CN104764706A - Melamine dual-mode sensor based on Au-Fe3O4 composite nanoparticles and preparation method thereof - Google Patents
Melamine dual-mode sensor based on Au-Fe3O4 composite nanoparticles and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a melamine dual-mode sensor based on Au-Fe3O4 composite nanoparticles and a preparation method thereof. The invention relates to the field of nuclear magnetic resonance sensing. First, oleylamine oleic acid on the surfaces of the Au-Fe3O4 composite nanoparticles is stripped through NOBF4; and a specific receptor unit modifies the surfaces of the composite nanoparticles stripped by NOBF4 under the strong coordination effect of an Au-S bond, thus obtaining target composite nanoparticles which can be used for preparing the melamine dual-mode sensor. Compared with prior art, the dual-mode sensor provided by the invention has the advantages that in the presence of melamine, dispersed-state nanoparticles are induced to aggregate so that the transverse relaxation time of water protons around the nanoparticles and the ultraviolet absorption spectrum of the nanoparticles are changed. According to the sensor, melamine is detected with both an ultraviolet absorption spectrum method and a nuclear magnetic resonance method; therefore, the sensor has the advantages of wide application range, high selectivity and high interference resistance. A method is provided for realizing fast application under different actual situations.
Description
Technical field
The present invention relates to nuclear magnetic resonance sensory field, especially relate to a kind of based on Au-Fe
3o
4double mode sensor of melamine of composite nanoparticle and its preparation method and application.
Background technology
Sensor is a kind of device, can accept specified measuring range and be translated into device or the device of useful signal according to certain rule.Sensor can be divided three classes, i.e. physical sensors, chemical sensor and biology sensor.Physical sensors is the sensor of detecting physical quantities, and it utilizes some physical influence, measured physical quantity is transformed into the device of the signal of the form of energy being convenient to process.The signal of its signal exported and input has the relation determined.Main physical sensors has electro-optical pickoff, piezoelectric sensor, piezoresistive transducer, electromagnetic sensor, thermoelectric transducer, fiber optic sensor etc.Chemical sensor chemistry or physical responses measure chemical substance, in contrast to the sense organ of people, and chemical sensor corresponds to sense of smell and the gustatory organ of people substantially.But be not the simulation of simple human organs, the not sensitive Cucumber of organ of people can also be experienced, as H
2, CO.Biology sensor applies certain bio-sensing primitive usually to detect chemical substance, its concentration is converted to the instrument that electric signal carries out detecting.The advantage of biology sensor is selection function biological substance to molecular structure.All these devices must be connected with certain sensing device, so just occurred response may be detected.Building block mainly comprises: analyze matter, recognition unit, transmitter, measurement mechanism.
The method of domestic and international inspection melamine mainly contains high performance liquid chromatography, liquid chromatography-mass spectrography/mass spectroscopy, gas chromatography-mass spectrography, gas chromatography-mass spectrum/mass spectroscopy, the methods such as immune response, it is low that these methods have detection limit, the advantages such as measurement result is accurate, but shortcoming is also quite outstanding, as expensive equipment, not easily popularize, reagent is not easily preserved, and particularly the pre-treatment of sample is very complicated, needs professional to operate, consuming time longer, testing cost is high.
UV, visible light spectrophotometer is as the modal spectroanalysis instrument of one, utilize the uv-vis spectra Absorption Characteristics of classical Au nano particle, add and analyze after thing owing to changing the virgin state of original Au nano particle, cause absorption spectrum to change, by detecting, these small changes detection is to be detected analyses thing.Au nano particle ultraviolet-visible spectrophotometry can be detected very intuitively by the change of color in addition, and this just substantially increases the convenience of detection.
Nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) be that nuclear magnetic moment acts in stationary magnetic field and high frequency magnetic field simultaneously, and the resonance absorption phenomenon occurred when meeting certain condition, be the technology that a kind of energy variation utilizing atomic nucleus in magnetic field obtains about nuclear information.What observe nuclear magnetic resonance (NMR) signal the earliest is two laboratories of the U.S., they in the same period interior diverse ways observed NMR phenomenon: the research group that the Bloch F. of a Ge Shi Stanford University leads, the research group that the Purcell E.M. of another Ze Shi Harvard University leads.NMR technology is mainly used in nuclear physics research aspect at first, and measure various nuclear magnetic moments etc. with it, in the structure measurement of chemical molecular, obtained huge progress afterwards, therefore Bloch and Purcell two people obtains the Nobel Prize in physics of nineteen fifty-two.Wherein, the NMR signal of what Purcell observed is solidifying solid matter, the NMR signal of what Bloch observed is water.NMR technology is mainly used in following three large fields: (1) is chemically determining the chemical structural formula of molecule and intermolecular interaction; (2) in biological chemistry, determine the 3D structure of protein molecule and explain the relevance of its structure sequence and function; (3) medically utilize proton to produce and have the internal body organs of anatomical function and the image of tissue, i.e. the clinical diagnosis function of Magnetic resonance imaging (MRI), the contrast preparation that great majority exist at present is divided into T
1contrast preparation (such as: Gd class, Mn class) and T
2contrast preparation (such as: Fe class), these contrast preparation with magnetic core are by changing local or overall T
1, T
2relaxation time reaches raising signal difference, thus realizes radiography enhancing function.These contrast preparation are modified by modifying targeting factor, or specific recognition unit, produce nmr sensor (MR Sensor).
Nmr sensor mainly relies on the magnetic property of surface-functionalized contrast preparation originally under different conditions (dispersed and polymeric form) to change, and causes the relaxation time of surrounding water molecules or proton to change, thus reaches the object of detection.Such as: heavy metal particles detects (Hg
2+, Pb
2+, Zn
2+), Viral diagnosis, Small molecular detection, Bacteria Detection etc.The people such as Hakho Lee, Ralph Weissleder, Lee Josephson have done a large amount of work in nmr sensor, based on the large molecule of magnetic nano particle subsystem Fast nondestructive evaluation, Small molecular, interaction etc. between molecule, amplifies the change of visual inspection magnetic signal by data.Nmr sensor as a kind of newly, convenient, simple detection method, its Cleaning Principle in different modes, how to apply more widely and also need further to explore and research.
The visual field that the public come into by melamine is due to Chinese milk powder contamination accident in 2008, event cause is that the baby much eating the baby milk powder that Sanlu Group is produced is found to suffer from kidney stone, finds industrial chemicals melamine (having high content nitrogen 66%) subsequently in its milk powder.In milk powder producing process, add industrial chemicals melamine, be mixed with the cyanuric acid be mixed in the middle of melamine simultaneously.Because human body cannot transform this two kinds of materials, final melamine and cyanuric acid are transported to kidney by blood, two kinds of materials meet, and by the interaction of hydrogen bond, again form water-fast macromolecular complex with network, and deposit, form calculus, result causes the physical blockage of renal tubule, causes urine to get rid of smoothly, make kidney ponding, finally cause kidney failure.
Based on Au-Fe
3o
4composite nano materials, modified specificity identification by body unit, be combined with melamine by hydrogen bond, impel the change of composite nano materials generation state, detect the change of its spectral signal by visible spectrum in addition, utilize the signal intensity of its magnetic property of magnetic resonance imager record.This compound substance has merged the advantage that uv-vis spectra detects and magnetic resonance imaging detects, and has very wide application prospect, has not only enriched the detection method of melamine, the range of application of the composite nano materials also expanded.
Summary of the invention
Object of the present invention is exactly provide a kind of based on Au-Fe to overcome defect that above-mentioned prior art exists
3o
4composite nanoparticle detects the Synthesis and applications of the double mode sensor of melamine.
That is, the present invention has three objects:
1, the present invention aims to provide a kind of double mode sensor detecting melamine.
2, present invention also offers the preparation method of above-mentioned double mode sensor.
3, the present invention by above-mentioned double mode sensor application in the detection of melamine.
Object of the present invention can be achieved through the following technical solutions:
A kind of based on Au-Fe
3o
4the preparation method of the double mode sensor of melamine of composite nanoparticle, comprises the following steps:
(1) specific receptor unit is prepared
(2) Au-Fe is prepared
3o
4composite nanoparticle;
(3) preparation is modified with the Au-Fe of specific receptor unit
3o
4composite nanoparticle (is abbreviated as MTT@Au-Fe
3o
4composite nanoparticle):
NOBF
4dMF solution join Au-Fe
3o
4in the hexane solution of composite nanoparticle, vibration is rocked, nano particle enters into DMF solution, normal hexane and the toluene solution of removing oil reservoir volume ratio 1:1 are centrifugal, the nanoparticle dispersion obtained is in DMF, add specific receptor unit prepared by step (1) again, oscillating reactions 24-48 hour, obtain the Au-Fe by coordination modified receptor unit
3o
4the DMF solution of nano particle, dialysis.
Step (1) is prepared specific receptor unit and is comprised the following steps:
(1.1) different sulphur cyanato-ethyl formate is dissolved in acetone;
(1.2) 2-amino-2-thiazole woods is dissolved in CH
2cl
2in;
(1.3) (1.2) gained solution is added drop-wise in (1.1) gained solution, the mixed solution heating obtained, keeps 0.5h, collecting precipitation, filters, and with acetone washing, obtains
(1.4) get
join in HCl, under argon atmosphere, add hot reflux, in course of reaction, detect H with Lead acetate paper
2s, after having reacted, filtration washing, drying obtains white solid specific receptor unit
The mol ratio of described different sulphur cyanato-ethyl formate and 2-amino-2-thiazole woods is (1.2-1.5): 1.
Step (2) prepares Au-Fe
3o
4composite nano-granule submethod is as follows:
(2.1) Au nano particle synthesis:
Get HAuCl
4(H
2o)
3joining in naphthane and oleyl amine mixed solution, is about 60-85 DEG C in temperature, keeps 4-6 hour, cool to room temperature, and it is centrifugal to add ethanol, is dispersed in normal hexane;
(2.2) Au-Fe
3o
4nano particle synthesizes:
At oleyl amine, oleic acid, in octadecylene dicyandiamide solution, adds Au nano particle, magnetic agitation, is heated to 120-135 DEG C, and nitrogen flows down and keeps 20-60 minute.Slowly be heated to 220-260 DEG C and keep 30-90 minute, be cooled to room temperature.Sudden and violent leakage 1h in atmosphere, centrifugal, obtain Au-Fe
3o
4nanoparticle dispersion is in normal hexane.
In step (3), described NOBF
4dMF solution be saturated solution; The time that described vibration is rocked is 3-5 minute; Specific receptor unit and Au-Fe
3o
4the proportioning that adds be 10-20mg:50-100mg.
A kind of adopt above-mentioned preparation method to obtain based on Au-Fe
3o
4the double mode sensor of melamine of composite nanoparticle is a kind of water miscible composite nanoparticle containing specific receptor unit.
A kind of based on Au-Fe
3o
4the application of the double mode sensor of melamine of composite nanoparticle, detects melamine jointly by ultraviolet absorption spectroscopy and nuclear magnetic resonance method two kinds of methods.
The present invention is by having the Au-Fe modified by body unit of specific recognition
3o
4composite nanoparticle, under the effect of melamine, induction Au-Fe
3o
4composite nanoparticle carries out self assembly.In the process, one side Au-Fe
3o
4the self assembly of composite nanoparticle can change the absorption intensity of the UV-vis of composite nanoparticle and the wavelength of absorption peak, this change can by ultraviolet-visible pectrophotometer record, on the other hand, the self assembly of composite nanoparticle can change the relaxation rate of ambient water proton, this change can be detected by nuclear magnetic resonance analyser, thus realizes the double mode detection to melamine.
The present invention is owing to adopting novel specific receptor unit, and specific receptor unit is modified on nano particle by coordination strong between Au-S, in addition, and Au-Fe
3o
4composite nanoparticle make use of the optical property of Au and the magnetic performance of Fe.Double mode detection based on above two kinds of performances substantially reduces testing cost, improves detection efficiency, achieves the detection under varying environment condition, has larger actual application prospect.
Compared with prior art, beneficial effect of the present invention is:
Double mode sensor prepared by the present invention has applied range, and selectivity is high, and antijamming capability is strong.Method is provided for realizing application fast under different actual conditions.
The present invention, when the detection by Ultravioblet spectrophotometer, by the change of solution colour, can realize visual testing process.
Double mode sensor operations prepared by the present invention is simple, and reaction degree of controllability is high, expands the range of application of nanometer technology.
Accompanying drawing explanation
Fig. 1 is specific receptor unit prepared in embodiment 1
1h NMR spectrogram.
Fig. 2 is the transmission electron microscope picture of Au nano particle prepared in embodiment 1.
Fig. 3 is the uv absorption spectra of Au nano particle prepared in embodiment 1.
Fig. 4 is Au-Fe prepared in embodiment 1
3o
4the transmission electron microscope picture of nano particle.
Fig. 5 is Au-Fe prepared in embodiment 1
3o
4the uv absorption spectra of nano particle.
Fig. 6 is Au-Fe prepared in embodiment 1
3o
4the hydration particle diameter of nano particle.
Fig. 7 is Au-Fe prepared in embodiment 1
3o
4the infrared spectrum of nano particle.
Fig. 8 is the Au-Fe containing specific receptor unit prepared in embodiment 1
3o
4the hydration particle diameter of nano particle.
Fig. 9 is the Au-Fe containing specific receptor unit prepared in embodiment 1
3o
4the uv absorption spectra of nano particle.
Figure 10 is the Au-Fe containing specific receptor unit prepared in embodiment 1
3o
4the infrared spectrum of nano particle.
Figure 11 is the Au-Fe containing specific receptor unit prepared in embodiment 1
3o
4composite nanoparticle 0,2,4,6,8,10 ... the solution medium ultraviolet absorption spectrum change of the melamine of 20 μMs.
Figure 12 is the Au-Fe containing specific receptor unit prepared in embodiment 1
3o
4composite nanoparticle 20 μMs of uracils, cytimidine, thymidine solution medium ultraviolet absorption spectrum change.
Figure 13 is the Au-Fe containing specific receptor unit prepared in embodiment 1
3o
4composite nanoparticle 0,5,10,15,20 ... Δ T in the solution of the melamine of 40 μMs
2be worth change.
Figure 14 is the Au-Fe containing specific receptor unit prepared in embodiment 1
3o
4composite nanoparticle is Δ T in 30 μMs of uracils, cytimidine, thymidine solution
2the change of value.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
(1) preparation of specific receptor unit.
(1.1) get 1.42mL different sulphur cyanato-ethyl formate (12mmol), be dissolved in 100mL acetone.
(1.2) get 1.022g 2-amino-2-thiazole woods (10mmol), be dissolved in 200mL CH
2cl
2in.
(1.3) step (1.2) gained solution is added drop-wise in step (1.1) gained solution slowly, the mixed solution obtained is heated to 50 DEG C, keeps 0.5h, is precipitated, and filters, washs with acetone.Obtain
(1.4) 2.00g is got
(10.7mmol) join 100mL 18%HCl, under argon atmosphere, add hot reflux 6.5h detect H with Lead acetate paper in course of reaction
2s, after question response terminates, cooling, filter, drying obtains white solid specific receptor unit
Specific receptor unit
1h NMR spectrogram as shown in Figure 1.In Fig. 1,
1H NMR(DMSO-d
6)：δ＝2.66(m,3,CH
2S+SH),δ＝3.77(m,2,CH
2N),δ＝11.45(s,2,2NH)
(2) Au-Fe
3o
4prepared by nano particle.
Get 100mg HAuCl
4(H
2o)
3join in 10mL naphthane and 1mL oleyl amine mixed solution, form red solution, solution is heated to about 70 DEG C, and keep 5h, solution becomes dark brown red, cool to room temperature, and it is centrifugal to add ethanol, is dispersed in normal hexane, obtains golden nanometer particle.
At 1mL oleyl amine, in the mixed solution of 1mL oleic acid and 20mL octadecylene, add 2mL Au nano particle (10-20mg), mix, be heated to 120-135 DEG C, magnetic agitation, nitrogen flows down and keeps 20-60 minute.Slowly be heated to 240 DEG C (5 DEG C/4min) and keep 30-90 minute, remove thermal source and be cooled to room temperature.Sudden and violent leakage in atmosphere 1h to form Fe
3o
4nano particle, it is centrifugal to add isopropyl alcohol, and is dispersed in normal hexane, obtains Au-Fe
3o
4nano particle.
As shown in Figure 2, as seen from Figure 2, Au nano particle has extraordinary dispersiveness to the transmission electron microscope picture of golden nanometer particle in normal hexane, and size is homogeneous, the seed that the Au nano particle obtained reacts as next step; Uv absorption spectra as shown in Figure 3.
Au-Fe
3o
4the transmission electron microscope picture of nano particle as shown in Figure 4; Uv absorption spectra as shown in Figure 5; Hydration grain-size graph as shown in Figure 6; Infrared spectrum as shown in Figure 7.
(3) based on Au-Fe
3o
4nano particle detects the preparation of the double mode sensor of melamine.
Get 0.1g NOBF
4be dissolved in 10mL DMF, ultrasonic dissolution.Get ~ 50mg Au-Fe
3o
4nanoparticle dispersion is to 10mL normal hexane.NOBF
4dMF solution join Au-Fe
3o
4in the hexane solution of nano particle, vibration is rocked, and nano particle enters into DMF solution, with normal hexane and toluene (1:1) centrifugal.Be distributed in DMF.Add 15mg specific receptor unit again, shaking table, oscillating reactions 48 hours.Obtain the Au-Fe by coordination modified receptor unit
3o
4the DMF solution of nano particle, dialyses 48 hours.
The time that described vibration is rocked is 3 ~ 5min.
Au-Fe containing specific receptor unit
3o
4the hydration particle diameter of composite nanoparticle as shown in Figure 8; Uv absorption spectra as shown in Figure 9; Infared spectrum figure as shown in Figure 10.
Disperse MTT Au-Fe in aqueous as can be seen from Figure 8
3o
4the hydration kinetics diameter of composite nanoparticle is about 30nm, after its modification is described, and MTT@Au-Fe
3o
4composite nanoparticle has good dispersiveness, for next step practical application lays the foundation.
Fig. 7 and Figure 10 contrasts, and modified specificity is by after body unit, and the characteristic peak of-C-S-is positioned at 647cm
-1place, illustrates that specific receptor unit modifies Au-Fe by the bridge linking effect of Au-S key
3o
4composite nano-granule sub-surface.
Embodiment 2
(1) preparation of specific receptor unit is with embodiment 1.
(2) Au-Fe
3o
4the preparation of nano particle is with embodiment 1.
(3) based on Au-Fe
3o
4nano particle detects the preparation of the double mode sensor of melamine.
Get 0.1g NOBF
4be dissolved in 10mL DMF, ultrasonic dissolution.Get ~ 50mg Au-Fe
3o
4nanoparticle dispersion, to 10mL normal hexane, makes it to mix.NOBF
4dMF solution join Au-Fe
3o
4in the hexane solution of nano particle, vibration is rocked, and nano particle enters into DMF solution, with normal hexane and toluene (1:1) centrifugal.Be distributed in DMF.Add 20mg specific receptor unit again, shaking table oscillating reactions 48 hours.Obtain the Au-Fe by coordination modified receptor unit
3o
4the DMF solution of nano particle, dialyses 72 hours.
The time that described vibration is rocked is 3 ~ 5min.
Embodiment 3
(1) preparation of specific receptor unit is with embodiment 1.
(2) Au-Fe
3o
4the preparation of nano particle is with embodiment 1.
(3) based on Au-Fe
3o
4nano particle detects the preparation of the double mode sensor of melamine
Get 0.1g NOBF
4be dissolved in 10mL DMF, ultrasonic dissolution.Get ~ 100mg Au-Fe
3o
4nanoparticle dispersion, to 10mL normal hexane, makes it to mix.NOBF
4dMF solution join Au-Fe
3o
4in the hexane solution of nano particle, vibration is rocked, and nano particle enters into DMF solution, with normal hexane and toluene (1:1) centrifugal.Be distributed in DMF.Add 20mg specific receptor unit again, shaking table oscillating reactions 24 hours.Obtain the Au-Fe by coordination modified receptor unit
3o
4the DMF solution of nano particle, dialyses 72 hours.
The time that described vibration is rocked is 3 ~ 5min.
By obtained based on Au-Fe in embodiment 1
3o
4the double mode sensor that nano particle detects melamine detects melamine:
(1) ultraviolet spectroscopy is utilized to detect.
Be modified with the Au-Fe of specific receptor unit
3o
4add melamine in the solution of nano particle, make the concentration of melamine be respectively 0,2,4,6,8,10 ... 20 μMs, detect the change of the ultra-violet absorption spectrum caused by the concentration of different melamines.Result as shown in figure 11, along with the increase of melamine concentration, Au-Fe
3o
4the wavelength of the characteristic absorption peak of the ultra-violet absorption spectrum of composite nanoparticle is offset to 557nm by 543nm.The detectability of melamine is about 3.85 μMs.Along with the melamine concentration in solution increases, color is changed to blueness by aubergine.Be convenient to people's direct visual perception, convenient and practical.
Thymine, uracil, the cytimidine of 20 μMs is added in the solution of composite nanoparticle being modified with specific receptor unit, the change of the ultra-violet absorption spectrum relatively caused by the material with analog structure, detects the selectivity of this sensor material to melamine.Result as shown in figure 12.
(2) nuclear magnetic resonance method is utilized to detect.
In the solution of composite nanoparticle being modified with specific receptor unit, add melamine, make the concentration of melamine be respectively 0,5,10,15 ... 40 μMs, detect the Δ T caused by the concentration of different melamines
2the change of value.As shown in figure 13, along with the increase of melamine concentration, Δ T2 value becomes greatly result gradually, when the concentration of melamine is 35 μMs, and Δ T
2change be about 139.4ms.The lowest detectable limit of melamine is about 2.76 μMs.
In the solution of composite nanoparticle being modified with specific receptor unit, add 30 μMs of thymines, uracil, cytimidines, compare the Δ T caused by the material with analog structure
2the change of value, detects the selectivity of this sensor material to melamine.Result is as Figure 14.
Above-mentioned is can understand and use invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (6)
1. one kind based on Au-Fe
3o
4the preparation method of the double mode sensor of melamine of composite nanoparticle, is characterized in that, comprise the following steps:
(1) specific receptor unit is prepared
(2) Au-Fe is prepared
3o
4composite nanoparticle;
(3) preparation is modified with the Au-Fe of specific receptor unit
3o
4composite nanoparticle:
NOBF
4dMF solution join Au-Fe
3o
4in the hexane solution of composite nanoparticle, vibration is rocked, nano particle enters into DMF solution, normal hexane and the toluene solution of removing oil reservoir volume ratio 1:1 are centrifugal, the nanoparticle dispersion obtained is in DMF, add specific receptor unit prepared by step (1) again, oscillating reactions 24-48 hour, obtain the Au-Fe by coordination modified receptor unit
3o
4the DMF solution of nano particle, dialysis.
2. one according to claim 1 is based on Au-Fe
3o
4the preparation method of the double mode sensor of melamine of composite nanoparticle, is characterized in that, step (1) is prepared specific receptor unit and comprised the following steps:
(1.1) different sulphur cyanato-ethyl formate is dissolved in acetone;
(1.2) 2-amino-2-thiazole woods is dissolved in CH
2cl
2in;
(1.3) (1.2) gained solution is added drop-wise in (1.1) gained solution, the mixed solution heating obtained, keeps 0.5h, collecting precipitation, filters, and with acetone washing, obtains
(1.4) get
join in HCl, under argon atmosphere, add hot reflux, in course of reaction, detect H with Lead acetate paper
2s, after having reacted, filtration washing, drying obtains white solid specific receptor unit
3. one according to claim 2 is based on Au-Fe
3o
4the preparation method of the double mode sensor of melamine of composite nanoparticle, is characterized in that, the mol ratio of described different sulphur cyanato-ethyl formate and 2-amino-2-thiazole woods is (1.2-1.5): 1.
4. one according to claim 1 is based on Au-Fe
3o
4the preparation method of the double mode sensor of melamine of composite nanoparticle, is characterized in that, in step (3), and described NOBF
4dMF solution be saturated solution; The time that described vibration is rocked is 3-5 minute; Specific receptor unit and Au-Fe
3o
4the proportioning that adds be 10-20mg:50-100mg.
5. one kind adopt preparation method according to claim 1 obtain based on Au-Fe
3o
4the double mode sensor of melamine of composite nanoparticle.
6. one kind as claimed in claim 5 based on Au-Fe
3o
4the application of the double mode sensor of melamine of composite nanoparticle, is characterized in that, jointly detects melamine by ultraviolet absorption spectroscopy and nuclear magnetic resonance method two kinds of methods.
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| CN106596617A (en) * | 2016-12-21 | 2017-04-26 | 厦门大学 | Magnetic resonance imaging (MRI)-based new melamine detection method |
| CN108333536A (en) * | 2017-01-20 | 2018-07-27 | 国家纳米科学中心 | The Magnetic Sensor and its construction method, purposes read based on longitudinal relaxation time signal |
| CN113567398A (en) * | 2020-04-28 | 2021-10-29 | 南开大学 | Lead ion concentration detection method based on dark field spectrum detection technology |
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| CN113567398A (en) * | 2020-04-28 | 2021-10-29 | 南开大学 | Lead ion concentration detection method based on dark field spectrum detection technology |
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