CN100498324C - Method for preparing porous chemical electrode - Google Patents
Method for preparing porous chemical electrode Download PDFInfo
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- CN100498324C CN100498324C CNB2007100209981A CN200710020998A CN100498324C CN 100498324 C CN100498324 C CN 100498324C CN B2007100209981 A CNB2007100209981 A CN B2007100209981A CN 200710020998 A CN200710020998 A CN 200710020998A CN 100498324 C CN100498324 C CN 100498324C
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Abstract
A method for preparing porous chemical electrode includes grinding presoma of pyrrole and packing material as well as nano-microball template as per mass ratio of 1-1.5:3-4.5:1-2 and mixing them to be paste mixture, filling said paste mixture into hollow glass tube, inserting copper wire in said glass tube to lead electrode out, soaking electrode in initiator solution in concentration of 0.01-1.5moI/L for making said paste mixture be integral-polymerized then placing electrode into agitated extraction agent at temperature of 5-40deg.c for removing off nano-microball template.
Description
One, technical field
The invention belongs to the biology sensor preparing technical field, particularly a kind of preparation method of porous chemical electrode.
Two, background technology
Electrochemica biological sensor is that a class is converted into the sensor that can detect electric signal directly or indirectly with the combination of the specificity between the biomacromolecule.The research of carbon paste electrode starts from 20th century the eighties, and is once causing showing great attention to of people, and cost is cheap especially because its method for making is simple especially, is considered to prepare and use the Perfected process of disposable electrode.But along with deepening continuously of research, people find that also this type of electrode exists the shortcoming of poor reproducibility as a result and unsuitable long preservation, has hindered the practical application in bioanalysis.Trace it to its cause, may mainly contain: each process of (1) electrode preparation is not to repeat fully and quantitatively carry out, and electrode surface character such as specific surface area, adsorption activity site what etc., also highly consistent; (2) the withered electrode body that causes of the volatilization of bonding agent paraffin wet goods is tight mutually and lost efficacy.Though it is many electrode to be carried out the report of various modifications and modification, for example adopt epoxy resin or conducting resinl etc. as bonding agent, the electrode body phase character integral body that obtains is better than the result that paraffin oil obtains as bonding agent, but can not fundamentally solve the problem of existence.
Three, summary of the invention
The invention provides a kind of preparation method of porous chemical electrode, this method technology is simple, with low cost.The electrode sensitivity that is obtained by the present invention obtains to significantly improve, and has long-lasting, the parallel reliability of preservation and the good advantage of selectivity.
The technology of the present invention solution is: a kind of preparation method of porous chemical electrode, the double glazing pipe is cleaned, with presoma, filler and Nano microsphere template are the ratio grinding of 1～1.5:3～4.5:1～2 according to mass ratio, be mixed into pasty mixture, gained carbon paste potpourri is inserted in the double glazing pipe, compacting, at the copper conductor of double glazing pipe central authorities insertion as extraction electrode, electrode is immersed at normal temperatures in the initiator solution that concentration is 0.01～1.5mol/L then, make the pasty mixture generation bulk polymerization that is filled in the glass tube at last electrode be put into the extractant of stirring, extracting in 5 ℃～40 ℃ temperature range, remove the Nano microsphere template, above-mentioned presoma is the pyrroles, a kind of or derivatives thereof example in thiophene and the aniline: filler is carbon dust or mica powder, and the Nano microsphere template is the pipe/polyhenylethylene nano microsphere template, polypropylene nano microsphere template or monox Si02 Nano microsphere template; Initiating agent is ferric trichloride or iron sulfate; Extractant is toluene, dimethylbenzene, ethyl acetate and normal butyl alcohol or hydrofluorite.
The electrode body phase specific surface area that is made by the present invention is big, and when electrode body phase specific surface area was enough big, the difference of upgrading surface nature between cross section or different electrode just was not enough to impact analysis result's parallel reliability; On the other hand, might partly improve the long-lasting of carbon paste electrode although use as epoxy resin or conducting resinl etc., the use of bonding agent can be stopped up some ducts, influences the consistance of porous between different interfaces or different electrode.For this reason, the direct nano-form that the present invention proposes porous chemical electrode is induced synthetic, can significantly improve the sensitivity of respective electrochemical sensor, significantly improves the parallel reliability that it preserves long-lasting and analysis result simultaneously, and obtains good selectivity.This porous chemical electrode has following advantage: (1) entire electrode is a continuous integral body, does not contain bonding agent and the problems that can avoid bonding agent to bring; (2) this electrode specific surface area is big, N atom or other functional group that can form hydrogen bond with biomacromolecule is rich on the surface again, thereby biomacromolecule absorption/fixed amount increased greatly, and upgrade between the cross section and between different electrode surface nature difference little, so collimation is good; But because of the even adjustable and functionalization in aperture, so selectivity is good.Therefore, the sensitivity of this electrode obtains to significantly improve, and the preservation of electrode is long-lasting has also obtained remarkable improvement with the parallel reliability of analysis result, and also has good selectivity, helps the absorption, fixing of biomacromolecule, the raising detection sensitivity.Technology of the present invention is simple, and is with low cost, and electrode is highly sensitive, is convenient to preserve.
The electrode that the present invention makes is tested, squeeze before the experiment and remove last time to test a bit of tubing pasty mixture contacted with test material, on smooth pan paper, polish then, to form new electrode surface, respectively at a. pure carbon paste electrode dag wherein: the paraffin oil mass ratio is 80:20; B. modification carbon paste electrode CNT wherein: dag: the paraffin oil mass ratio is 5:75:20; C. behind the surperficial fixed dna of the electrode of gained of the present invention, adopt SLV galvanochemistry screen dna electrochemical signals, experiment as shown in Figure 2, the result shows: volt-ampere curve an oxidation peak occurs about+1.1V, corresponding to the adenine A residue in the oligonucleotides.And, the oxidation peak current a maximum on the electrode of gained of the present invention, the nano-sized carbon paste electrode takes second place, the peak current c minimum on the pure carbon paste electrode.This may be owing to compare with the pure carbon paste electrode, mixing of CNT increased adsorption surface area, absorption and the fixed amount of DNA are increased, and the electrode of gained of the present invention is owing to increased the specific surface area of electrode greatly for cavernous structure, increased absorption and the fixed amount of DNA greatly, peak current is increased.
The present invention has avoided the use bonding agent, has not avoided the withered electrode body that causes of the volatilization of bonding agent such as paraffin wet goods tight mutually and lost efficacy, and has increased the specific surface area of electrode greatly, has improved the sensitivity of electrode greatly.In addition, preparation technology of the present invention is simple, cost is low, consumptive material is few, has to preserve parallel reliability and the good advantage of selectivity long-lasting, analysis result.
Four, description of drawings
Fig. 1 is porous " chemical electrode " preparation route map.Wherein 1 is electrode cable, and 2 is glass tube, and 3 is organic polymer Nano microsphere template, and 4 is polymeric precursor and filler.
Fig. 2 is that the electrochemical signals of porous " chemical electrode ", nano-sized carbon paste electrode and pure carbon paste electrode adsorption of DNA compares.Wherein a is porous " chemical electrode ", b is the nano-sized carbon paste electrode, and the c oxidation peak that to be pure carbon paste electrode volt-ampere curve occur about+1.1V is corresponding to the adenine A residue in the oligonucleotides, peak current is big more to show that adenine A residue is many more, and promptly the amount of adsorption of DNA is many more.
Five, embodiment
A kind of preparation method of porous chemical electrode, be that the double glazing pipe is cleaned, with presoma, filler and Nano microsphere template are the ratio grinding of 1～1.5:3～4.5:1～2 according to mass ratio, be mixed into pasty mixture, gained carbon paste potpourri is inserted in the double glazing pipe, compacting, at the copper conductor of double glazing pipe central authorities insertion as extraction electrode, electrode is immersed at normal temperatures in the initiator solution that concentration is 0.01～1.5mol/L then, make the pasty mixture generation bulk polymerization that is filled in the glass tube at last electrode be put into the extractant of stirring, extracting in 5 ℃～40 ℃ temperature range, remove the Nano microsphere template, above-mentioned presoma is the pyrroles, a kind of or derivatives thereof example in thiophene and the aniline; Filler is carbon dust or mica powder, and the Nano microsphere template is pipe/polyhenylethylene nano microsphere template, polypropylene nano microsphere template or silicon oxide sio 2 Nano microsphere templates; Initiating agent is ferric trichloride or iron sulfate; Extractant is toluene, dimethylbenzene, ethyl acetate and normal butyl alcohol or hydrofluorite.
Related content of the present invention is described below in more detail.
One, the direct nano-form of porous chemical electrode is induced synthetic
(1) the homogeneous diameter polystyrene is the preparation of PS microballoon
The method for preparing the pipe/polyhenylethylene nano microballoon mainly contains suspension polymerization, microemulsion polymerization method and decentralized polymerization etc., and wherein microemulsion polymerization method can be divided into again according to the adding situation of surfactant soap and soap-free polymerization method.Secondly the factor that influences PS Nano microsphere diameter is the influence of preparation temperature and initiating agent and spreading agent or stabilizing agent mainly from the difference of method.Generally easily generate micron-sized microballoon, can obtain the microballoon of 100-200 nanometer diameter scope by controlled condition.
(2) the integrated polymerization of conducting polymer under Nano microsphere templates such as PS
Insert in the glass tube of certain internal diameter optimizing the microballoon such as presoma, PS of proportioning and the potpourri of filler, insert plain conductor, be immersed in then in the solution that contains initiating agent, make the potpourri bulk polymerization that is filled in the glass tube.
(3) Nano microsphere template extracting such as PS after the polymerization
After bulk polymerization is finished, need Nano microsphere template extractings such as PS is clean, finish the whole porous structure that after the template agent electrode is remained intact in extracting simultaneously.
Two, the surface nature of porous chemical electrode and functionalization
(1) surface nature
Character of " porous chemical electrode " inside surface such as specific surface area, pore diameter distribution, surface functional group etc. have decisive influence to the absorption of biomacromolecule/fixing and detection sensitivity to it in bioanalysis.The porous chemical electrode specific surface area of the present invention exploitation than conventional carbon paste electrode big more than 100 times and pore size distribution even, have more surface functional group for further functionalization.
(2) surface-functionalized
The surface-functionalized meaning that two importances are arranged: a. obviously, any electrochemica biological sensor is not omnipotent.For " porous chemical electrode " that obtain can be used widely, it is carried out surface-functionalized modification is necessary; B. another very important meaning is: because " porous chemical electrode " has abundant inner duct, by big minute period of the day from 11 p.m. to 1 a.m of absorption fixed biologically, capillarity may make biomacromolecule diffuse to the electrode depths rapidly, also may cause simultaneously the fixedly difficult reproduction of result of this absorption, thereby the reappearance of impact analysis.One effectively the way of control be the inside surface of " porous chemical electrode " to be carried out targetedly functionalization with going up specific functional group according to the character of desiring to catch biomacromolecule, strong interaction can take place and can catch the big molecule of the target organism that flows through effectively in these specific functional groups with the biomacromolecule that catches, prevent and suppress the latter's STOCHASTIC DIFFUSION, make the latter be completely fixed near in the electrode zone of electrode surface.The a large amount of N-H groups that exist of " porous chemical electrode " polypyrrole that the present invention obtains utilization or azole derivatives and other can be for the functional groups of functionalization, " porous chemical electrode " carried out functionalization such as amination, sulfhydrylation, aldehyde radicalization, streptavidinization or biotinylation, help electrode being carried out modification targetedly, further ensured the reliability of " porous chemical electrode " at different detected objects or detection method.
Three, the application of porous chemical electrode
The present invention has a wide range of applications, for example aspect bio-sensing, by the qualitative classification that detects the object biomacromolecule, mainly can be divided in DNA detection, protein detection, cell detection or tissue, the blood other composition such as amino acid, sugar, metabolic product etc.His abiotic big Molecular Detection that the present invention also can be widely used in it.
Four, embodiment
(1) ps microballoon preparation
Styrene and MAA all need decompression distillation refining, and water is ultrapure water or distilled water.Get a 250ml there-necked flask, middle mouth is put stirring arm, mouthful with hollow plug clog on one side, do reinforced usefulness, the slotting spherical condensation tube of another mouthful.In there-necked flask, add 90ml water earlier, in addition water-soluble to separate 0.25gKPS stand-by for 10ml, add 9ml styrene and 1mlMAA again, vigorous stirring under 300r/min, be heated to boiling, promptly occur in the spherical condensation tube refluxing, reflux and between the first segment and the second joint condenser pipe, be advisable, keep refluxing 15-30 minutes, add previous ready KPS solution at last.Heated condition keeps down can making the PS microballoon that particle diameter is 99nm in 2 hours.Can control the PS diameter of micro ball by cinnamic consumption in the control experiment, as shown in table 1.
The relation of table 1 styrene consumption and PS microspherulite diameter
| Styrene/ml | Water/ml | MAA/ml | KPS/g | Particle diameter/nm |
| 9 | 100 | 1 | 0.25 | 99 |
| 15 | 100 | 1 | 0.25 | 160 |
| 30 | 100 | 1 | 0.25 | 219 |
| 35 | 100 | 1 | 0.25 | 217 |
| 45 | 100 | 1 | 0.25 | 248 |
(2) porous chemical electrode preparation
The double glazing pipe that now with the internal diameter is 4mm is an example, it is cleaned dry for standby.With pyrroles, carbon dust and pipe/polyhenylethylene nano microballoon three ratio with 1～1.5:3～4.5:1～2, in mortar, be mixed into pasty state, then gained carbon paste potpourri is inserted in the glass tube, compacting, pipe central authorities insert a copper conductor.The glass tube that will be filled with the carbon paste potpourri again immerses the FeCl of 0.5mol/L
3In the solution, soak at normal temperatures and made the abundant polymerization of pyrroles in 4 hours, the polyreaction formula is specific as follows:
The first step, monomer are oxidized to the radical cation of delocalization, and it has very high spin density on a position.In second step, the monomer free radical forms dimer by a position free radical lotus root connection, emits 2 protons then, produces neutral dimer.Then dimer is oxidized to the dimer free radical, with other monomer free radical or dimer free radical, oligomer free radical reaction, polymeric chain is increased, and lotus root connection oxidizing process repeats down like this, is terminated up to chain growth.
Polymerization back water is well rinsed well, oven dry, and in the toluene solution that electrode immerse is stirred 6 hours again, the PS microsphere template is removed in extracting can obtain porous " chemical electrode ".
(3) practical application effect of prepared porous electrode
For the specific surface area that further specifies porous chemical electrode is big, highly sensitive, respectively at a. pure carbon paste electrode dag wherein: the paraffin oil mass ratio is 80:20; B. modification carbon paste electrode CNT wherein: dag: the paraffin oil mass ratio is 5:75:20; C. behind the surperficial fixed dna of porous " chemistry " electrode, adopt SLV galvanochemistry screen dna electrochemical signals, experiment as shown in Figure 2, the result shows: volt-ampere curve is about+1.1V
An oxidation peak appears, corresponding to the adenine A residue in the oligonucleotides.And, the oxidation peak current a maximum on porous " chemistry " electrode, the nano-sized carbon paste electrode takes second place, the peak current c minimum on the pure carbon paste electrode.This is owing to compare with the pure carbon paste electrode, mixing of CNT increased adsorption surface area, the absorption of DNA and fixed amount are increased, and porous chemical electrode is owing to increased the specific surface area of electrode greatly for cavernous structure, increased absorption and the fixed amount of DNA greatly, peak current is increased.Further optimization experiment condition, the sensitivity that can further improve electrode is expected to improve 2-3 the order of magnitude than traditional pure carbon paste electrode.
Claims (1)
1, a kind of preparation method of porous chemical electrode, it is characterized in that the double glazing pipe is cleaned, with presoma, filler and Nano microsphere template are the ratio grinding of 1～1.5:3～4.5:1～2 according to mass ratio, be mixed into pasty mixture, the gained pasty mixture is inserted in the double glazing pipe, compacting, at the copper conductor of double glazing pipe central authorities insertion as extraction electrode, then electrode being immersed at normal temperatures concentration is in several initiator solution of 0.01～1.5mol, make the pasty mixture generation bulk polymerization that is filled in the glass tube at last electrode be put into the extractant of stirring, extracting in 5 ℃～40 ℃ temperature range, remove the Nano microsphere template, above-mentioned presoma is the pyrroles, a kind of or derivatives thereof in thiophene and the aniline, filler is carbon dust or mica powder, and the Nano microsphere template is the pipe/polyhenylethylene nano microsphere template, polypropylene nano microsphere template or silicon oxide sio 2 Nano microsphere templates; Initiating agent is ferric trichloride or iron sulfate; Extractant is toluene, dimethylbenzene, ethyl acetate, normal butyl alcohol or hydrofluorite.
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| CN102323315B (en) * | 2011-06-03 | 2013-06-12 | 浙江大学 | Carbon paste electrode based on doped polyphenylacetylene and carbon nano tube and preparation process of carbon paste electrode |
| CN102269730B (en) * | 2011-07-04 | 2013-12-18 | 中国科学院长春应用化学研究所 | Carbon paste electrode and preparation method thereof |
| CN107884449A (en) * | 2017-11-06 | 2018-04-06 | 钟永松 | One kind is directed to H2The high gas sensor of selectivity |
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| Title |
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| 多孔陶瓷制备技术研究进展. 钱军民等.兵器材料科学与工程，第28卷第5期. 2005 |
| 多孔陶瓷制备技术研究进展. 钱军民等.兵器材料科学与工程，第28卷第5期. 2005 * |
| 有机大分子在有序多孔材料制备中的应用. 陈鸿奎等.高分子材料科学与工程，第20卷第4期. 2004 |
| 有机大分子在有序多孔材料制备中的应用. 陈鸿奎等.高分子材料科学与工程，第20卷第4期. 2004 * |
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Effective date of registration: 20140820 Address after: Wang Yuan Cun Da Gong Zhen Haian County in Jiangsu province 226623 18 Nantong City Group Building 1 Patentee after: Jiangsu Xinye Heavy Industry Co., Ltd. Patentee after: Southeast University Address before: 210096 Jiangsu city Nanjing Province four pailou No. 2 Patentee before: Southeast University |