated by external magnetic field, washing is replaced 3 times with sub-boiling water and absolute ethyl alcohol, vacuum 70 DEG C of dryings, cooling, obtains SSA-SMNPs.
The average grain diameter of the SSA-SMNPs obtained by the present embodiment is 12.4nm, and its saturation magnetization is 70.1emug at 300k -1.
Embodiment 3
1) preparation of MNPs
By Fe 3+: Fe 2+the ratio of the amount of substance of=1.3:1 accurately takes FeCl 36H 2o and FeCl 24H 2o; (deoxygenated water is the sub-boiling water of deoxygenation to add deoxygenated water; the consumption of deoxygenated water calculates by every 0.01mol molysite (comprising divalent iron salt and trivalent iron salt) 50mL deoxygenated water); ultrasonic 30min; then proceed in 500mL three-neck flask; 90 DEG C are stirred 20min with 1000rpm under nitrogen protection, add rapidly ammoniacal liquor (concentration is 28%) and regulate the pH of solution to be 9, slaking 120min.Reactant mixture is cooled to room temperature, is separated by external magnetic field, uses sub-boiling water and absolute ethyl alcohol to replace washing 3 times, vacuum 60 DEG C of dryings, and cooling, obtains MNPs;
2) preparation of SMNPs
Above-mentioned obtained MNPs3g is dissolved in 200mL ethanol and sub-boiling water (1.5:1, v/v) ultrasonic disperse 50min in, add TEOS (addition of TEOS adds 3mLTEOS by 1gMNPs and calculates), proceed in 500mL three-neck flask, nitrogen protection, pH to 9 is adjusted with ammoniacal liquor, with 1000rpm stirring reaction 1h under 70 DEG C of conditions, reactant mixture is cooled to room temperature, external magnetic field is separated, and uses sub-boiling water and absolute ethyl alcohol to replace washing 3 times, vacuum 60 DEG C of dryings, cooling, obtains SMNPs;
3) preparation of SSA-SMNPs
3.1) take 2.5gSSA (two hydration 5-sulphosalicylic acids) in 100mL three-neck flask, put into 2 zeolites, add 50mLSOCl 2with the formamide accounting for SSA mole dosage 55%, at oil bath 100 DEG C reaction 10h, after reactant is cooled to room temperature, steam except excessive SOCl with Rotary Evaporators 55 DEG C 2, obtain 5-sulfosalisylic acyl chlorides;
3.2) above-mentioned obtained SMNPs is got and excessive 5-sulfosalisylic acyl chlorides (mass ratio of SMNPs and 5-sulfosalisylic acyl chlorides is 1:6) is placed in and reacts molten container, add the anhydrous pyridine being equivalent to SMNPs8% quality, stirring reaction 12h under the condition of 0 DEG C, then be separated by external magnetic field, washing is replaced 3 times with sub-boiling water and absolute ethyl alcohol, vacuum 60 DEG C of dryings, cooling, obtains SSA-SMNPs.
The average grain diameter of the SSA-SMNPs obtained by the present embodiment is 11.5nm, and its saturation magnetization is 71.2emug at 300k -1.
Embodiment 4
1) preparation of MNPs
By Fe 3+: Fe 2+the ratio of the amount of substance of=1:1 accurately takes FeCl 36H 2o and FeCl 24H 2o; (deoxygenated water is the sub-boiling water of deoxygenation to add 150mL deoxygenated water; the consumption of deoxygenated water calculates by every 0.01mol molysite (comprising divalent iron salt and trivalent iron salt) 150mL deoxygenated water); ultrasonic 30min; then proceed in 500mL three-neck flask; under argon shield, 65 DEG C are stirred 30min with 1000rpm, add rapidly ammoniacal liquor and regulate the pH of solution to be 10, slaking 90min.Reactant mixture is cooled to room temperature, is separated by external magnetic field, uses sub-boiling water and absolute ethyl alcohol to replace washing 3 times, vacuum 80 DEG C of dryings, and cooling, obtains MNPs;
2) preparation of SMNPs
Above-mentioned obtained MNPs4g is dissolved in 200mL ethanol and sub-boiling water (0.8:1, v/v) ultrasonic disperse 10min in, add TEOS (addition of TEOS adds 5mLTEOS by 1gMNPs and calculates), proceed in 500mL three-neck flask, argon shield, pH to 10 is adjusted with ammoniacal liquor, with 1000rpm stirring reaction 16h under 70 DEG C of conditions, reactant mixture is cooled to room temperature, external magnetic field is separated, and uses sub-boiling water and absolute ethyl alcohol to replace washing 3 times, vacuum 80 DEG C of dryings, cooling, obtains SMNPs;
3) preparation of SSA-SMNPs
3.1) take 2.5gSSA (two hydration 5-sulphosalicylic acids) in 100mL three-neck flask, put into 2 zeolites, add 30mLSOCl 2with the formamide accounting for SSA mole dosage 30%, at oil bath 120 DEG C reaction 5h, after reactant is cooled to room temperature, steam except excessive SOCl with Rotary Evaporators 55 DEG C 2, obtain 5-sulfosalisylic acyl chlorides;
3.2) above-mentioned obtained SMNPs is got and excessive 5-sulfosalisylic acyl chlorides (mass ratio of SMNPs and 5-sulfosalisylic acyl chlorides is 1:4) is placed in and reacts molten container, add the anhydrous pyridine being equivalent to SMNPs6% quality, stirring reaction 20h under the condition of 5 DEG C, then be separated by external magnetic field, washing is replaced 3 times with sub-boiling water and absolute ethyl alcohol, vacuum 50 DEG C of dryings, cooling, obtains SSA-SMNPs.
The average grain diameter of the SSA-SMNPs obtained by the present embodiment is 10.2nm, and its saturation magnetization is 75.1emug at 300k -1.
Experimental example: adopt the obtained SSA-SMNPs magnetic nano-particle of embodiment 1 to the absorption, the employing CE-ETAAS GC-MS mensuration that contain selenium fluid sample
1, instrument and condition of work
TAS-986 atomic absorption spectrophotometer (Beijing Puxi General Instrument Co., Ltd), selenium hollow cathode lamp (Beijing Shuguangming Electronic Lighting Instrument Co., Ltd.), SpectrumTwoFT-IR infrared spectrometer (PerkinElmer), RigakuD/max2500/pc type x-ray powder diffraction instrument (Rigaku); MPMS-XL-7 superconductive quantum interference magnetic measurement system (QuantumDesign company of the U.S.); JEM-2100 transmission electron microscope (Japan); PE2400II elemental analyser (PerkinElmer); Sprayer device (see the .Talanta109 such as Deng Biyang (2013) 128 ~ 132); Spinner device (Kodak instrucment and meter plant of Jiangyin City), HV-303P1 high-voltage power supply power supply (Tianjin torch Science and Technology Ltd.), molten silicon quartz capillary (Hebei sharp Feng chromatogram Yongnian company), the electrodeless constant speed stirrer of DW-3 digital display (Ying Yu Yu Hua instrument plant of Gongyi City), SYZ-550 quartz high purity water distiller (Jiangsu Qin Hua glass apparatus factory).
2, reagent
FeCl 24H 2o, FeCl 36H 2o, ethyl orthosilicate (Tetraethylsilicate, TEOS), ammoniacal liquor, two hydration 5-sulphosalicylic acids (SSA), NaOH, hydrochloric acid, sodium phosphate (Na 3pO 412H 2and sodium hydrogen phosphate (Na O) 2hPO 412H 2o) (Xi Long Chemical Co., Ltd.), absolute ethyl alcohol, glacial acetic acid (Guangdong Guanghua Science and Technology Co., Ltd.), glycerine, Na 2cO 3(Shantou City's brilliance laboratory), thionyl chloride (SOCl 2, Tianjin Zhi Yuan Chemical Co., Ltd.), methyl alcohol (Shanghai Reagent Company), softex kw (CTAB, in Hunan, Hunan chemical reagent development centre).
It is pure that experiment agents useful for same is analysis; Experimental water is sub-boiling water.
3, the introducing of sample
The volume injecting sample is subject to the impacts such as sample injection time, sample introduction pressure, sample character and capillary pipe length, and experiment uses the argon pressure of 0.04MPa sample solution to be introduced capillary, sample injection time 10s, sampling volume about 0.5 μ L.New molten silicon pretreatment: use CH 3oH rinses 30min, then uses 0.1molL -1naOH rinses 40min, finally rinses 10min with sub-boiling water.Before each experiment, rinse 8min with cushioning liquid.0.1molL is used after experiment -1naOH rinses 10min, rinses 15min with sub-boiling water.On pretreatment, all samples all ultrasonic process 10min removes bubble, prevents electrophoresis process from producing cutout phenomenon.During experiment, be first full of whole section of capillary, then hydrodynamic injection with cushioning liquid, after sample introduction, change cushioning liquid, use ETAAS to detect by the condition of work of following table 1 and table 2.
Table 1 Capillary Electrophoresis and atomic absorption spectrography (AAS) running parameter
Table 2 Electrothermal Atomic Absorption heating schedule
4, sample pretreatment
In experiment survey fermented bean curd liquid and the fermented bean curd waste water that water sample takes from the same fermented bean curd factory in Guilin.Be collected latter first standing one day, then use Filter paper filtering, then filter with sand core funnel, finally use 0.45 μm of membrane filtration.Solution after filtration saves backup.
5, solid phase extraction procedure
Get 10mL sample solution (i.e. the solution of the rear gained of above-mentioned 4th filtration) and, in beaker, use 0.1molL -1hCl solution regulates pH to 4, adds the SSA-SMNPs magnetic nano-particle that 10mg embodiment 1 is obtained.Mixed liquor ultrasonic absorption 5min, is separated by external magnetic field.Then 0.5mLNa is added 2cO 3solution (0.5molL -1) carry out wash-out, by ultrasonic for new mixed solution 4min, be separated by external magnetic field, collect supernatant with PTEF pipe, adopt CE-ETAAS to measure, in triplicate.Blank solution as above method preparation.
6, working curve, detectability and repeatability
Under above-mentioned table 1 and table 2 experiment condition, 5ngmL is to concentration -1se (VI), Se (IV), SeMet and SeCys 2mixed standard solution continuous 6 times measure, its relative standard deviation (RSD, n=6) is respectively 2.2%, 0.7%, 2.5% and 2.9%.Se (VI), Se (IV), SeMet and SeCys 2detection limit (3 σ, n=11) be respectively 0.18,0.17,0.54 and 0.49ngmL -1.The range of linearity, enrichment factor EF (before the slope of curve/enrichment of EF=enrichment post-equalization calibration curve slope) and linearly dependent coefficient are in table 3, and working curve is as shown in Fig. 6 ~ 10.Recycling is one of key factor of assessment sorptive material, and experiment obtains SSA-SMNPs particle and can reuse 3 times and carry out quantitative recovery experiment.
Table 3 range of linearity and coefficient correlation (n=6)
7, sample analysis
Under the experiment condition of above-mentioned table 1 and table 2, the Se (VI) in waste water fermented bean curd factory discharged with CE-ETAAS and fermented bean curd liquid, Se (IV), SeMet and SeCys 2se form measures, as shown in Figure 10.Contrast hybrid standard electrophoresis (in Figure 10 curve A) is known, and there are Se (VI) and Se (IV) two kinds of Se form in fermented bean curd waste water, its content is respectively 3.83ngmL -1and 2.62ngmL -1.Se (VI), Se (IV), SeMet and SeCys is there is in fermented bean curd liquid 2four kinds of Se form, its content is respectively 6.39ngmL -1, 4.08ngmL -1, 2.77ngmL -1and 4ngmL -1.No matter that the content of inorganic selenium form in fermented bean curd waste water or fermented bean curd liquid is higher than Organic Selenium form content.
Under the experiment condition of above-mentioned table 1 and table 2, adopt CE – ETAAS method to the Se (VI) in fermented bean curd waste water and fermented bean curd liquid, Se (IV), SeMet and SeCys 2carry out recovery testu, to obtain its rate of recovery scope be 99.14% ~ 104.5%, RSD scope is 0.82% ~ 3.5%.The results are shown in Table 4 and table 5.
Se (IV) and Se (VI) analysis result and the rate of recovery (n=6) in table 4 fermented bean curd waste water and fermented bean curd liquid
Water1 is fermented bean curd factory waste water; Water2 is fermented bean curd liquid.
SeMet and SeCys in table 5 fermented bean curd waste water and fermented bean curd liquid 2analysis result and the rate of recovery (n=6)
Water1 is fermented bean curd factory waste water; Water2 is fermented bean curd liquid.
8, conclusion
The SSA-SMNPs magnetic nano-particle obtained by the described method of invention has good suction-operated to plasma selenium, and establishes the method for CE-ETAAS combination analysis Se form.Obtained SSA-SMNPs magnetic nano-particle is to Se (VI), Se (IV), SeMet and SeCys 2enrichment factor be respectively 12,18,21 and 29, detect and be limited to 0.17 ~ 0.54ngmL -1.Obtained SSA-SMNPs magnetic nano-particle is applied to the Se (VI) in fermented bean curd waste liquid and fermented bean curd liquid, Se (IV), SeMet and SeCys 2analyze, there is good effect.SSA-SMNPs magnetic nano-particle of the present invention and method are that the Determination of Trace Selenium form in research environment water sample provides new analysis means.

Claims (5)

  1. The Fe of 1.5-sulfosalisylic acid functionalization 3o 4the synthetic method of magnetic nano-particle, is characterized in that: the Fe of described 5-sulphosalicylic acid functionalization 3o 4the structural formula of magnetic nano-particle is as follows:
    Wherein, represent Fe 3o 4magnetic nano-particle;
    The Fe of described 5-sulphosalicylic acid functionalization 3o 4the synthetic method of magnetic nano-particle is: first adopt coprecipitation to prepare Fe 3o 4magnetic nano-particle, then with ethyl orthosilicate to Fe 3o 4magnetic nano-particle carries out coated, obtains Fe 3o 4/ SiO 2magnetic nano-particle, gained Fe 3o 4/ SiO 2magnetic nano-particle again with 5-sulfosalisylic acyl chloride reaction, namely obtain the Fe of 5-sulphosalicylic acid functionalization 3o 4magnetic nano-particle; Described 5-sulfosalisylic acyl chlorides reacts obtained by two hydration 5-sulphosalicylic acids and excessive thionyl chloride under catalyst formamide existent condition.
  2. 2. the Fe of 5-sulphosalicylic acid functionalization according to claim 1 3o 4the synthetic method of magnetic nano-particle, is characterized in that: specifically comprise the following steps:
    1) Fe 3o 4the preparation of magnetic nano-particle
    Coprecipitation is adopted to prepare Fe 3o 4magnetic nano-particle;
    2) Fe 3o 4/ SiO 2the preparation of magnetic nano-particle
    Get Fe 3o 4magnetic nano-particle is placed in alcohol/aqueous solution; ethyl orthosilicate is added wherein after ultrasonic disperse; under protective atmosphere; regulate pH=4 ~ 5 or pH=9 ~ 10 of solution; and under 70 ~ 90 DEG C of conditions stirring reaction 1 ~ 16h, reactant mixture use external magnetic field be separated, washing; drying, obtains Fe 3o 4/ SiO 2magnetic nano-particle;
    3) Fe 3o 4/ SiO 2the sulfo group functionalization of magnetic nano-particle
    3.1) get two hydration 5-sulphosalicylic acids and add excessive thionyl chloride, then add catalyst formamide, in 100 ~ 120 DEG C of reaction 5 ~ 12h, steam except excessive thionyl chloride after reactant cooling, obtain 5-sulfosalisylic acyl chlorides;
    3.2) Fe is got 3o 4/ SiO 2magnetic nano-particle and excessive 5-sulfosalisylic acyl chlorides are placed in reaction vessel, add catalyst pyridine, and in 0 ~ 10 DEG C of stirring reaction 12 ~ 24h, reactant mixture uses external magnetic field to be separated, and washing is dry, obtains the Fe of 5-sulphosalicylic acid functionalization 3o 4magnetic nano-particle.
  3. 3. the Fe of 5-sulphosalicylic acid functionalization according to claim 2 3o 4the synthetic method of magnetic nano-particle, is characterized in that: step 2) in, the alcohol in described alcohol/aqueous solution is glycerine or ethanol, and the volume ratio of alcohol and water is 0.6 ~ 1.5:1.
  4. 4. the Fe of 5-sulphosalicylic acid functionalization according to claim 2 3o 4the synthetic method of magnetic nano-particle, is characterized in that: step 3.1) in, the consumption of catalyst formamide is 20 ~ 55% of two hydration 5-sulphosalicylic acid moles.
  5. 5. the Fe of 5-sulphosalicylic acid functionalization according to claim 2 3o 4the synthetic method of magnetic nano-particle, is characterized in that: step 3.2) in, catalyst pyridine is anhydrous pyridine, and its consumption is Fe 3o 4/ SiO 25 ~ 10% of magnetic nano particle protonatomic mass.
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