CN101408524A - Solution for eliminating nano electrochemical sensor passivation and method for eliminating passivation thereof - Google Patents

Solution for eliminating nano electrochemical sensor passivation and method for eliminating passivation thereof Download PDF

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Publication number
CN101408524A
CN101408524A CNA2008100489065A CN200810048906A CN101408524A CN 101408524 A CN101408524 A CN 101408524A CN A2008100489065 A CNA2008100489065 A CN A2008100489065A CN 200810048906 A CN200810048906 A CN 200810048906A CN 101408524 A CN101408524 A CN 101408524A
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electrochemical sensor
passivation
nano
eliminating
solution
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CNA2008100489065A
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胡胜水
胡成国
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Wuhan University WHU
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Wuhan University WHU
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Abstract

The invention discloses a solution used for eliminating the passivation of a nanometer electrochemical sensor and a method for eliminating the passivation thereof. The original-position surface finishing, the dynamic protection and the passivation prevention of nanometer materials can be realized on the basis of the reversible absorption of water-solubility functional surface active substance on the surfaces of nanometer sensitive materials. Compared with the existing nanometer electrochemical sensor which realizes the passivation prevention on the basis of the covering protection from various expensive polymer materials, the invention uses a surfactant agent which is low in price and forms a dynamic unimolecule protection layer on the interface original position of a sensor sensitive layer of the solution, thereby the solution has the characteristics of simple use, low cost and easy property regulation and control of the protection layer, thus being beneficial for the dispersion of bulk substrates, such as biomacromolecule, and the like; in addition, the passivation prevention of various nanometer electrochemical sensors can be effectively realized, and the wide application prospect can be brought.

Description

Eliminate the solution of nano electrochemical sensor passivation and eliminate the method for passivation with it
Technical field
The present invention relates to a kind of solution of eliminating nano electrochemical sensor passivation and with its method of eliminating passivation, be applicable to that elimination is the passivation of the electrochemical sensor that makes up of sensitive material with the nano material.
Background technology
Form the nano particle of nano material,, can cause increasing sharply of surface atom number and surface area when its diameter is reduced to nanoscale.Simultaneously, because it is more to be in the atomicity on surface, the crystal field environment of surface atom is different with inner atom with binding energy, cause lacking adjacent atom around the surface atom, many dangling bonds are arranged, have unsaturated character, easily combine and settle out, cause surface atom to have very big chemical activity with other atom.Therefore, be that the electrochemical sensor that sensitive material makes up has the sensitivity more much higher than conventional material with the nano material.Yet just because of the high chemical activity and the strong adsorptive power of nano material upper surface atom, it is easy to combine and be passivated with other inert atom in actual use, thereby has reduced the analytical performance of electrochemical sensor.In order to overcome this problem; the sensitive membrane of electrochemical sensor of being everlasting covers one deck polymeric membrane outward again; to get rid of irreversible adsorption and the passivation of possible chaff interference on the nano material sensitive layer; this method can overcome the problem of passivation of some electrochemical sensors to a certain extent; but often cost is higher for used polymer protection material, and the type of macromolecular material is also limited.In addition, polymer protective film is immobilized at sensor surface, and its structure is difficult to control as required, and prepared sensor also be difficult to be realized regeneration, and insensitive etc. to the biomacromolecule response, these have all limited its practical application under given conditions.
Summary of the invention
The purpose of this invention is to provide a kind of solution that can effectively overcome nano electrochemical sensor passivation and eliminate the method for passivation with it; for the immobilized type covered with protective film of the macromolecule of routine; that this method is implemented is simple, with low cost, range of application is wider, have better anti-passivation effect, the easier regulation and control of protective seam, can strengthen the sensitivity, selectivity of sensor etc. as required.
Realize that the technical scheme that the object of the invention provides is: the solution of eliminating nano electrochemical sensor passivation is the supporting electrolyte solution that comprises kation, negative ion or the neutral surface active agent of water-soluble strand and two strands.Used water-soluble strand and double-stranded kation, negative ion or neutral surface active agent are DTAB, Tetradecyl Trimethyl Ammonium Bromide, myristyl pyridinium bromide, cetyl trimethyl ammonium bromide, cetyl pyridinium bromide, octadecyl trimethylammonium bromide, lauryl sodium sulfate, sodium dodecylsulphonate, sodium dodecyl benzenylsulfonate or Triton X-100.
The method of eliminating the nano electrochemical sensor passivation effect is to eliminate nano electrochemical sensor passivation with the supporting electrolyte solution that comprises water-soluble strand and double-stranded kation, negative ion and neutral surface active agent.Water-soluble strand and double-stranded kation, negative ion and neutral surface active agent are joined in the supporting electrolyte solution; surface reactive material forms dynamic protective layer in the reversibility absorption original position of modifying on the nano sensitive material on electrochemical sensor electrodes surface, realizes eliminating nano electrochemical sensor passivation.Used water-soluble strand and double-stranded kation, negative ion or neutral surface active agent are DTAB, Tetradecyl Trimethyl Ammonium Bromide, myristyl pyridinium bromide, cetyl trimethyl ammonium bromide, cetyl pyridinium bromide, octadecyl trimethylammonium bromide, lauryl sodium sulfate, sodium dodecylsulphonate, sodium dodecyl benzenylsulfonate or Triton X-100.
The nano sensitive material of described nano electrochemical sensor is a carbon nanomaterial, and carbon nanomaterial is Single Walled Carbon Nanotube, multi-walled carbon nano-tubes or carbon nano-fiber.
Directly join above-mentioned water-soluble strand and kation, negative ion or the neutral surface active agent's of two strands functionalized surface active substance in the supporting electrolyte solution; form dynamic protective layer by reversibility absorption original position, utilize surface reactive material to adsorb the dynamic monomolecular adsorption layer that forms and realize anti-passivation in the reversibility on nanometer sensitive membrane surface on the nano sensitive material surface.Form the dynamic protection film based on the reversibility absorption original position of functionalized surface active substance on the nanometer sensitive membrane of electrochemical sensor; when strengthening the substrate enrichment, avoid substrate or chaff interference to contact, thereby eliminate the passivation effect of electrochemical sensor with the direct of sensitive layer.The present invention can overcome analysis substrate or irreversible adsorption and the deposition of chaff interference on high-ratio surface, high-activity nano sensitive material that the electrochemical sensor that makes up based on nano sensitive material is run into fully in electrochemical measurement, thoroughly solve the common problem of passivation of nano electrochemical sensor, reach the purpose that improves sensor performance and prolong sensor life-time.
The present invention has following advantage:
1. employed protective agent is the surfactant of commercialization large-scale production, and use cost is cheap, and available product type is abundant.
2. the present invention is based on the protection that mode that original position absorption forms the dynamic protection film realizes the nanometer sensitive membrane, and its protective layer structure and character can be regulated and control as required, and the protective seam renewal speed is fast, and anti-passivation ability is strong.
3. for the immobilized macromolecular material diaphragm of costliness, dynamic protection film density provided by the present invention is moderate, is fit to have diffusion and the Electrochemical Detection of larger volume biomacromolecule.
4. the present invention is simple to operate, has stronger expansibility and application prospects.
Description of drawings
Fig. 1 is to 4.0 * 10 with the various surfactants of concentration -6The sensitization figure that the mol/L estradiol responds on the carbon nano-tube electrochemical sensor.
Fig. 2 does not add Surfactant CTAB, the continuous electrochemical response diagram of estradiol on the carbon nano-tube electrochemical sensor.
Fig. 3 is after adding Surfactant CTAB, the continuous electrochemical response diagram of estradiol on the carbon nano-tube electrochemical sensor.
Curve 1~7 is respectively DTAB (LTAB), octadecyl trimethylammonium bromide (STAB), is cetyl trimethyl ammonium bromide (CTAB), myristyl pyridinium bromide (TPB), anionic (SDS), neutral surface active agent Qu Latong (Triton X-100) and the sensitization curve that does not add surfactant among the figure.
Embodiment
The present invention is described further below in conjunction with the drawings and specific embodiments.
The solution that the present invention eliminates nano electrochemical sensor passivation is the supporting electrolyte solution that comprises water-soluble strand and double-stranded kation, negative ion and neutral surface active agent.Used water-soluble strand and double-stranded kation, negative ion or neutral surface active agent are DTAB, Tetradecyl Trimethyl Ammonium Bromide, myristyl pyridinium bromide, cetyl trimethyl ammonium bromide, cetyl pyridinium bromide, octadecyl trimethylammonium bromide, lauryl sodium sulfate, sodium dodecylsulphonate, sodium dodecyl benzenylsulfonate or Triton X-100.
The method of eliminating the nano electrochemical sensor passivation effect is to eliminate nano electrochemical sensor passivation with the supporting electrolyte solution that comprises water-soluble strand and double-stranded kation, negative ion and neutral surface active agent.Water-soluble strand and double-stranded kation, negative ion and neutral surface active agent are joined in the supporting electrolyte solution; surface reactive material forms dynamic protective layer in the reversibility absorption original position of modifying on the nano sensitive material on electrochemical sensor electrodes surface, realizes eliminating nano electrochemical sensor passivation.The nano sensitive material of nano electrochemical sensor is a carbon nanomaterial, and carbon nanomaterial is Single Walled Carbon Nanotube, multi-walled carbon nano-tubes or carbon nano-fiber.
The nano sensitive material of used nano electrochemical sensor is a carbon nanomaterial, and carbon nanomaterial comprises Single Walled Carbon Nanotube, multi-walled carbon nano-tubes and carbon nano-fiber.
As shown in Figure 1,1~4 be respectively cationic surfactant DTAB (LTAB), myristyl pyridinium bromide (TPB), cetyl trimethyl ammonium bromide (CTAB), octadecyl trimethylammonium bromide (STAB)) add and can effectively realize the sensitization curve of electrochemical sensor the estradiol detection.5 is that anionic (SDS) adds the sensitization curve that can realize effectively that electrochemical sensor detects estradiol.6 is that neutral surface active agent Qu Latong (TritonX-100) adds the sensitization curve that can realize effectively that electrochemical sensor detects estradiol.Wherein the effect of enhanced sensitivity of cetyl trimethyl ammonium bromide is best, sees curve 3.
Fig. 2 and Fig. 3 show that then the adding of surfactant can be eliminated the passivation effect of substrate to carbon nano-tube sensitive layer in the electrochemical sensor fully, make that electrochemical sensor shows fabulous stability.
When surfactant-free existed, substrate directly was adsorbed on carbon nanometer sensitive membrane surface, and the firm avtive spot that is adsorbed on sensitive membrane of electric inert products that electrochemical reaction produced takes place, and made sensor generation passivation, and response performance descends; When adding surfactant; surfactant adsorbs original position fast in the reversibility on carbon nanometer sensitive membrane surface and forms one deck dynamic protective layer; this layer protective seam has stronger accumulation ability to substrate; avoided substrate to contact simultaneously with the direct of sensitive membrane; after electrochemical reaction is finished; the electric inert products that generates with the desorption of adsorption layer of surface active agent from the sensitive layer desorption get off, thereby realize the protection and the renewal of sensitive layer.

Claims (7)

1. solution of eliminating nano electrochemical sensor passivation is characterized in that: this solution is the supporting electrolyte solution that comprises water-soluble strand and double-stranded kation, negative ion or neutral surface active agent.
2. according to the solution of the described elimination nano electrochemical sensor passivation of claim 1, it is characterized in that: water-soluble strand and double-stranded kation, negative ion or neutral surface active agent are DTAB, Tetradecyl Trimethyl Ammonium Bromide, myristyl pyridinium bromide, cetyl trimethyl ammonium bromide, cetyl pyridinium bromide, octadecyl trimethylammonium bromide, lauryl sodium sulfate, sodium dodecylsulphonate, sodium dodecyl benzenylsulfonate or Triton X-100.
3. a method of eliminating nano electrochemical sensor passivation is characterized in that: use the kation, negative ion or the neutral surface active agent's that comprise water-soluble strand and two strands supporting electrolyte solution to eliminate nano electrochemical sensor passivation.
4. according to the method for the described elimination nano electrochemical sensor passivation of claim 3; it is characterized in that: water-soluble strand and double-stranded kation, negative ion or neutral surface active agent are joined in the supporting electrolyte solution; surface reactive material forms dynamic protective layer in the reversibility absorption original position of modifying on the nano sensitive material on electrochemical sensor electrodes surface, realizes eliminating nano electrochemical sensor passivation.
5. according to the method for claim 3 or 4 described elimination nano electrochemical sensor passivations, it is characterized in that: used water-soluble strand and double-stranded kation, negative ion or neutral surface active agent are DTAB, Tetradecyl Trimethyl Ammonium Bromide, myristyl pyridinium bromide, cetyl trimethyl ammonium bromide, cetyl pyridinium bromide, octadecyl trimethylammonium bromide, lauryl sodium sulfate, sodium dodecylsulphonate, sodium dodecyl benzenylsulfonate or Triton X-100.
6. according to the method for the described elimination nano electrochemical sensor passivation of claim 4, it is characterized in that: the nano sensitive material of nano electrochemical sensor is a carbon nanomaterial.
7. according to the method for the described elimination nano electrochemical sensor passivation of claim 6, it is characterized in that: used carbon nanomaterial is Single Walled Carbon Nanotube, multi-walled carbon nano-tubes or carbon nano-fiber.
CNA2008100489065A 2008-08-19 2008-08-19 Solution for eliminating nano electrochemical sensor passivation and method for eliminating passivation thereof Pending CN101408524A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113252759A (en) * 2015-02-20 2021-08-13 德尔格安全股份两合公司 Electrochemical gas sensor and electrolyte for electrochemical gas sensor

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113252759A (en) * 2015-02-20 2021-08-13 德尔格安全股份两合公司 Electrochemical gas sensor and electrolyte for electrochemical gas sensor

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Application publication date: 20090415