CN104090008A - Preparation method of electrochemical sensor based on mesoporous silica modified electrode - Google Patents
Preparation method of electrochemical sensor based on mesoporous silica modified electrode Download PDFInfo
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- CN104090008A CN104090008A CN201410367527.8A CN201410367527A CN104090008A CN 104090008 A CN104090008 A CN 104090008A CN 201410367527 A CN201410367527 A CN 201410367527A CN 104090008 A CN104090008 A CN 104090008A
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Abstract
The invention relates to a novel electrochemical sensor which comprises a magnetic electrode and is suitable for simultaneously detecting amiodarone (AM) and atenolol (AT). According to the novel electrochemical sensor, functionalized ammonia propyl is fixed to the surface of MCM-41 silica through reflux reaction between MCM-41 and 3-ammonia propyl triethoxysilane in methylbenzene; mesoporous silica is integrated with magnetic nanoparticles to form a porous magnetic nanocomposite electrode-MCM-41-nPrNH2; MCM-41-nPrNH2 loaded with Fe2O3 can enhance anode current by absorbing amiodarone and atenolol on the surface of the electrode; the MCM-41-nPrNH2 is good in selective voltammetric response to display of AM and AT. The electrochemical sensor is capable of simultaneously detecting the AM and the AT in drugs, has the characteristics of quickness, sensitivity, low cost, high selectivity and the like and has wide application prospects in the treatment field of cardiovascular diseases.
Description
Technical field
The present invention relates to a kind of preparation method of electrochemical sensor, relate in particular to a kind of preparation method of the electrochemical sensor based on the functional mesoporous silica modified electrode of magnetic nanoparticle doping simultaneously detecting for amiodarone and atenolol.
Background technology
In recent years, mesopore molecular sieve has caused a lot of concerns in electrochemical sensing field, mainly because it has good performance, as large surface area, large pore volume and narrow pore diameter distribution, and mesopore molecular sieve or a kind of efficiently, stablize, can be recycled and Eco-friendly material.Mobile crystalline material-41 (MCM-41) is a kind of mesoporous material with the unidirectional pore structure of one dimension six side, and this material is conventionally synthetic as structure directing agent with cationic surfactant under alkali condition.Silica MCM-41 mesopore molecular sieve surface is almost electric neutrality and acid site is few, has seriously limited its application.
In biofluid and drug sample, the detection of medicine is all very important to fields such as clinical chemistry, toxicology and pharmacy researchs, in the result for the treatment of of biofluid Chinese traditional medicine and its concentration, also has and contacts very closely; Therefore, can enough simple and quick methods detect multiple cardiovascular drugs, it is very important that the concentration of Cardiovarscular medicine used is carried out to immediately monitoring simultaneously.But in prior art, when using galvanochemistry sensing equipment relevant with other to cardiovascular drugs, the research of context of detection is also considerably less.
Electrochemical techniques have been used to the detection of multi-medicament compound, and conventionally do not have derivatization reaction, it is contemplated that and build a kind of electrochemical sensor, for these medicines of sensitiveer detection.But the report up to the present, also with electrochemical sensor, amiodarone (AM) and atenolol (AT) not being detected simultaneously.
Summary of the invention
The present invention relates to a kind of novel electrochemical sensor with magnetic pole simultaneously detecting for amiodarone (AM) and atenolol (AT).In order to overcome MCM-41 mesopore molecular sieve surface, be almost electroneutral feature, the present invention reacts in reflux in toluene with 3-aminopropyl triethoxysilane by MCM-41, the aminopropyl of functionalization is fixed to the surface of MCM-41 monox, form a kind of poroid magnetic nanometer composite material, combine the advantage of mesopore silicon oxide and magnetic nanoparticle., by magnetic field, measured object is separated easily from sample meanwhile, and do not needed to use extra organic solvent or the extra complicated programs such as filtration.
The preparation method who the present invention relates to a kind of electrochemical sensor simultaneously detecting for amiodarone and atenolol based on the functional mesoporous silica modified electrode of magnetic nanoparticle doping, its step is as follows:
(1) preparation of the colloidal suspensions of iron oxide magnetic nano particle: FeCl
36H
2o and FeCl
24H
2o is at N
2under atmosphere, be dissolved in distilled water, wherein, FeCl
36H
2o, FeCl
24H
2mass volume ratio (the w/w/v of O, distilled water, g/g/mL) be 100:50:1000～100:50:2000, the solution obtaining dropwise joins in the hydroxylamine solution that contains cetyl trimethyl ammonium bromide, forms a kind of colloidal suspensions of iron oxide magnetic nano particle.Cetyl trimethyl ammonium bromide and FeCl
36H
2the mass ratio (w/w, g/g) of O is 1:2～2:1, and the volume ratio (v/v, mL/mL) of hydroxylamine solution and distilled water is 1:2～2:1, and the concentration range of hydroxylamine solution is 1.5～5.5mol/L.
(2) Fe
2o
3-MCM-41-nPrNH
2synthetic: magnetic MCM-41 (Fe
2o
3-MCM-41) by iron oxide magnetic nano particle colloidal suspensions prepared by step (1), join magnetic force in the hydroxylamine solution that contains cetyl trimethyl ammonium bromide and mix rear ultrasonic agitation 1～3h, add after sodium silicate 35～60 ℃ to stir 12～20h, solid is leached, with the ammonium nitrate washing that contains ethanol 3～8 times; Synthetic material is removed to surfactant at 370～400 ℃ of calcining 6～8h, at this moment Fe
3o
4-MCM-41 just changes Fe into
2o
3-MCM-41, by Fe
2o
3-MCM-41 reacts and prepares Fe in reflux in toluene with 3-aminopropyl triethoxysilane
2o
3-MCM-41-nPrNH
2;
Wherein, volume ratio (the v/v/v of iron oxide magnetic nano particle colloidal suspensions, hydroxylamine solution and sodium silicate, mL/mL/mL) be: 10:100:1～10:250:5, mass volume ratio (the w/v of cetyl trimethyl ammonium bromide and hydroxylamine solution, g/mL) be 1:300～1:500, the concentration range of hydroxylamine solution is 1.5～5.5mol/L.
(3) Fe
2o
3-MCM-41-nPrNH
2the preparation of modified electrode: by carbon dust and Fe
2o
3-MCM-41-nPrNH
2with the ratio of mass ratio 85:15～95:5, mix, then to add mass percent be 15～25% mineral oil, hand mix is pastel, in mortar, grind 25～40min after drying at room temperature preserve; By pastel solid insert a cavity (diameter 2.5～3.5mm of polyfluortetraethylene pipe end, the degree of depth is 0.8～1.2mm) in, with a copper cash as connection, by electrode surface on pan paper gently friction carry out smooth treatment (this method is also used for to the electrode processing of regenerating), obtain Fe
2o
3-MCM-41-nPrNH
2modified electrode.
The inventive method relates to a kind of based on Fe
2o
3-MCM-41-nPrNH
2the preparation method of the electrochemical sensor of modified electrode, and detect for amiodarone and atenolol medicine time a kind of sensitive, cheap, detection method fast with high selectivity is provided.The electrochemical sensor modified electrode the present invention relates to also has the advantages such as repeatability, the wide range of linearity, low detectability, anti-surface contamination.Due to MCM-41-nPrNH
2and Fe
2o
3between there is very strong adhesion, and MCM-41-nPrNH
2solubleness in water is very low, and therefore, related electrochemical sensor of the present invention is highly stable.Load has Fe
2o
3mCM-41-nPrNH
2can strengthen anode current by electrode surface absorption amiodarone and atenolol, amiodarone and atenolol have been shown to good selectivity volt-ampere response, in medicine the two time the well-adapted method that provides is provided.
Embodiment
In order to deepen the understanding of the present invention, below in conjunction with implementing, the invention will be further described.
The preparation method of the electrochemical sensor simultaneously detecting for amiodarone and atenolol based on the functional mesoporous silica modified electrode of magnetic nanoparticle doping, its step is as follows:
(1) preparation of the colloidal suspensions of iron oxide magnetic nano particle: 3.0gFeCl
36H
2o and 1.5gFeCl
24H
2o is at N
2under atmosphere, be dissolved in 50mL distilled water, the solution obtaining dropwise joins in the hydroxylamine solution of the 50mL2.0mol/L that contains 1.5g cetyl trimethyl ammonium bromide, forms a kind of colloidal suspensions of iron oxide magnetic nano particle.
(2) Fe
2o
3-MCM-41-nPrNH
2synthetic: iron oxide magnetic nano particle colloidal suspensions prepared by 30mL step (1) joins in the hydroxylamine solution of the 500mL2.0mol/L that contains 1.5g cetyl trimethyl ammonium bromide, after magnetic force mixes, ultrasonic agitation is 1 hour, add after the sodium silicate of 10mL 40 ℃ to stir 18h, solid is leached, with the ammonium nitrate washing that contains ethanol 3 times; At 400 ℃ of calcining 6h, remove surfactant, at this moment Fe
3o
4-MCM-41 just changes Fe into
2o
3-MCM-41, by Fe
2o
3-MCM-41 reacts and prepares Fe in reflux in toluene with 3-aminopropyl triethoxysilane
2o
3-MCM-41-nPrNH
2.
(3) Fe
2o
3-MCM-41-nPrNH
2the preparation of modified electrode: by carbon dust and Fe
2o
3-MCM-41-nPrNH
2after mixing with the ratio of mass ratio 90:10, adding mass percent is 20% mineral oil, and hand mix is pastel, in mortar, grind 30min after drying at room temperature preserve; By pastel solid insert in a cavity (diameter 3mm, the degree of depth is 0.8mm) of polyfluortetraethylene pipe end, with a copper cash as connection, by electrode surface on pan paper gently friction carry out smooth treatment, obtain Fe
2o
3-MCM-41-nPrNH
2modified electrode.
Claims (6)
1. a preparation method for the electrochemical sensor simultaneously detecting for amiodarone and atenolol based on mesopore silicon oxide modified electrode, its step is as follows:
(1) preparation of the colloidal suspensions of iron oxide magnetic nano particle: FeCl
36H
2o and FeCl
24H
2o is at N
2under atmosphere, be dissolved in distilled water, the solution obtaining dropwise joins in the hydroxylamine solution that contains cetyl trimethyl ammonium bromide, forms a kind of colloidal suspensions of iron oxide magnetic nano particle; Wherein, described FeCl
36H
2o, FeCl
24H
2the mass volume ratio (w/w/v, g/g/mL) of O and distilled water is 100:50:1000～100:50:2000, described cetyl trimethyl ammonium bromide and FeCl
36H
2the mass ratio (w/w, g/g) of O is 1:2～2:1, and the volume ratio (v/v, mL/mL) of described hydroxylamine solution and distilled water is 1:2～2:1, and the concentration range of described hydroxylamine solution is 1.5～5.5mol/L;
(2) Fe
2o
3-MCM-41-nPrNH
2synthetic: magnetic MCM-41 (Fe
2o
3-MCM-41) by iron oxide magnetic nano particle colloidal suspensions prepared by step (1), join magnetic force in the hydroxylamine solution that contains cetyl trimethyl ammonium bromide and mix rear ultrasonic agitation 1～3h, add after sodium silicate 35～60 ℃ to stir 12～20h, solid is leached, with the ammonium nitrate washing that contains ethanol 3～8 times; Synthetic material is removed to surfactant at 370～400 ℃ of calcining 6～8h, at this moment Fe
3o
4-MCM-41 just changes Fe into
2o
3-MCM-41, by Fe
2o
3-MCM-41 reacts and prepares Fe in reflux in toluene with 3-aminopropyl triethoxysilane
2o
3-MCM-41-nPrNH
2;
Wherein, volume ratio (the v/v/v of described iron oxide magnetic nano particle colloidal suspensions, hydroxylamine solution and sodium silicate, mL/mL/mL) be 10:100:1～10:250:5, mass volume ratio (the w/v of described cetyl trimethyl ammonium bromide and hydroxylamine solution, g/mL) be 1:300～1:500, the concentration range of described hydroxylamine solution is 1.5～5.5mol/L;
(3) Fe
2o
3-MCM-41-nPrNH
2the preparation of modified electrode: by carbon dust and Fe
2o
3-MCM-41-nPrNH
2with the ratio of mass ratio 85:15～95:5, mix, then to add mass ratio be 15～25% mineral oil, hand mix is pastel, in mortar, grind 25～40min after drying at room temperature preserve; By pastel solid insert in cavity polyfluortetraethylene pipe end, diameter 2.5～3.5mm degree of depth 0.8～1.2mm, with a copper cash as connection, by electrode surface on pan paper gently friction carry out smooth treatment, obtain Fe
2o
3-MCM-41-nPrNH
2modified electrode.
2. the preparation method of electrochemical sensor according to claim 1, is characterized in that: the described FeCl of step (1)
36H
2o, FeCl
24H
2the mass volume ratio (w/w/v, g/g/mL) of O and distilled water is 30:15:500, described cetyl trimethyl ammonium bromide and FeCl
36H
2the mass ratio (w/w, g/g) of O is 1:2, and the volume ratio (v/v, mL/mL) of described hydroxylamine solution and distilled water is 1:1, and the concentration of described hydroxylamine solution is 2.0mol/L.
3. the preparation method of electrochemical sensor according to claim 1, it is characterized in that: the volume ratio (v/v/v of the described iron oxide magnetic nano particle of step (2) colloidal suspensions, hydroxylamine solution and sodium silicate, mL/mL/mL) be 30:500:10, mass volume ratio (the w/v of described cetyl trimethyl ammonium bromide and hydroxylamine solution, g/mL) be 3:1000, the concentration of described hydroxylamine solution is 2.0mol/L.
4. the preparation method of electrochemical sensor according to claim 1, is characterized in that: the described carbon dust of step (3) and Fe
2o
3-MCM-41-nPrNH
2the mixing quality of potpourri is than being 90:10, and the mass percent of described mineral oil and said mixture is 20%.
5. the preparation method of electrochemical sensor according to claim 1, is characterized in that: the described milling time of step (3) is 30min.
6. the preparation method of electrochemical sensor according to claim 1, is characterized in that: the described polyfluortetraethylene pipe end cavity diameter of step (3) is 3mm, and the degree of depth is 0.8mm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105806910A (en) * | 2016-03-18 | 2016-07-27 | 中国科学院成都生物研究所 | Biosensor achieving AChE oriented immobilization and preparation method and application of biosensor |
| CN106610396A (en) * | 2015-10-27 | 2017-05-03 | 济南大学 | Preparation method and use of MCM-41 mesoporous molecular sieve-modified carbon paste electrode |
-
2014
- 2014-07-29 CN CN201410367527.8A patent/CN104090008A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| MOHAMMAD HASANZADEH, ET AL.: "Magnetic nanoparticles incorporated on functionalized mesoporous silica: an advanced electrochemical sensor for simultaneous determination of amiodarone and atenolol", 《RSC ADV. 》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106610396A (en) * | 2015-10-27 | 2017-05-03 | 济南大学 | Preparation method and use of MCM-41 mesoporous molecular sieve-modified carbon paste electrode |
| CN105806910A (en) * | 2016-03-18 | 2016-07-27 | 中国科学院成都生物研究所 | Biosensor achieving AChE oriented immobilization and preparation method and application of biosensor |
| CN105806910B (en) * | 2016-03-18 | 2018-11-13 | 中国科学院成都生物研究所 | A kind of biosensor and its preparation method and application of AChE enzymes directional at-tachment |
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Application publication date: 20141008 |