CN103920168A - Nuclear magnetic resonance sensor for detecting melamine based on magnetic nanoparticles, and preparation method and application thereof - Google Patents
Nuclear magnetic resonance sensor for detecting melamine based on magnetic nanoparticles, and preparation method and application thereof Download PDFInfo
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- CN103920168A CN103920168A CN201410098595.9A CN201410098595A CN103920168A CN 103920168 A CN103920168 A CN 103920168A CN 201410098595 A CN201410098595 A CN 201410098595A CN 103920168 A CN103920168 A CN 103920168A
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Abstract
The invention discloses a nuclear magnetic resonance sensor for detecting melamine based on magnetic nanoparticles. The nuclear magnetic resonance sensor is a Fe/Fe3O4 magnetic nanoparticle containing an acceptor unit which is capable of specific recognition of melamine and having water-solubility, superparamagnetism, uniform particle size distribution and a particle size of about 10 to 20 nm. A preparation method for the sensor comprises the following steps: preparation of a Fe/Fe3O4 magnetic nanoparticle through high temperature pyrolysis; preparation of Dopa-PEG and Dopa-acceptor unit by using N-hydroxy succinimide and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride; and preparation of a target nanoparticle for preparation of the nuclear magnetic resonance sensor used for detecting melamine in virtue of coordination of oxygen and connection of the nanoparticle. The preparation method provided by the invention has the advantages of easiness, safety, economy and easy availability of raw materials and good process controllability. According to the invention, a novel prospect--a nanometer magnetic resonance sensor is provided for application of a nanometer magnetic resonance contrast agent material, and the research area of nano-materials is broadened.
Description
Technical field
The present invention relates to nuclear magnetic resonance, NMR sensory field, be specially a kind of nmr sensor that detects tripolycyanamide based on magnetic nano-particle and its preparation method and application.
Background technology
Sensor is a kind of device, is to detect or measure a kind of physical property line item of going forward side by side, and shows or otherwise responds.Sensor can be divided three classes, i.e. 1. physical sensors is used for measuring distance, quality, temperature, pressure etc.; 2. chemical sensor, by chemistry or physical responses mensuration chemical substance; 3. biosensor, conventionally applies certain bio-sensing primitive and detects chemical substance.All these devices must be connected with certain sensing device, occurred response so just may be detected.Building block mainly comprises: analyze matter, recognition unit, transmitter, measuring device.
Nuclear magnetic resonance, NMR is because 1. MRI (NMR (Nuclear Magnetic Resonance)-imaging, or magnetic imaging) has fabulous resolving power to soft tissue.Inspection to positions such as bladder, rectum, uterus, vagina, BJMs is better than CT; 2. various parameters can be used for imaging, and multiple imaging parameters can provide abundant diagnostic message, and this makes medical diagnosis and convenient to the research of human body metabolism and function, effectively.It is large that the T1 value of for example hepatitis and liver cirrhosis becomes, and the T1 value of hepatocarcinoma is larger, makes t1 weighted image, can distinguish liver's benign tumor and malignant tumor; 3. by regulating magnetic field can freely select desired profile.Can obtain the image that other imaging technique can not approach or be difficult to approach position.Sagittal plane, coronalplane, axial imaging can be made, the transverse section vertical with people's long axis of body can only be obtained unlike CT; 4. human body is not had to ionization radiation injury; 5. the non-vanishing nuclear element of all spins can be in order to imaging in principle, and such as hydrogen (H), carbon (C), nitrogen (N), phosphorus (P) etc., become the most important detection method of the present and the future.The contrast agent that most exists is divided into T1 contrast agent (for example: Gd class, Mn class) and T2 contrast agent (for example: Fe class), these contrast agent with magnetic core reach raising signal difference, thereby realize radiography enhancement function by changing part or overall T1, T2 relaxation time.These contrast agent are modified by modifying targeting factor, or specific recognition unit, nmr sensor (MR Sensor) produced.
Each each side of extensive use of nmr sensor at present and life, such as: heavy metal particles detects (Hg
2+, Zn
2+), viral detection, protein, micromolecule, antibacterial etc.Nmr sensor mainly rely on surface-functionalized contrast agent this in different conditions (monomer and polymeric form) under magnetic property change, cause that the relaxation time of ambient water molecule or proton changes, thereby reach the object of detection.For example: Hyun Jung Chung, Cesar M.Castro, Hyungsoon Lm, Hakho Lee, Ralph Weissleder have synthesized magnetic DNA nanosystems and carried out the phenotype of fast detecting antibacterial, amplify the variation of visual inspection magnetic signal by data.Simultaneously nmr sensor as a kind of new, convenient, simple detection method, its under different mode detection principle, how more widely application also needs further to explore and research.
Tripolycyanamide has high content nitrogen (66%), is often used to add the content that improves nitrogen in milk product to, meets the requirement of national standard to protein content in milk product.But especially can produce obvious toxicity to baby and house pet.In milk powder production process, add industrial chemicals tripolycyanamide, mixed simultaneously and be mixed in the central cyanuric acid of tripolycyanamide.Because human body cannot transform this two kinds of materials, final tripolycyanamide 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 tubules, causes urine to get rid of smoothly, make kidney hydrops, finally cause kidney exhaustion.
The present invention is based on the magnetic Nano material of good biocompatibility, what modified specificity was identified is subject to body unit, is combined with tripolycyanamide by hydrogen bond, impels the change of magnetic Nano material generation state, and the change of recording relaxation time realizes its efficient detection.At present, adopt the report of magnetic Nano material detection tripolycyanamide few, the present invention had both enriched the detection method of tripolycyanamide, had also expanded the range of application of magnetic Nano material.
Summary of the invention
The nmr sensor that the object of the present invention is to provide a kind of detection tripolycyanamide based on magnetic nano-particle provides the preparation method of above-mentioned nmr sensor simultaneously, and is applied to the detection of tripolycyanamide.
Technical scheme of the present invention is:
A preparation method for the nmr sensor of the detection tripolycyanamide based on magnetic nano-particle, comprises the following steps:
(1) preparation of specific receptor unit:: 1,8-diazabicylo 11 carbon-7-alkene (DBU) is 1:1 with the mol ratio of 2-benzyl acetate bromide, cyanuric acid excessive (cyanuric acid: 2-benzyl acetate bromide=3:1～5:1), under the condition of nitrogen or noble gas, in dry DMF solvent, 70 DEG C of isothermal reaction 10-20h, purification obtains benzyl ester, hydrolysis, acidify, extracts and obtains specific receptor unit with THF;
(2) Fe/Fe that contains specific receptor unit
3o
4the preparation of magnetic nano-particle: step (1) gained specific receptor unit and Polyethylene Glycol monocarboxylic acid are dissolved in respectively to pyridine, add respectively bridging agent, activation 0.5h～2h; Respectively the chloroformic solution that is dissolved with condensing agent and dopamine hydrochloride is added in the solution that above-mentioned activation is good, magnetic agitation 4～8h, merges solution, adds Fe/Fe
3o
4magnetic nano-particle, reaction 10-20h is by normal hexane precipitation, centrifugal.
Described purification is: by column chromatography separating-purifying, CH
2cl
2: MeOH=96:4.
The benzyl ester obtaining is in dense NaOH Water Under solution, and making the pH value of solution with concentrated hydrochloric acid acidify is 1.
Described bridging agent is that N-hydroxy-succinamide is; Described condensing agent is 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride.
Described Fe/Fe
3o
4the preparation method of magnetic nano-particle is: under nitrogen or noble gas atmosphere, and taking octadecylene as solvent, Fe (CO)
5as source of iron, oleyl amine is surfactant and stabilizing agent, and hexadecylamine hydrochloride strengthens degree of crystallinity, and Pintsch process is prepared Fe/Fe
3o
4magnetic nano-particle material; The condition of described high temperature is 180-200 DEG C; Octadecylene, Fe (CO)
5, oleyl amine and hexadecylamine hydrochloride proportioning be 20mL:0.7mL:0.2mL:0.1mg.
The nmr sensor based on magnetic nano-particle detection tripolycyanamide of being prepared by said method, is a kind of water miscible magnetic nano-particle that contains specific receptor unit, and size is about 10～20nm.
The present invention, by the identification ability of specific receptor unit to tripolycyanamide, carries out the targeting experiment of tripolycyanamide, and induction magnetic nano-particle carries out self assembly.In this process, the self assembly meeting of magnetic nano-particle changes the relaxation rate of ambient water proton, and this change can be detected by nuclear magnetic resonance analyser, thereby realizes the detection to tripolycyanamide; Preparation method of the present invention is simple and safe, and raw material economy, is easy to get, and process controllability is strong; The present invention, for the application of nano magnetic resonance contrast agent material provides a kind of new prospect-nano magnetic resonance sensor, has enriched the research field of nano material.
Brief description of the drawings
Fig. 1 is the 1H NMR spectrogram of the prepared specific receptor unit of embodiment 1.
Fig. 2 is the TEM figure of the prepared magnetic nano-particle of embodiment 2.
Fig. 3 is the DLS of the prepared magnetic nano-particle of embodiment 2.
Fig. 4 is the X ray diffracting spectrum of the prepared magnetic nano-particle of embodiment 2.
Fig. 5 is the infrared spectrum of the prepared magnetic nano-particle of embodiment 2.
Fig. 6 is the TEM figure of the prepared magnetic nano-particle that contains specific receptor unit of embodiment 3.
Fig. 7 is the infrared spectrum of the prepared magnetic nano-particle that contains specific receptor unit of embodiment 3.
Fig. 8 is the prepared Fe/Fe that contains specific receptor unit of embodiment 3
3o
4the DLS of nanoparticle.
Fig. 9 is the DLS that the magnetic nano-particle that contains specific receptor unit in embodiment 5 adds 30 μ M melamine solution.
Figure 10 is the magnetic nano-particle that contains specific receptor unit in embodiment 50,2,4,6,8,10,12 ... the rate of change of △ T2 value in the solution of the tripolycyanamide of 30 μ M.
Figure 11 is the variation of magnetic nano-particle △ T2 value in 30 μ M uracil, cytosine, thymus pyrimidine solution of containing specific receptor unit in embodiment 6.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
(1) get 5.0g cyanuric acid and join the dry DMF of 150mL, then add 1.15mLDBU, 1.2mL2-benzyl acetate bromide, under Ar atmosphere, stirring at normal temperature 1h, is then heated to 70 DEG C, more than keeping 12h, after reaction finishes, cool to room temperature, DMF is removed in distilling under reduced pressure, the solid obtaining THF washing and filtering, the filtrate that obtains is concentrated, filters and is dried, the column chromatography (SiO for solid obtaining with cold water washing
2, CH
2cl
2/ MeOH, 24:1) separating-purifying, obtain white solid benzyl ester.
(2) get 477mg NaOH and be dissolved in 15mL H
2in O, mix homogeneously, adds 661mg benzyl ester, stirs and spends the night at normal temperatures, after reaction finishes, uses 36wt%HCl acidify, PH=1, and H is removed in distilling under reduced pressure
2o, the material obtaining filters and extracts repeatedly with THF, and concentrated filtrate, obtains white solid specific receptor unit.
The prepared specific receptor unit of the present embodiment
1h NMR spectrogram as shown in Figure 1.
Embodiment 2:
Get 20mL octadecylene with graduated cylinder, get 0.2mL oleyl amine with pipet, get 0.1gHDAHCl with analytical balance, join in there-necked flask, mix homogeneously, magnetic agitation deaeration, the time is approximately controlled at 1h.Temperature is raised to 120 DEG C, keeps 30min.Be heated to 180 DEG C, use N
2gas protection, fast injection 0.7mL Fe (CO)
5, keep mixing speed maximum.Keep after 20min at 180 DEG C, injection oleic acid (0.3mL, 1mmol), continues to keep 10min.Remove thermal source, be cooled to room temperature, exposure air.Centrifugal (12000rpm, 10min), until wash clean.The Fe/Fe obtaining
3o
4nanoparticle is dispersed in normal hexane.
The TEM of the prepared magnetic nano-particle of the present embodiment schemes as shown in Figure 2; DLS as shown in Figure 3; X ray diffracting spectrum as shown in Figure 4; Infrared spectrum as shown in Figure 5.
Embodiment 3:
(1) analytical balance takes and be dissolved in 5mL pyridine by body unit (m=16.84mg, M=187.11g/mol, n=0.09mmol), adds N-hydroxy-succinamide 25mg, and reaction 1h, obtains solution A; Analytical balance takes Polyethylene Glycol monocarboxylic acid (m=60mg, M=2000g/mol, n=0.03mmol) and is dissolved in 5mL pyridine, adds N-hydroxy-succinamide 10mg, and reaction 1h, obtains solution B.
(2) analytical balance takes Dopa-HCl (m=15.2mg, M=189.68g/mol, n=0.08mmol), 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride 25mg is dissolved in 1mL chloroform, ultrasonic making is uniformly dispersed, and obtains solution A '; Analytical balance takes Dopa-HCl (m=4mg, M=189.68g/mol, n=0.02mmol), 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride 10mg is dissolved in 1mL chloroform, and ultrasonic making is uniformly dispersed, and obtains solution B '; Solution A ' join in solution A solution B ' join in solution B.
(3) magnetic agitation 4h, the two merging; Add 15～25mg Fe/Fe
3o
4nanoparticle, shaking table spends the night.By normal hexane precipitation, water is from first pass, and all the other are centrifugal with ethanol.
Fig. 6 is the TEM figure of the prepared magnetic nano-particle that contains specific receptor unit of the present embodiment;
Fig. 7 is the infrared spectrum of the prepared magnetic nano-particle that contains specific receptor unit of the present embodiment;
Fig. 8 is the prepared Fe/Fe that contains specific receptor unit of the present embodiment
3o
4the DLS of nanoparticle.
Embodiment 4:
(1) analytical balance takes and be dissolved in 5mL pyridine by body unit (m=16.84mg, M=187.11g/mol, n=0.09mmol), adds N-hydroxy-succinamide 25mg, and reaction 1h, obtains solution A; Analytical balance takes Polyethylene Glycol monocarboxylic acid (m=30mg, M=2000g/mol, n=0.015mmol) and is dissolved in 5mL pyridine, adds N-hydroxy-succinamide 10mg, and reaction 1h, obtains solution B;
(2) analytical balance takes Dopa-HCl (m=15.2mg, M=189.68g/mol, n=0.08mmol), 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride 25mg is dissolved in 1mL chloroform, ultrasonic making is uniformly dispersed, and obtains solution A '; Analytical balance takes Dopa-HCl (m=2mg, M=189.68g/mol, n=0.01mmol), 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride 10mg is dissolved in 1mL chloroform, and ultrasonic making is uniformly dispersed, and obtains solution B '; Solution A ' join in solution A solution B ' join in solution B;
(3) magnetic agitation 4h, the two merging; Add 15～20mg nanoparticle, shaking table spends the night.By normal hexane precipitation, water is from first pass, and all the other are centrifugal with ethanol.
Embodiment 5:
In the solution of the nanoparticle that is modified with specific receptor unit that contains 0.032mM Fe, add cyanuric acid, make the concentration of cyanuric acid be respectively 0,2,4,6,8,10,12 ... 30 μ M.
Fig. 9 is the DLS that the magnetic nano-particle that contains specific receptor unit in the present embodiment adds 30 μ M melamine solution.
Detect the rate of change of the △ T2 value being caused by the concentration of different tripolycyanamide; Result as shown in figure 10.Along with the increase of melamine concentration, △ T2 value becomes greatly gradually, and in the time that the concentration of tripolycyanamide is 30 μ M, the rate of change of △ T2 is about 0.406.The lowest detectable limit of tripolycyanamide is about 2 μ M.
Embodiment 6:
In the solution of the nanoparticle that is modified with specific receptor unit that contains 0.032mM Fe, add 30 μ M thymus pyrimidines, uracil, cytosine, relatively, by the variation of the caused △ T2 of the material with analog structure value, detect the selectivity of this magnetic resonance contrast agent sensor material to tripolycyanamide.Result is as Figure 11.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the disclosed content of this embodiment.Do not depart from the equivalence or the amendment that under principles of this disclosure, complete so every, all fall into the scope of protection of the invention.
Claims (10)
1. the preparation method that detects the nmr sensor of tripolycyanamide based on magnetic nano-particle, is characterized in that, comprises the following steps:
(1) preparation of specific receptor unit: 1,8-diazabicylo 11 carbon-7-alkene (DBU) is 1:1 with the mol ratio of 2-benzyl acetate bromide, cyanuric acid excessive (cyanuric acid: 2-benzyl acetate bromide=3:1～5:1), under the condition of nitrogen or noble gas, in dry DMF solvent, 70 DEG C of isothermal reaction 10-20h, purification obtains benzyl ester, hydrolysis, acidify, extracts and obtains specific receptor unit with THF;
(2) Fe/Fe that contains specific receptor unit
3o
4the preparation of magnetic nano-particle: step (1) gained specific receptor unit and Polyethylene Glycol monocarboxylic acid are dissolved in respectively to pyridine, add respectively bridging agent, activation 0.5h～2h; Respectively the chloroform that is dissolved with condensing agent and dopamine hydrochloride is added in the solution that above-mentioned activation is good, magnetic agitation 4～8h, merges solution, adds Fe/Fe
3o
4magnetic nano-particle, reaction 10-20h is by normal hexane precipitation, centrifugal.
2. preparation method according to claim 1, is characterized in that, described purification is: by column chromatography separating-purifying, CH
2cl
2: MeOH=96:4.
3. preparation method according to claim 1, is characterized in that, the benzyl ester obtaining is in dense NaOH Water Under solution, and making the pH value of solution with concentrated hydrochloric acid acidify is 1.
4. preparation method according to claim 1, is characterized in that, described bridging agent is that N-hydroxy-succinamide is; Described condensing agent is 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride.
5. preparation method according to claim 1, is characterized in that, described Fe/Fe
3o
4the preparation method of magnetic nano-particle is: under nitrogen or noble gas atmosphere, and taking octadecylene as solvent, Fe (CO)
5as source of iron, oleyl amine is surfactant and stabilizing agent, and hexadecylamine hydrochloride strengthens degree of crystallinity, and Pintsch process is prepared Fe/Fe
3o
4magnetic nano-particle material.
6. preparation method according to claim 5, is characterized in that, the condition of described high temperature is 180-200 DEG C.
7. preparation method according to claim 5, is characterized in that, octadecylene, Fe (CO)
5, oleyl amine and hexadecylamine hydrochloride proportioning be 20mL:0.7mL:0.2mL:0.1mg.
8. the nmr sensor that detects tripolycyanamide based on magnetic nano-particle, is characterized in that, is prepared by method described in claim 1-7 any one.
9. sensor according to claim 8, is characterized in that, it is a kind of water miscible magnetic nano-particle that contains specific receptor unit, and size is about 10～20nm.
10. the sensor described in claim 8 or 9 detects for tripolycyanamide.
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Cited By (6)
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| CN104447592A (en) * | 2014-11-07 | 2015-03-25 | 东南大学 | Cyanuric acid derivative, disc-like liquid crystal material and melamine detection method |
| CN105136834A (en) * | 2015-07-14 | 2015-12-09 | 上海师范大学 | 3, 4-dihydroxyphenylpropionic acid modified Fe/Fe3O4nanoparticles, its preparation method and application |
| CN105741993A (en) * | 2016-02-03 | 2016-07-06 | 上海师范大学 | Azide dopamine and carboxyl polyethylene glycol-modified Fe/Fe3O4 nanoparticle and preparation and application |
| CN106033066A (en) * | 2015-03-11 | 2016-10-19 | 中国科学院宁波材料技术与工程研究所 | A method of rapidly detecting metal ions and small-molecule compounds through nuclear magnetic resonance |
| CN106596617A (en) * | 2016-12-21 | 2017-04-26 | 厦门大学 | Magnetic resonance imaging (MRI)-based new melamine detection method |
| CN109856348A (en) * | 2019-03-08 | 2019-06-07 | 浙江省食品药品检验研究院 | A kind of method of melamine in quick measurement meat |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447592A (en) * | 2014-11-07 | 2015-03-25 | 东南大学 | Cyanuric acid derivative, disc-like liquid crystal material and melamine detection method |
| CN104447592B (en) * | 2014-11-07 | 2016-08-17 | 东南大学 | Cyanuric acid derivative, discotic mesogenic material and tripolycyanamide detection method |
| CN106033066A (en) * | 2015-03-11 | 2016-10-19 | 中国科学院宁波材料技术与工程研究所 | A method of rapidly detecting metal ions and small-molecule compounds through nuclear magnetic resonance |
| CN105136834A (en) * | 2015-07-14 | 2015-12-09 | 上海师范大学 | 3, 4-dihydroxyphenylpropionic acid modified Fe/Fe3O4nanoparticles, its preparation method and application |
| CN105741993A (en) * | 2016-02-03 | 2016-07-06 | 上海师范大学 | Azide dopamine and carboxyl polyethylene glycol-modified Fe/Fe3O4 nanoparticle and preparation and application |
| CN106596617A (en) * | 2016-12-21 | 2017-04-26 | 厦门大学 | Magnetic resonance imaging (MRI)-based new melamine detection method |
| CN106596617B (en) * | 2016-12-21 | 2018-01-02 | 厦门大学 | One kind is based on the melamine detection method of magnetic resonance imaging (MRI) |
| CN109856348A (en) * | 2019-03-08 | 2019-06-07 | 浙江省食品药品检验研究院 | A kind of method of melamine in quick measurement meat |
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