阅读说明：本技术 高灵敏的Fe-PANI/Pt@Au多巴胺电化学检测电极及其制备 (Highly sensitive Fe-PANI/Pt@Au dopamine electrochemical detection electrode and its preparation ) 是由 林玲玲 游东宏 庄凰龙 叶陈清 李武连 于 2019-07-29 设计创作，主要内容包括：本发明提供了一种高灵敏的铁掺杂的聚苯胺/Pt@Au双金属纳米复合材料多巴胺电化学检测电极及其制备方法。所述方法包括：S1,将苯胺单体加入二氯甲烷溶液超声分散形成有机相溶液；S2,往有机相溶液中加入N-甲基吡咯烷酮水溶液、氯金酸溶液与氯化铁溶液避光搅拌后静置；S3,将过硫酸铵-盐酸溶加入步骤S2中反应溶液中,静置反应后滤到固体产物；S4,将固体产物清洗、过滤、自然晾干得到Fe-PANI/Au；S5,取Fe-PANI/Au分散纯水中,加入氯铂酸溶液和抗坏血酸溶液；S6,取少量浓盐酸加入S5的反应溶液中搅拌一段时候后过滤、晾干得到Fe-PANI/Pt@Au；S7,将玻碳电极研磨抛光后备用；S8,取Fe-PANI/Pt@Au分散于乙醇中,加入Nafion溶液超声分散形成悬浮液；S9,取悬浮液滴加到步骤S7抛光后的玻碳电极表面。(The present invention provides a kind of highly sensitive polyaniline/Pt@Au bimetal nano composite material dopamine electrochemical detection electrodes of Fe2O3 doping and preparation method thereof.The described method includes: S1, is added dichloromethane solution ultrasonic disperse for aniline monomer and forms organic phase solution；S2 is added after N-Methyl pyrrolidone aqueous solution, chlorauric acid solution and ferric chloride solution are protected from light stirring into organic phase solution and stands；S3, solid product is arrived in filter after reaction in reaction solution, being stood in the molten addition step S2 of ammonium persulfate-hydrochloric acid；Solid product cleaning, filtering, naturally dry are obtained Fe-PANI/Au by S4；S5 takes in Fe-PANI/Au dispersion pure water, platinum acid chloride solution and ascorbic acid solution is added；S6 is filtered after taking a small amount of concentrated hydrochloric acid to be added in the reaction solution of S5 when stirring one section, is dried to obtain Fe-PANI/Pt@Au；S7, will be spare after glass-carbon electrode grinding and polishing；S8 takes Fe-PANI/Pt@Au to be scattered in ethyl alcohol, and Nafion solution ultrasonic disperse is added and forms suspension；S9 takes hanging drop to be added to the glassy carbon electrode surface after step S7 polishing.)

1. a kind of preparation method of highly sensitive Fe-PANI/[email protected] dopamine electrochemical detection electrode, which is characterized in that including Following steps:

S1, ultrasound in 50mL dichloromethane solution, which is added, in 0.5mL aniline monomer its evenly dispersed formed transparent uniform Machine phase solution；

S2, the gold chloride for being successively slowly added to the 24.28mM of 0.103ml into the organic phase solution under agitation are molten Liquid, 50mL 0.2mol/L N-Methyl pyrrolidone aqueous solution and 0.05mL 0.5mol/L ferric chloride solution, at room temperature It is stood after being protected from light stirring a period of time；

0.3g ammonium persulfate is added in the hydrochloric acid solution of the 2mol/L of 8.6mL and forms ammonium persulfate-hydrochloric acid solution by S3, incited somebody to action Ammonium sulfate-hydrochloric acid solution is slowly added in step S2 in reaction solution, uses organic system membrane filtration after standing reaction a period of time Obtain solid product；

Solid product cleaning, filtering, naturally dry are obtained Fe-PANI/Au powder by S4；

S5 takes the Fe-PANI/Au powder of 25~35mg to be scattered in 15-18.2M Ω pure water, sequentially adds under agitation The platinum acid chloride solution of the 8.228mM of 0.9mL and the 100mM ascorbic acid solution of 0.3mL, are protected from light are stirred to react 10- at room temperature 30h；

S6 takes 0.5mL concentrated hydrochloric acid to be added in the reaction solution of S5 and stirs a period of time, then with 0.22 μm of hole after reaction The water system membrane filtration of diameter obtains solid product, and solid product cleaning, filtering, naturally dry are obtained Fe-PANI/[email protected] Au powder；

S7, by the glass-carbon electrode successively use 3 μm, 1 μm, 0.3 μm, after the alumina powder grinding and polishing of 50nm it is spare；

S8 takes the Fe-PANI/[email protected] powder ultrasonic disperse of 1~3mg in 0.5mL dehydrated alcohol, is added 5~15 μ L's Nafion solution ultrasonic disperse forms it into uniform suspension；

S9, the glassy carbon electrode surface for taking the suspension of 10-40 μ L to be added drop-wise to after step S7 polishing with 10-20 μ L/ times, stands to molten Continue that suspension is added dropwise after liquid volatilization, operation finally obtains Fe-PANI/Pt Au modified electrode repeatedly.

2. preparation method as described in claim 1, which is characterized in that in step s 2, mixed solution is protected from light the time and is 10-50h。

3. preparation method as described in claim 1, which is characterized in that in step s3, after ammonium persulfate-hydrochloric acid solution is added The standing reaction time is 15-35min.

4. preparation method as described in claim 1, which is characterized in that in step s 4, the step of solid product is cleaned packet It includes:

The solid product is successively cleaned filtration product with distilled water, hydrochloric acid solution, ethanol washing by S41, hydrochloric acid solution it is dense Degree range is 0.1-2mol/L.

5. preparation method as described in claim 1, which is characterized in that in step s 5, take the Fe-PANI/Au of 25~35mg Powder is scattered in 15-18.2M Ω pure water, sequentially add under agitation the 8.228mM of 0.9mL platinum acid chloride solution and The 100mM ascorbic acid solution of 0.3mL, being protected from light the step of being stirred to react 10-30h at room temperature includes:

S51 takes the Fe-PANI/Au powder of 30mg to be scattered in 18.2M Ω pure water, sequentially adds 0.9mL's under agitation The platinum acid chloride solution of 8.228mM and the 100mM ascorbic acid solution of 0.3mL, are protected from light are stirred to react 20h at room temperature.

6. preparation method as described in claim 1, which is characterized in that in step s 6, after reaction, take the dense salt of 0.5mL Acid, which is added in the reaction solution of S5, is stirred to react the time as 20min-1h.

7. preparation method as described in claim 1, which is characterized in that in step s 6, the step of solid product is cleaned packet It includes:

The solid product is successively cleaned filtration product with distilled water, hydrochloric acid solution, ethanol washing by S61, hydrochloric acid solution it is dense Degree range is 0.1-2mol/L.

8. preparation method as described in claim 1, which is characterized in that in step s 8, the Fe-PANI/ for taking 1~3mg In 0.5mL dehydrated alcohol, the Nafion solution ultrasonic disperse that 5~15 μ L are added forms it into [email protected] powder ultrasonic disperse The step of even suspension includes:

S81 takes the Fe-PANI/[email protected] powder ultrasonic disperse of 2mg in 0.5mL dehydrated alcohol, and the Nafion that 10 μ L are added is molten Liquid ultrasonic disperse forms it into uniform suspension.

9. preparation method as described in claim 1, which is characterized in that in step s 9, the suspension for taking 10-40 μ L with The 10-20 μ L/ times glassy carbon electrode surface being added drop-wise to after step S7 polishing, standing continue that suspension is added dropwise after solution evaporation, instead Operating the step of finally obtaining Fe-PANI/[email protected] modified electrode again includes:

S91 takes the suspension of 20 μ L to be directly added drop-wise to the glassy carbon electrode surface after step S5 polishing, stands and obtain after solution evaporation To Fe-PANI/[email protected] modified electrode.

10. a kind of highly sensitive Fe-PANI/[email protected] dopamine electrochemical detection electrode, which is characterized in that described highly sensitive Fe-PANI/[email protected] dopamine electrochemical detection electrode is to be prepared by the method for any one of claim 1-9；It is tested Environment are as follows: using Fe-PANI modified electrode as working electrode, graphite electrode or platinum electrode be extremely to join to electrode, the sweet common-battery of saturation DPV test is carried out than electrode, wherein potential range -0.1V-0.9V (vs.SCE), scan amplitude 50mV, pulse width 50ms, entire environment of testing carry out in the phosphate buffer of pH=6.6-7.2.

Technical field

The present invention relates to a kind of highly sensitive Fe-PANI/[email protected] dopamine electrochemical detection electrodes and its preparation.

Background technique

Dopamine (DA) is a kind of catecholamines being present in nervous centralis, angiocarpy, kidney and endocrine system Neurotransmitter, and in human body can the behaviors such as thinking, work, movement to people have an impact.Dopamine is in human body just Chang Hanliang is 0.2-0.4g/ml, and the content distribution of specific region influences the coordination of hypophysis endocrine dysfunction in human brain.Work as people It can cause such as schizophrenia, parkinsonism, heart failure, neuromuscular disorders disease when the content of dopamine is too low in body Disease.Otherwise DA content is excessive, people can be allowed to feel excited, happy, be easy addicted.In addition in terms of medicine, dopamine also often by with In diseases such as treatment renal failure, depression and endotoxin septicemia.Therefore, carry out dopamine analyzing detecting method to exist The quality controlling party face of research neuro-physiology and related drugs has great importance, and examines selectively, in high sensitivity The concentration for surveying neurotransmitter dopamine, has important application value to these diseases are diagnosed on a molecular scale.

Since the research that the importance scientists of dopamine detection are always being dedicated to dopamine detection obtains Gao Ling Quick, selective, quick dopamine detection technique method.At present the common detection method of dopamine have fluorescent spectrometry, Colleges and universities' liquid phase method, capillary electrophoresis etc., and electrochemical detection method is due to easy to operate, highly sensitive, selectively good etc. excellent Point becomes the common method of dopamine detection.So in brain and body fluid, the redox peaks of dopamine, ascorbic acid, uric acid Current potential is more close to limit Electrochemical Detection DA technology, can increase the mass transfer rate of DA using modified electrode, improves measurement Sensitivity and anti-interference ability, therefore many scientific research personnel research electrochemical method is improved using modified electrode.

In recent years, metal/conducting polymer that metal and conductive polymer polymer are formed in nanometer range is compound to be received Rice material causes the extensive concern of people because of its special function and effect.Studies have shown that by nanogold such as Au, Pt, Ag, Cu Belong to particle and introduce polyaniline, the electric conductivity and electrochemical response performance of polyaniline can be improved, while also retaining clipped wire The physical and chemical properties of sub- script.Polyaniline/metal composite nano material is in Electrochemical Detection human-body biological sensory field Research has become the big hot spot of current one.Preparation highly sensitive, selective enumeration method polyaniline/metal composite for dopamine Material modified electrode is with good application prospect.

Summary of the invention

The present invention provides a kind of highly sensitive Fe-PANI/[email protected] dopamine electrochemical detection electrodes and its preparation, can Effectively to solve the sensitivity in dopamine detection process and the interference problem of uric acid, ascorbic acid.

The present invention is implemented as follows:

A kind of preparation method of highly sensitive Fe-PANI/[email protected] dopamine electrochemical detection electrode, comprising the following steps:

S1, ultrasound in 50mL dichloromethane solution, which is added, in 0.5mL aniline monomer keeps its evenly dispersed formation transparent uniform Organic phase solution；

S2 is successively slowly added to the gold chloride of the 24.28mM of 0.103ml into the organic phase solution under agitation Solution, 50mL 0.2mol/L N-Methyl pyrrolidone aqueous solution and 0.05mL 0.5mol/L ferric chloride solution, room temperature Under be protected from light stirring a period of time after stand；

0.3g ammonium persulfate is added in the hydrochloric acid solution of the 2mol/L of 8.6mL and forms ammonium persulfate-hydrochloric acid solution by S3, Ammonium persulfate-hydrochloric acid solution is slowly added in step S2 in reaction solution, uses organic system filter membrane after standing reaction a period of time Solid product is obtained by filtration；

Solid product cleaning, filtering, naturally dry are obtained Fe-PANI/Au powder by S4；

S5 takes the Fe-PANI/Au powder of 25~35mg to be scattered in 15-18.2M Ω pure water, under agitation successively The platinum acid chloride solution of the 8.228mM of 0.9mL and the 100mM ascorbic acid solution of 0.3mL is added, is protected from light is stirred to react at room temperature 10-30h；

S6 takes 0.5mL concentrated hydrochloric acid to be added in the reaction solution of S5 and stirs a period of time, then with 0.22 μ after reaction The water system membrane filtration in the aperture m obtains solid product, and solid product cleaning, filtering, naturally dry are obtained Fe-PANI/ [email protected] powder；

S7, by the glass-carbon electrode successively use 3 μm, 1 μm, 0.3 μm, after the alumina powder grinding and polishing of 50nm it is spare；

S8 takes the Fe-PANI/[email protected] powder ultrasonic disperse of 1~3mg in 0.5mL dehydrated alcohol, is added 5~15 μ L's Nafion solution ultrasonic disperse forms it into finely dispersed suspension；

S9, the glassy carbon electrode surface for taking the suspension of 10-40 μ L to be added drop-wise to after step S7 polishing with 10-20 μ L/ times, stands Continue that suspension is added dropwise after solution evaporation, operation finally obtains Fe-PANI/Pt Au modified electrode repeatedly.

The present invention furthermore provides a kind of highly sensitive Fe-PANI/[email protected] dopamine electricity obtained by the above method Chemical detection electrode；It tests environment are as follows: using Fe-PANI/Pt Au modified electrode as working electrode, graphite electrode or platinum electrode To carry out DPV test to electrode, the sweet common-battery of saturation extremely reference electrode, wherein potential range -0.1V-0.9V (vs.SCE) is swept Retouching amplitude is 50mV, pulse width 50ms, and entire environment of testing carries out in the phosphate buffer of pH=6.6-7.2.

The beneficial effects of the present invention are: when Fe-PANI/[email protected] nanocomposite modified electrode is used for the detection of DA, In Under the conditions of UA is existing, the detection of DA will not be interfered；AA electrochemical response on modified electrode is weaker simultaneously, to detection System does not interfere.System is limited to 0.001 μM to DA detection.It is that detection is limited to 0.1 μM to UA.

Detailed description of the invention

It, below will be to use required in embodiment in order to illustrate more clearly of the technical solution of embodiment of the present invention Attached drawing be briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not to be seen as It is the restriction to range, it for those of ordinary skill in the art, without creative efforts, can be with root Other relevant attached drawings are obtained according to these attached drawings.

Fig. 1 is in 0.1M, the phosphate buffer that pH is 6.8, and the AA of UA, 2mM of 1mM, 200 μM of DA are in PANI/[email protected] DPV figure on Au modified electrode.Fig. 2 be in 0.1M, in the phosphate buffer that pH is 6.8, the AA of UA, 1mM of 1mM, 200 μM DPV figure of the DA on Fe-PANI/Pt modified electrode.

It is 0.1M that Fig. 3, which is in concentration, and AA, 200 μM of the DA of UA, 2mM of 1mM are in Fe- in the phosphate buffer that pH is 6.8 DPV figure on PANI/[email protected] modified electrode.

It is 0.1M that Fig. 4, which is in concentration, and pH is in 6.8 phosphate buffer, various concentration DA modifies in Fe-PANI/[email protected] DPV figure on electrode.

Fig. 5 is the linear relationship curve graph of DA concentration and peak current.

It is 0.1M that Fig. 6, which is in concentration, and pH is in 6.8 phosphate buffer, a series of concentration UA repairs in Fe-PANI/[email protected] Adorn the DPV figure on electrode.

Fig. 7 is the linear relationship curve graph of UA concentration and peak current.

Specific embodiment

To keep the purposes, technical schemes and advantages of embodiment of the present invention clearer, implement below in conjunction with the present invention The technical solution in embodiment of the present invention is clearly and completely described in attached drawing in mode, it is clear that described reality The mode of applying is some embodiments of the invention, rather than whole embodiments.Based on the embodiment in the present invention, ability Domain those of ordinary skill every other embodiment obtained without creative efforts, belongs to the present invention The range of protection.Therefore, the detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit below and is wanted The scope of the present invention of protection is sought, but is merely representative of selected embodiment of the invention.Based on the embodiment in the present invention, Every other embodiment obtained by those of ordinary skill in the art without making creative efforts belongs to this Invent the range of protection.

The embodiment of the present invention provides a kind of preparation side of highly sensitive Fe-PANI/[email protected] dopamine electrochemical detection electrode Method, comprising the following steps:

S1, ultrasound in 50mL dichloromethane solution, which is added, in 0.5mL aniline monomer keeps its evenly dispersed formation transparent uniform Organic phase solution；

S2 is successively slowly added to the gold chloride of the 24.28mM of 0.103ml into the organic phase solution under agitation Solution, 50mL 0.2mol/L N-Methyl pyrrolidone aqueous solution and 0.05mL 0.5mol/L ferric chloride solution, room temperature Under be protected from light stirring a period of time after stand；

0.3g ammonium persulfate is added in the hydrochloric acid solution of the 2mol/L of 8.6mL and forms ammonium persulfate-hydrochloric acid solution by S3, Ammonium persulfate-hydrochloric acid solution is slowly added in step S2 in reaction solution, uses organic system filter membrane after standing reaction a period of time Solid product is obtained by filtration；

Solid product cleaning, filtering, naturally dry are obtained Fe-PANI/Au powder by S4；

S5 takes the Fe-PANI/Au powder of 25~35mg to be scattered in 15-18.2M Ω pure water, under agitation successively The platinum acid chloride solution of the 8.228mM of 0.9mL and the 100mM ascorbic acid solution of 0.3mL is added, is protected from light is stirred to react at room temperature 10-30h；

S6 takes 0.5mL concentrated hydrochloric acid to be added in the reaction solution of S5 and stirs a period of time, then with 0.22 μ after reaction The water system membrane filtration in the aperture m obtains solid product, and solid product cleaning, filtering, naturally dry are obtained Fe-PANI/ [email protected] powder；

S7, by the glass-carbon electrode successively use 3 μm, 1 μm, 0.3 μm, after the alumina powder grinding and polishing of 50nm it is spare；

S8 takes the Fe-PANI/[email protected] powder ultrasonic disperse of 1~3mg in 0.5mL dehydrated alcohol, is added 5~15 μ L's Nafion solution ultrasonic disperse forms it into uniform suspension；

S9, the glassy carbon electrode surface for taking the suspension of 10-40 μ L to be added drop-wise to after step S7 polishing with 10-20 μ L/ times, stands Continue that suspension is added dropwise after solution evaporation, operation finally obtains Fe-PANI/Pt Au modified electrode repeatedly.

The test environment of the Fe-PANI/Pt Au modified electrode are as follows: using Fe-PANI/Pt Au modified electrode as work electricity Pole, graphite electrode or platinum electrode are to carry out DPV test to electrode, the sweet common-battery of saturation extremely reference electrode, wherein potential range- 0.1V-0.9V (vs.SCE), scan amplitude 50mV, pulse width 50ms, entire environment of testing is in pH=6.6-7.2 hair phosphoric acid It is carried out in buffer.As further improved, in step s 2, it is 10-50h that mixed solution, which is protected from light the time,.As into One step is improved, in addition, the pH value of environment also has larger impact to test, when pH=6.6-7.2 is more than in entire test When this range, the proton doping level of polyaniline changes, to influence to detect the anti-interference of substance, sensitivity and steady It is qualitative, it is therefore preferred that entirely test environment carries out in the phosphate buffer of pH=6.8-7.2.

As further improved, in step s3, being added after ammonium persulfate-hydrochloric acid solution and standing the reaction time is 15- 35min。

As further improved, in step s 4, the step of solid product is cleaned, includes:

The solid product is successively cleaned filtration product, hydrochloric acid solution with distilled water, hydrochloric acid solution, ethanol washing by S41 Concentration range be 0.1-2mol/L.In step in S41, hydrochloric acid solution clean so that polyaniline keep certain electric conductivity and Dispersibility.The hydrochloric acid cleaning solution of right excessively high solubility will influence the cleaning of product simultaneously so that polyaniline is easily dispersed into homogeneous solution Destroy filtering film layer.Therefore it is furthermore preferred that the concentration range of the hydrochloric acid solution is 0.1-1.2mol/L.

As further improved, in step s 5, the Fe-PANI/Au powder of 25~35mg is taken to be scattered in 15-18.2M In Ω pure water, the platinum acid chloride solution of the 8.228mM of 0.9mL and the 100mM ascorbic acid of 0.3mL are sequentially added under agitation Solution, being protected from light the step of being stirred to react 10-30h at room temperature includes:

S51 takes the Fe-PANI/Au powder of 30mg to be scattered in 18.2M Ω pure water, sequentially adds under agitation The platinum acid chloride solution of the 8.228mM of 0.9mL and the 100mM ascorbic acid solution of 0.3mL, are protected from light are stirred to react 20h at room temperature.

As further improved, in step s 6, after reaction, take 0.5mL concentrated hydrochloric acid that the reaction solution of S5 is added In be stirred to react the time be 20min-1h.

As further improved, in step s 6, the step of solid product is cleaned, includes:

The solid product is successively cleaned filtration product, hydrochloric acid solution with distilled water, hydrochloric acid solution, ethanol washing by S61 Concentration range be 0.1-2mol/L.

As further improved, in step s 8, the Fe-PANI/[email protected] powder ultrasonic disperse for taking 1~3mg in In 0.5mL dehydrated alcohol, Nafion solution ultrasonic disperse the step of forming it into uniform suspension packet of 5~15 μ L is added It includes:

S81 takes the Fe-PANI/[email protected] powder ultrasonic disperse of 2mg in 0.5mL dehydrated alcohol, is added 10 μ L's Nafion solution ultrasonic disperse forms it into uniform suspension.

As further improved, in step s 9, the suspension for taking 10-40 μ L is added drop-wise to step with 10-20 μ L/ times Glassy carbon electrode surface after rapid S7 polishing, standing continue that suspension is added dropwise after solution evaporation, and operation finally obtains Fe- repeatedly The step of PANI/[email protected] modified electrode includes:

S91 takes the suspension of 20 μ L to be directly added drop-wise to the glassy carbon electrode surface after step S5 polishing, stands to solution evaporation After obtain Fe-PANI/[email protected] modified electrode.