CN104142355A - Nuclear magnetic resonance sensor for detecting Cd<2+> ions based on magnetic nanoparticles and preparation method of sensor - Google Patents
Nuclear magnetic resonance sensor for detecting Cd<2+> ions based on magnetic nanoparticles and preparation method of sensor Download PDFInfo
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- CN104142355A CN104142355A CN201410193198.XA CN201410193198A CN104142355A CN 104142355 A CN104142355 A CN 104142355A CN 201410193198 A CN201410193198 A CN 201410193198A CN 104142355 A CN104142355 A CN 104142355A
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Abstract
The invention discloses a nuclear magnetic resonance sensor for detecting Cd<+2> ions and a preparation method of the sensor. The sensor is a magnetic nanoparticle which contains a receptor unit with specific identification effect on Cd<2+> ions, wherein the sensor has water solubility, superparamagnetism and uniformly distributed particle diameter which is about 10-20nm. The preparation method of the sensor comprises the following steps: pyrolyzing at high temperature to prepare the magnetic nanoparticle; preparing the receptor unit by using 2-chloro-3',4'-dihydroxyacetophenone, sodium azide and ethyl propiolate, connecting the receptor unit with the nanoparticle through oxygen coordination to acquire a target nanoparticle which can be used for preparing the nuclear magnetic resonance sensor for the Cd<2+> ions. The preparation method is simple and safe, raw materials are economical and easily available and the process controllability is high; a novel prospect, namely a nano magnetic resonance sensor, is provided for the application of a nano magnetic resonance contrast agent material; and the research field of the nano materials is enriched.
Description
Technical field
The present invention relates to nuclear magnetic resonance sensory field, be specially a kind of based on magnetic nano-particle detection Cd
2+nmr sensor and preparation method thereof.
Background technology
Sensor (English name: transducer/sensor) be a kind of pick-up unit, can receive signal, and energy signal transmission, be for conversion into according to certain rules the information output of electric signal or other desired forms, to meet the requirements such as transmission, processing, storage, demonstration, record and control of information.It is to realize the primary link that automatically detects and automatically control.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. biology sensor, conventionally applies certain bio-sensing primitive and detects chemical substance.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.
Nuclear magnetic resonance is to utilize nuclear spin to produce magnetic moment, and sample is put into additional intensity magnetic field, and reset under externally-applied magnetic field in the magnetic field of nuclear spin itself, and most of nuclear spin meetings are in low-energy state.I apply in addition electromagnetic field and interfere the nuclear spin of low-energy state to turn to high-energy state, return equilibrium state and just can discharge radio frequency, Here it is NMR signal.Utilize such process, we can carry out the research of molecular science, as molecular structure, dynamic etc.MR is a kind of biological magnetic spin imaging technique, and it is the feature of utilizing nuclear spin campaign, in externally-applied magnetic field, produces signal after radio-frequency pulse excites, and with detector, detects and input computing machine, through processing conversion, shows image on screen.The quantity of information that MR provides is not only greater than other the many Imagings in Medical Imaging, and is different from existing Imaging, and therefore, it has very large potential superiority to the diagnosis of disease.It can directly make the body tomographic image on transversal section, sagittal plane, coronal-plane and various inclined-planes, can not produce the artifact in CT detection; Do not need injection of contrast medium; Without ionising radiation, body is not had to harmful effect.The contrast preparation with magnetic core reaches raising signal difference by changing part or whole T1, T2 relaxation time, thereby realize radiography, strengthens function.These contrast preparation are modified by modifying targeting factor, or specific recognition unit, nmr sensor (MR Sensor) produced.
Each each side of widespread use of nmr sensor at present and life, such as: heavy metal particles detects (Hg
2+, Zn
2+), viral detection, protein, little molecule, bacterium etc.Nmr sensor mainly rely on surface-functionalized contrast preparation 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.Simultaneously nmr sensor is as a kind of new, convenient, simple detection method, its detection principle under different mode, how more widely application also needs further to explore and research.
The burning that cadmium derives from fossil fuel comprises coal and oil, and the burning disposal of municipal refuse; Cadmium also may derive from the smelting factory of zinc, lead or copper.For non-smoker, food is the largest source of cadmium, and these foods are mainly derived from the soil that uses perphosphate fertilizer and crossed by contaminated wastewater.And be non-smoker's twice for the content of cadmium in their body of smoker.The acute effects of cadmium (short-term) enters the lungs such as major effect lung cancer, bronchiolitis and pulmonary emphysema to stimulate by exposed suction.Chronic (long-term) suction or oral cavity contact cadmium, make cadmium in the accumulation of kidney and cause kidney trouble, and affecting liver, lung, bone, immune system, blood and nervous system simultaneously.In animal, cadmium is proved to be a kind of poisonous substance that affects growth, can cause fetal anomaly, disturb metabolism and the neurodevelopment of fetus impaired, although also there is no at present conclusive evidence in the mankind.Zooscopy shows, is exposed in the environment containing cadmium, and the occurrence probability of lung cancer can increase greatly.
Magnetic Nano material based on good biocompatibility, modified specificity identification be subject to body unit, ligand interaction, impels the change of magnetic Nano material generation state, the change of recording spin spinrelaxation realizes its efficient detection.In view of the harm of cadmium ion, develop a kind of detection method of rapid sensitive, both expanded the range of application of magnetic Nano material, there is again certain social effect.
Summary of the invention
The object of the present invention is to provide a kind of based on magnetic nano-particle detection Cd
2+nmr sensor and preparation method thereof, to being applied to Cd
2+the detection of ion.
Technical scheme of the present invention is:
Based on magnetic nano-particle inspection Cd
2+the preparation method of the nmr sensor of ion, is characterized in that, comprises the following steps:
(1) preparation of specific receptor unit: chloracetyl catechol and the substituted acetyl catechol of Sodium azide reaction preparation; Substituted chloracetyl catechol is reacted and is spent the night in water with ethyl propiolate, through column chromatography separating-purifying, obtains specific receptor recognition unit;
(2) preparation of the magnetic nano-particle that contains specific receptor unit: (1) gained material and magnetic nano-particle are dissolved in to organic solvent, and homogeneous reaction is spent the night.
In step (2), magnetic nano-particle is known manganese, the Fe of zinc doping
3o
4nano particle.Described organic solvent is pyridine.
Prepared by said method examines Cd based on magnetic nano-particle
2+the nmr sensor of ion, it is a kind of magnetic nano-particle that contains specific receptor unit, has water-solublely, particle size is about 10～20nm.
By specific receptor unit to Cd
2+the recognition capability of ion, carries out Cd
2+the target experiment of ion, 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 Cd
2+the detection of ion.
Preparation method of the present invention is simple and safe, and starting material economy, is easy to get, and process controllability is strong.
The application that the present invention is 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
Fig. 1 is the mass spectrogram of the specific receptor unit of embodiment 1.
Fig. 2 is the infrared spectrum of the magnetic nano-particle that contains specific receptor unit of embodiment 1.
Fig. 3 is the DLS of the nano particle that contains specific receptor unit of embodiment 1.
Fig. 4 is that the magnetic nano-particle that contains specific receptor unit in embodiment 2 is adding 300nMCd
2+dLS.
Fig. 5 is the magnetic nano-particle that contains specific receptor unit in embodiment 20,10,20,30,40,50,60 ... the Cd of 300nM
2+the rate of change of Δ T2 value in the solution of ion.
Fig. 6 is the variation of magnetic nano-particle Δ T2 value in 300nM different metal particle solution of containing specific receptor unit in embodiment 3.
Embodiment
Below in conjunction with example, the present invention will be further described
Embodiment 1:
(1) specific receptor unit is synthetic:
With analytical balance, take the chloracetyl catechol of 1.0g, the Sodium azide of 250mg, in there-necked flask, adds the DMSO of 15mL.At room temperature react 2h, add the frozen water of 50mL, use extracted with diethyl ether three times.Organic phase washes and uses Na with water
2cO
3dry.Organic phase obtains powdered samples through decompression distillation; With analytical balance, take the synthetic sample dissolution of 380mg at 15mLH
2in the mixed liquor of O and the tert-butyl alcohol, mix, add the ethyl propiolate of 100 μ L, stir and spend the night at normal temperatures, after reaction finishes, thickening filtration, obtains black solid.
(2) the detection Cd based on magnetic nano-particle
2+the preparation of nmr sensor:
Analytical balance takes 40～80mg and is subject to body unit, is dissolved in 5mL pyridine, mixes, and adds 10～25mg nano particle, and shaking table spends the night, centrifugal, is distributed in water.
Embodiment 2:
In the solution of the nano particle that is modified with specific receptor unit that contains 6.07mM Fe, add Cd
2+ion, makes Cd
2+the concentration of ion is respectively 0,10,20,30,40,50,60 ... 300nM, detects by different Cd
2+the rate of change of the △ T2 value that the concentration of ion causes; Result as shown in Figure 5.Along with the increase of melamine concentration, △ T2 value becomes greatly gradually, works as Cd
2+when the concentration of ion is 300nM, the rate of change of △ T2 is about 1.Cd
2+the lowest detectable limit of ion is about 3.8nM.
Embodiment 3:
In the solution of the nano particle that is modified with specific receptor unit that contains 6.07mM Fe, add the metallic ion that 300nM is different, relatively, by the variation of the caused △ T2 of the material with analog structure value, detect this magnetic resonance contrast agent sensor material to Cd
2+the selectivity of ion.Result is as Fig. 6.
Claims (4)
1. based on magnetic nano-particle inspection Cd
2+the preparation method of the nmr sensor of ion, is characterized in that, comprises the following steps:
(1) preparation of specific receptor unit: chloracetyl catechol and the substituted acetyl catechol of Sodium azide reaction preparation; Substituted chloracetyl catechol is reacted and is spent the night in water with ethyl propiolate, through column chromatography separating-purifying, obtains specific receptor recognition unit;
(2) preparation of the magnetic nano-particle that contains specific receptor unit: (1) gained material and magnetic nano-particle are dissolved in to organic solvent, ligand exchange reaction occurs.
2. according to claim 1 based on magnetic nano-particle inspection Cd
2+the preparation method of the nmr sensor of ion, is characterized in that, in step (2), magnetic nano-particle is the Fe of manganese, zinc doping
3o
4nano particle, described organic solvent is pyridine.
3. one kind based on magnetic nano-particle Cd
2+the nmr sensor of ion, is characterized in that, according to method preparation described in claim 1-2 any one.
4. according to claim 4 based on magnetic nano-particle inspection Cd
2+the nmr sensor of ion, is characterized in that, it is a kind of magnetic nano-particle that contains specific receptor unit, has water-solublely, and particle size is about 10～20nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104535601A (en) * | 2014-12-19 | 2015-04-22 | 上海师范大学 | Dual-mode sensor for detecting Cd<2+> based on magnetic nanoparticles and preparation method of dual-mode sensor |
| 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 |
| 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 |
| CN107991336A (en) * | 2017-11-28 | 2018-05-04 | 南京林业大学 | It is a kind of based on the quick of magnetic sensing while to detect, separate Pb in water2+And Cu2+Method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104535601A (en) * | 2014-12-19 | 2015-04-22 | 上海师范大学 | Dual-mode sensor for detecting Cd<2+> based on magnetic nanoparticles and preparation method of dual-mode sensor |
| CN104535601B (en) * | 2014-12-19 | 2017-01-11 | 上海师范大学 | Dual-mode sensor for detecting Cd2+ based on magnetic nanoparticles and preparation method of dual-mode sensor |
| 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 |
| CN107991336A (en) * | 2017-11-28 | 2018-05-04 | 南京林业大学 | It is a kind of based on the quick of magnetic sensing while to detect, separate Pb in water2+And Cu2+Method |
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| CN104142355B (en) | 2016-07-06 |
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