CN103920168B - Nmr sensor of tripolycyanamide and its preparation method and application is detected based on magnetic nano-particle - Google Patents
Nmr sensor of tripolycyanamide and its preparation method and application is detected based on magnetic nano-particle Download PDFInfo
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- CN103920168B CN103920168B CN201410098595.9A CN201410098595A CN103920168B CN 103920168 B CN103920168 B CN 103920168B CN 201410098595 A CN201410098595 A CN 201410098595A CN 103920168 B CN103920168 B CN 103920168B
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Abstract
The invention discloses a kind of nmr sensor detecting tripolycyanamide based on magnetic nano-particle, it is a kind of Fe/Fe by body unit containing having specific recognition effect to tripolycyanamide
3o
4magnetic nano-particle, have water solublity, superparamagnetism, even particle size distribution be about 10 ~ 20nm, preparation method is that high temperature pyrolysis prepares Fe/Fe
3o
4nanoparticle; Dopa-PEG and Dopa-is obtained by body unit by N-hydroxy-succinamide, 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, be connected with nanoparticle by the coordination of oxygen, obtain the nmr sensor target nanoparticle that may be used for preparing 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 is that 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.
Description
Technical field
The present invention relates to nuclear magnetic resonance, NMR sensory field, be specially a kind of nmr sensor based on magnetic nano-particle detection tripolycyanamide and its preparation method and application.
Background technology
Sensor is a kind of device, is to detect or measure a kind of physical property to go forward side by side line item, display or otherwise respond.Sensor can be divided three classes, i.e. 1. physical sensors, is used for measuring distance, quality, temperature, pressure etc.; 2. chemical sensor, measures chemical substance by chemistry or physical responses; 3. biosensor, certain bio-sensing primitive of application detects chemical substance usually.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, measuring device.
Nuclear magnetic resonance, NMR has fabulous resolving power to soft tissue due to 1. MRI (NMR (Nuclear Magnetic Resonance)-imaging, or magnetic imaging).CT is better than to the inspection at the positions such as bladder, rectum, uterus, vagina, BJM; 2. various parameter 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.The T1 value of such as hepatitis and liver cirrhosis becomes large, and the T1 value of hepatocarcinoma is larger, makes t1 weighted image, can distinguish liver's benign tumor and malignant tumor; 3. can unrestricted choice desired profile by adjustment magnetic field.Can obtain other imaging technique can not close to or the image that is difficult to close to position.Sagittal plane, coronalplane, axial imaging can be made, the transverse section with human body long axis normal can only be obtained unlike CT; 4. ionization radiation injury be there is no to human body; 5. the nuclear element that all spins are non-vanishing in principle can in order to imaging, 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 current great majority exist is divided into T1 contrast agent (such as: Gd class, Mn class) and T2 contrast agent (such as: Fe class), these contrast agent with magnetic core reach raising signal difference by change local or overall T1, T2 relaxation time, thus realize radiography enhancing function.These contrast agent are modified by modifying targeting factor, or specific recognition unit, produce nmr sensor (MRSensor).
Each each side of the extensive use of current nmr sensor and life, such as: heavy metal particles detects (Hg
2+, Zn
2+), Viral diagnosis, protein, micromolecule, antibacterial etc.Nmr sensor mainly rely on surface-functionalized contrast agent this under different conditions (monomer and polymeric form) magnetic property change, cause the relaxation time of surrounding water molecules or proton to change, thus reach the object of detection.Such as: HyunJungChung, CesarM.Castro, HyungsoonLm, HakhoLee, RalphWeissleder have synthesized the phenotype that magnetic DNA nanosystems carrys out quick bacterial detection, are amplified the change of visual inspection magnetic signal by data.Simultaneously nmr sensor as a kind of newly, convenient, simple detection method, its in different modes Cleaning Principle, how to apply more widely and also need further to explore and research.
Tripolycyanamide has high content nitrogen (66%), is often used to add the content improving 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 producing process, add industrial chemicals tripolycyanamide, be mixed with the cyanuric acid be mixed in the middle of tripolycyanamide simultaneously.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 failure.
The present invention is based on the magnetic Nano material of good biocompatibility, modified specificity identification by body unit, be combined with tripolycyanamide by hydrogen bond, impel the change of magnetic Nano material generation state, the change of recording relaxation time realizes its efficient detection.At present, adopt magnetic Nano material to detect the report of tripolycyanamide seldom, the present invention had both enriched the detection method of tripolycyanamide, have also been enlarged the range of application of magnetic Nano material.
Summary of the invention
The object of the present invention is to provide a kind of nmr sensor of the detection tripolycyanamide based on magnetic nano-particle, the preparation method of above-mentioned nmr sensor is provided simultaneously, and is applied to the detection of tripolycyanamide.
Technical scheme of the present invention is:
Based on a preparation method for the nmr sensor of the detection tripolycyanamide of magnetic nano-particle, comprise 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 with THF and obtains specific receptor unit;
(2) Fe/Fe containing specific receptor unit
3o
4the preparation of magnetic nano-particle: step (1) gained specific receptor unit and Polyethylene Glycol monocarboxylic acid are dissolved in pyridine respectively, add bridging agent respectively, activation 0.5h ~ 2h; Respectively the chloroformic solution being dissolved with condensing agent and dopamine hydrochloride is added in the good solution of above-mentioned activation, magnetic agitation 4 ~ 8h, merge solution, add Fe/Fe
3o
4magnetic nano-particle, reaction 10-20h is by normal hexane precipitation, centrifugal.
Described purification is: purified by pillar layer separation, CH
2cl
2: MeOH=96:4.
The benzyl ester obtained, in dense NaOH Water Under solution, makes the pH value of solution be 1 with concentrated hydrochloric acid acidify.
Described bridging agent is N-hydroxy-succinamide; 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, take 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 prepares 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 detecting tripolycyanamide based on magnetic nano-particle prepared by said method, be a kind of water miscible magnetic nano-particle containing specific receptor unit, size is about 10 ~ 20nm.
The present invention is by specific receptor unit to the identification ability of tripolycyanamide, and carry out the targeting experiment of tripolycyanamide, induction magnetic nano-particle carries out self assembly.In the process, the self assembly of magnetic nano-particle can change the relaxation rate of ambient water proton, and this change can be detected by nuclear magnetic resonance analyser, thus 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 is that 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.
Accompanying drawing explanation
The 1HNMR spectrogram of the specific receptor unit of Fig. 1 prepared by embodiment 1.
The TEM figure of the magnetic nano-particle of Fig. 2 prepared by embodiment 2.
The DLS of the magnetic nano-particle of Fig. 3 prepared by embodiment 2.
The X ray diffracting spectrum of the magnetic nano-particle of Fig. 4 prepared by embodiment 2.
The infrared spectrum of the magnetic nano-particle of Fig. 5 prepared by embodiment 2.
The TEM figure of the magnetic nano-particle containing specific receptor unit of Fig. 6 prepared by embodiment 3.
The infrared spectrum of the magnetic nano-particle containing specific receptor unit of Fig. 7 prepared by embodiment 3.
The Fe/Fe containing specific receptor unit of Fig. 8 prepared by embodiment 3
3o
4the DLS of nanoparticle.
Fig. 9 is the DLS that the magnetic nano-particle containing specific receptor unit in embodiment 5 adds 30 μMs of melamine solution.
Figure 10 be magnetic nano-particle containing 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 μMs.
Figure 11 is the change of the magnetic nano-particle △ T2 value in 30 μMs of uracil, cytosine, thymidine solution 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 the dry DMF that 5.0g cyanuric acid joins 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, keep more than 12h, after reaction terminates, cool to room temperature, distilling under reduced pressure removing DMF, the solid THF washing and filtering obtained, the filtrate obtained concentrates, and filters and drying, the solid column chromatography (SiO obtained with cold water washing
2, CH
2cl
2/ MeOH, 24:1) separating-purifying, obtain the solid benzyl ester of white.
(2) get 477mgNaOH and be dissolved in 15mLH
2in O, mix homogeneously, adds 661mg benzyl ester, stirs at normal temperatures and spends the night, after reaction terminates, use 36wt%HCl acidify, PH=1, distilling under reduced pressure removing H
2o, the material THF obtained filter and extract repeatedly, and concentrated filtrate, obtains white solid specific receptor unit.
Specific receptor unit prepared by the present embodiment
1hNMR spectrogram as shown in Figure 1.
Embodiment 2:
Get 20mL octadecylene with graduated cylinder, get 0.2mL oleyl amine, get 0.1gHDAHCl with analytical balance with pipet, join in there-necked flask, mix homogeneously, magnetic agitation deaeration, the time approximately controls at 1h.Temperature is raised to 120 DEG C, keeps 30min.Be heated to 180 DEG C, use N
2gas shielded, fast injection 0.7mLFe (CO)
5, keep mixing speed maximum.After keeping 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 obtained
3o
4nanoparticle dispersion is in normal hexane.
The TEM figure of the magnetic nano-particle prepared by the present embodiment 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 is 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, and 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, merges the two; Add 15 ~ 25mgFe/Fe
3o
4nanoparticle, incubator overnight.By normal hexane precipitation, with water from first pass, all the other are centrifugal with ethanol.
The TEM figure of the magnetic nano-particle containing specific receptor unit of Fig. 6 prepared by the present embodiment;
The infrared spectrum of the magnetic nano-particle containing specific receptor unit of Fig. 7 prepared by the present embodiment;
The Fe/Fe containing specific receptor unit of Fig. 8 prepared by the present embodiment
3o
4the DLS of nanoparticle.
Embodiment 4:
(1) analytical balance takes and is 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, and 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, merges the two; Add 15 ~ 20mg nanoparticle, incubator overnight.By normal hexane precipitation, with water from first pass, all the other are centrifugal with ethanol.
Embodiment 5:
Adding cyanuric acid containing being modified with in the solution of the nanoparticle of specific receptor unit of 0.032mMFe, making the concentration of cyanuric acid be respectively 0,2,4,6,8,10,12 ... 30 μMs.
Fig. 9 is the DLS that the magnetic nano-particle containing specific receptor unit in the present embodiment adds 30 μMs of melamine solution.
Detect the rate of change of the △ T2 value 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 when the concentration of tripolycyanamide is 30 μMs, the rate of change of △ T2 is about 0.406.The lowest detectable limit of tripolycyanamide is about 2 μMs.
Embodiment 6:
30 μMs of thymus pyrimidines, uracil, cytosine are being added containing being modified with in the solution of the nanoparticle of specific receptor unit of 0.032mMFe, the change of the △ T2 value relatively caused by the material with analog structure, detects this magnetic resonance contrast agent sensor material to the selectivity of 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 content disclosed in this embodiment.The equivalence completed under not departing from principles of this disclosure so every or amendment, all fall into the scope of protection of the invention.
Claims (10)
1. detect the preparation method of the nmr sensor of tripolycyanamide based on magnetic nano-particle, it is characterized in that, comprise 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: 2-benzyl acetate bromide=3:1 ~ 5:1, under the condition of noble gas, in dry DMF solvent, 70 DEG C of isothermal reaction 10-20h, purification obtains benzyl ester, hydrolysis, acidify, extracts with THF and obtains specific receptor unit;
(2) Fe/Fe containing specific receptor unit
3o
4the preparation of magnetic nano-particle: step (1) gained specific receptor unit and Polyethylene Glycol monocarboxylic acid are dissolved in pyridine respectively, add bridging agent respectively, activation 0.5h ~ 2h; Respectively the chloroform being dissolved with condensing agent and dopamine hydrochloride is added in the good solution of above-mentioned activation, magnetic agitation 4 ~ 8h, merge solution, add 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: purified by pillar layer separation, CH
2cl
2: MeOH=96:4.
3. preparation method according to claim 1, is characterized in that, the benzyl ester obtained, in dense NaOH Water Under solution, makes the pH value of solution be 1 with concentrated hydrochloric acid acidify.
4. preparation method according to claim 1, is characterized in that, described bridging agent is N-hydroxy-succinamide; 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 noble gas atmosphere, take 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 prepares 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. detect the nmr sensor of tripolycyanamide based on magnetic nano-particle, it is characterized in that, 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 containing specific receptor unit, and size is 10 ~ 20nm.
10. the application of the sensor described in claim 8 or 9 in tripolycyanamide detects.
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| CN104447592B (en) * | 2014-11-07 | 2016-08-17 | 东南大学 | Cyanuric acid derivative, discotic mesogenic material and tripolycyanamide detection method |
| CN106033066B (en) * | 2015-03-11 | 2018-08-28 | 中国科学院宁波材料技术与工程研究所 | A kind of method that nuclear magnetic resonance quickly detects metal ion and micromolecular compound |
| CN105136834B (en) * | 2015-07-14 | 2017-03-01 | 上海师范大学 | The Fe/Fe that 3,4 dihydroxyphenyl propionic acid are modified3O4Nanoparticle and its preparation method and application |
| CN105741993B (en) * | 2016-02-03 | 2017-11-03 | 上海师范大学 | Nitrine dopamine and the Fe/Fe of carboxy polyethylene glycol modification3O4Nano-particle and preparation and application |
| 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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