CN101281158A - DNA sensitivity electrode modified by hydrotalcite nanometer slice and preparation thereof - Google Patents
DNA sensitivity electrode modified by hydrotalcite nanometer slice and preparation thereof Download PDFInfo
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- CN101281158A CN101281158A CNA2008101120185A CN200810112018A CN101281158A CN 101281158 A CN101281158 A CN 101281158A CN A2008101120185 A CNA2008101120185 A CN A2008101120185A CN 200810112018 A CN200810112018 A CN 200810112018A CN 101281158 A CN101281158 A CN 101281158A
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Abstract
The invention relates to a DNA sensitive electrode decorated by hydrotalcite nano-chip and the preparation method thereof, which belongs to the field of electrochemical biosensors and preparation technology thereof. The sensitive electrode uses a glassy carbon electrode as the substrate electrode, and a sensitive film composed of double-strand DNA and co-aluminum hydrotalcite nano-chip is decorated on the surface of the substrate electrode. The preparation method of the sensitive electrode is as follows: the co-aluminum hydrotalcite nano-chip collosol is coated on the surface of the clean glassy carbon electrode; after dried at room temperature, the glassy carbon electrode is washed with second distilled water and dried, then the double-strand DNA solution is dropped on the surface of the hydrotalcite nano-chip; after dried at room temperature, the glassy carbon electrode is washed with second distilled water and dried, then the DNA sensitive electrode decorated by hydrotalcite nano-chip is prepared. The sensitive electrode has the advantages that the invention uses the properties of the hydrotalcite nano-chip, that is, the hydrotalcite nano-chip has large surface area, has high-density positive charge, has a lot of hydroxide radical on the surface and has good electric conductibility and so on, to realize the stability and fixing of mass DNA, and the electrode can be used in quantitative determination of phenol, which has good anti-interference performance.
Description
Technical field
The invention belongs to electrochemica biological sensor and preparing technical field thereof, particularly relate to DNA sensitive electrode of a kind of modified by hydrotalcite nanometer slice and preparation method thereof.
Background technology
Electrochemica biological sensor has characteristics such as stable performance, cheap, easy and simple to handle, easy microminiaturization, is used widely in all many-sides such as clinical diagnosis, Industry Control, food inspection, Pharmaceutical Analysis, environmental analysis, biochip and military fields.Wherein the electrochemical DNA sensor was receiving much concern in recent years, had been not limited to the test of gene order, more obtained bigger development at fermentation such as Pharmaceutical Analysis, pollutant tests, was the focus of current electrochemica biological sensor research field.As at document (1) Biosensors and Bioelectronics, 2006, among the 21:1777-1783, people such as Kavita Arora utilize electro-deposition method with polypyrrole-polyvinyl sulfonic acid salt composite film forming on indium tin oxide-coated glass, calf thymus double-stranded DNA (brief note is ds-DNA) are fixed on by the physisorption method to constitute the DNA sensitive electrode on the film then.This DNA sensitive electrode can be used for the detection of o-chlorphenol, and its range of linearity is 0.1-30ppm, illustrates that the DNA sensitive electrode can be used for the detection by quantitative of organic molecule.
But the electrochemical DNA sensor exist the DNA fixed amount little, easily reveal and problem such as anti-interference is relatively poor.In order to address the above problem, people introduce the electrochemical DNA biosensor system with nano material, utilize the specific surface area of nano material big, excellent properties such as high adsorption capacity, improve the performance index such as stability, sensitivity of DNA sensitive electrode.Up to the present, existing multiple nano material is applied to the preparation of DNA sensitive electrode, as nanometer Au, nanometer Si, nano Ce O
2Deng.At document (2) Talanta, 2006, among the 70:561-565, people such as Ke-Jun Feng are with nano Ce O
2With chitosan complexes at the glass-carbon electrode surface filming, fixing single stranded DNA (brief note for ss-DNA) on film is prepared the DNA sensitive electrode that detects carcinoma of the rectum dna fragmentation then.Result of study shows nano Ce O
2Introducing strengthened the electric conductivity of film and the fixed effect of ss-DNA, improved the sensitivity and the identification mispairing ability of DNA sensitive electrode.
Summary of the invention
The purpose of this invention is to provide DNA sensitive electrode of kind of modified by hydrotalcite nanometer slice and preparation method thereof, hydrotalcite nano piece is introduced in the DNA sensitive electrode.The hydrotalcite nano piece specific surface area is big, has the high density positive charge, can have the stronger electrostatic interaction of phosphoric acid skeleton formation of negative charge with DNA, and the absorption that helps DNA is fixed; The cobalt aluminum hydrotalcite nano piece has satisfactory electrical conductivity, helps improving the sensitivity of DNA sensitive electrode; Hydroxyl is rich on the hydrotalcite nano piece surface, can interact by hydrogen bond and DNA, so hydrotalcite nano piece has excellent biological compatibility as immobilization material.
The DNA sensitive electrode of modified by hydrotalcite nanometer slice provided by the invention, be to be basal electrode with the glass-carbon electrode, constitute sensitive membrane by double-stranded DNA (brief note is ds-DNA) and cobalt aluminum hydrotalcite nano piece and be modified at the basal electrode surface, wherein the content of ds-DNA is 2.1～4.2 μ g/mm
2, the content of cobalt aluminum hydrotalcite nano piece is 1.4～5.6 μ g/mm
2Described ds-DNA is a kind of in herring sperm dna or the salmon sperm dna.
The concrete steps of DNA sensitive electrode that the present invention prepares modified by hydrotalcite nanometer slice are as follows:
(1) preparation of hydrotalcite nano film sol
According to the Co/Al mol ratio is that 2: 1～4: 1 ratio takes by weighing Co (NO
3)
26H
2O and Al (NO
3)
39H
2O, being dissolved in and being made into metallic ion (Co+Al) total concentration in the deionized water is the salt solusion of 1.5～1.8mol/L; Taking by weighing NaOH is dissolved in and is made into the aqueous slkali that concentration is 2.8～3.5mol/L in the deionized water; It is back-mixing 1～2 minute in 300～1000 rev/mins the colloid mill that above-mentioned salt solusion and aqueous slkali are added revolution simultaneously, obtains pink suspending liquid; With suspending liquid under nitrogen protection in 90～100 ℃ of crystallization 6～8 hours, suction filtration, wash to filtrate pH value be 6～7, then filter cake is put into baking oven in 50～80 ℃ of dryings 12～48 hours, grind and promptly get cobalt aluminum hydrotalcite powder.The ratio that according to hydrotalcite quality/formamide volume is 0.5～2g/L joins above-mentioned cobalt aluminum hydrotalcite powder in the formamide, stirs 0.5～3 hour in 70～90 ℃ of constant temperature, can obtain settled solution, is the hydrotalcite nano film sol.
(2) preparation of the DNA sensitive electrode of modified by hydrotalcite nanometer slice
By 1.4～5.6 μ g/mm
2Usefulness measure above-mentioned hydrotalcite nano film sol and drip and be applied to clean glass-carbon electrode surface, 20～35 ℃ of dry backs with the redistilled water flushing, dry; Herring sperm or salmon sperm ds-DNA are mixed with the solution that concentration is 0.5～1g/L with redistilled water, again by 2.1～4.2 μ g/mm
2Usefulness measure this dna solution and drip and be coated on the hydrotalcite nano lamella, 20～35 ℃ of dryings and with the redistilled water flushing, dry, promptly get the DNA sensitive electrode of modified by hydrotalcite nanometer slice.
Redistilled water of the present invention is the distilled water through twice distillation.
Effect of the present invention can be found out from the DNA sensitive electrode test phenol with the modified by hydrotalcite nanometer slice of the inventive method preparation.As working electrode, platinum electrode is to electrode with the DNA sensitive electrode of modified by hydrotalcite nanometer slice, and the Ag/AgCl electrode is a contrast electrode, forms the electrochemical DNA sensor.It is the Tris-HCl buffer solution of indicator that the three-electrode system of this electrochemical DNA sensor is placed with the methylene blue, adopts the CHI660B electrochemical workstation of Shanghai occasion China instrument company that it is carried out the sign of chemical property.
Glass-carbon electrode, modified by hydrotalcite nanometer slice glass-carbon electrode, fixed the glass-carbon electrode of DNA and fixed DNA four kinds of working electrodes such as modified by hydrotalcite nanometer slice glass-carbon electrode cyclic voltammetry curve as shown in Figure 1, the introducing of hydrotalcite nano piece, strengthened the current-responsive of DNA sensitive electrode in containing the Tris-HCl buffer solution of methylene blue indicator effectively, shown that hydrotalcite nano piece has vital role to the sensitivity that improves the DNA sensitive electrode.The DNA sensitive electrode of modified by hydrotalcite nanometer slice can the Pyrogentisinic Acid detect, and the material that several interference phenol common in oil refining sewerage and chemical engineering sewage are tested has good antijamming capability, and mushing error is all less than 5% (as shown in table 1).The linear response range of the DNA sensitive electrode test phenol of modified by hydrotalcite nanometer slice is 4 * 10
-6～2 * 10
-5Mol/L (see figure 2), Pyrogentisinic Acid's minimum detectability are 2 * 10
-6Mol/L.The DNA sensitive electrode of modified by hydrotalcite nanometer slice has adaptability widely, all can realize Pyrogentisinic Acid's quantitative measurement (see figure 3) in the scope of pH value 5～11, particularly suits to use under slight alkali environment.The DNA sensitive electrode of modified by hydrotalcite nanometer slice does not destroy fixing DNA in the process of test phenol, can use repeatedly, follow-on test same concentrations phenol is more than 20 times, and the relative standard deviation of gained data shows good operational stability less than 2.5%.
Anti-interference when the DNA sensitive electrode of table 1. modified by hydrotalcite nanometer slice is tested phenol
| Interfering material (with the phenol concentration ratio be 1: 1) | Pyrogallol | Resorcinol | β-anthrol | Aniline | Sodium sulphide |
| Mushing error | 2.3％ | 4.4％ | 2.1％ | 1.6％ | 0.33％ |
Characteristics of the present invention are: adopt the DNA sensitive electrode of the modified by hydrotalcite nanometer slice of the inventive method preparation to carry out detection by quantitative to the phenol in oil refining sewerage and the chemical engineering sewage, and have linear response range, the higher detection sensitivity of stronger anti-interference, broad, the pH value scope of application, good operational stability and the storage stability (seeing embodiment) of broad.It is simple to adopt the inventive method to prepare the technology of DNA sensitive electrode of modified by hydrotalcite nanometer slice in addition, and production cost is lower.
Description of drawings:
Fig. 1 is glass-carbon electrode, modified by hydrotalcite nanometer slice glass-carbon electrode, fixed the glass-carbon electrode of DNA and fixed the cyclic voltammetry curve of four kinds of working electrodes such as modified by hydrotalcite nanometer slice glass-carbon electrode of DNA.Wherein,
Horizontal ordinate-voltage, unit: volt, contrast electrode is the Ag/AgCl electrode;
Ordinate-current density, unit: microampere/square centimeter.
The cyclic voltammetry curve of Fig. 1 a-glass-carbon electrode;
The cyclic voltammetry curve of the glass-carbon electrode of Fig. 1 b-modified by hydrotalcite nanometer slice;
Fig. 1 c-fixed cyclic voltammetry curve of the glass-carbon electrode of DNA;
The cyclic voltammetry curve of the glass-carbon electrode of the modified by hydrotalcite nanometer slice of Fig. 1 d-fixed DNA.
Fig. 2 is the current-responsive of the cyclic voltammetric test in the Tris-HCl buffer solution of 50mmol/L of indicator and the graph of a relation of phenol concentration for the DNA sensitive electrode of modified by hydrotalcite nanometer slice at the methylene blue with 20 μ mol/L.Wherein,
Horizontal ordinate-phenol concentration, unit: micromoles per liter;
Ordinate-current density, unit: microampere/square centimeter.
Fig. 3 is the cyclic voltammetric current-responsive of DNA sensitive electrode of modified by hydrotalcite nanometer slice and the graph of a relation of pH value.Wherein, horizontal ordinate-pH value; Ordinate-current density, unit: microampere/square centimeter.
Embodiment:
Embodiment 1
(1) preparation of hydrotalcite nano film sol
Take by weighing the Co (NO of 0.12mol
3)
26H
2Al (the NO of O and 0.06mol
3)
39H
2O is dissolved in the 100mL deionized water and is made into salt solusion; The NaOH that takes by weighing 0.35mol is dissolved in proportionaling alkali-forming solution in the 100mL deionized water.It is back-mixing 2 minutes in 400 rev/mins the colloid mill that aqueous slkali and salt solusion are added revolution simultaneously, obtains pink suspending liquid; Be transferred to suspending liquid in the four-hole boiling flask rapidly; under nitrogen protection in 100 ℃ of crystallization 6 hours, suction filtration, wash to filtrate pH value be 6; then filter cake is put into baking oven in 50 ℃ of dryings 48 hours, grinding and promptly getting the Co/Al mol ratio is 2: 1 cobalt aluminum hydrotalcite powder.Get this cobalt aluminum hydrotalcite 0.025g, join in the 50mL formamide, on magnetic stirring apparatus, 90 ℃ of constant temperature stir and can obtain the hydrotalcite nano film sol that concentration is 0.5g/L in 0.5 hour.
(2) preparation of the DNA sensitive electrode of modified by hydrotalcite nanometer slice
With concentration is that the hydrotalcite nano film sol 20 μ L of 0.5g/L drip and are coated in the glass-carbon electrode surface that diameter is the cleaning of 3mm, 20 ℃ of dry down backs with the redistilled water flushing, dry; With herring sperm ds-DNA is the solution of 0.5g/L with the redistilled water compound concentration, then this dna solution 30 μ L are dripped the glass-carbon electrode surface that is coated in modified by hydrotalcite nanometer slice, 20 ℃ down dry and with the redistilled water flushing, dry, promptly make the DNA sensitive electrode of modified by hydrotalcite nanometer slice.
DNA sensitive electrode with modified by hydrotalcite nanometer slice is a working electrode, and platinum electrode is to electrode, and the Ag/AgCl electrode is a contrast electrode, and experimental temperature is 25 ± 3 ℃, and test system is 20 μ mol/L MB～50mmol/LTris-HCl buffer solution of pH=7.5.The cyclic voltammetric test shows, the introducing of hydrotalcite nano piece has strengthened the current-responsive (as shown in Figure 1) of DNA sensitive electrode in containing the Tris-HCl buffer solution of methylene blue indicator effectively; Adopt cyclic voltammetry to detect the DNA sensitive electrode Pyrogentisinic Acid's of modified by hydrotalcite nanometer slice response, the relation curve of phenol concentration and current-responsive as shown in Figure 2, its range of linearity is 4 * 10
-6～2 * 10
-5Mol/L detects and is limited to 2 * 10
-6Mol/L; Is 1 * 10 with this DNA sensitive electrode to concentration
-5The phenol solution of mol/L is carried out 20 tests continuously, and the relative standard deviation of gained data is 1.2%, and operational stability is good; When pyrogallol, resorcinol, β-anthrol, aniline and sodium sulphide were 1: 1 with the phenol concentration ratio, mushing error was all less than 5% (being shown in Table 1).This electrode is preserved after-current response in 10 months and is 59% of initial value.
(1) preparation of hydrotalcite nano film sol
Take by weighing the Co (NO of 0.12mol
3)
26H
2Al (the NO of O and 0.04mol
3)
39H
2O is dissolved in the 100mL deionized water and is made into salt solusion; The NaOH that takes by weighing 0.31mol is dissolved in proportionaling alkali-forming solution in the 100mL deionized water.It is back-mixing 1.5 minutes in 700 rev/mins the colloid mill that aqueous slkali and salt solusion are added revolution simultaneously, obtains pink suspending liquid; Be transferred to suspending liquid in the four-hole boiling flask rapidly; under nitrogen protection in 90 ℃ of crystallization 7 hours, suction filtration, wash to filtrate pH value be 6.5; then filter cake is put into baking oven in 70 ℃ of dryings 24 hours, grinding and promptly getting the Co/Al mol ratio is 3: 1 cobalt aluminum hydrotalcite powder.Get this cobalt aluminum hydrotalcite 0.05g, join in the 50mL formamide, on magnetic stirring apparatus, 80 ℃ of constant temperature stir and can obtain the hydrotalcite nano film sol that concentration is 1g/L in 2 hours.
(2) preparation of the DNA sensitive electrode of modified by hydrotalcite nanometer slice
With concentration is that the hydrotalcite nano film sol 20 μ L of 1g/L drip and are coated in the glass-carbon electrode surface that diameter is the cleaning of 3mm, 25 ℃ of dry down backs with the redistilled water flushing, dry; With herring sperm ds-DNA is the solution of 0.8g/L with the redistilled water compound concentration, then this dna solution 20 μ L are dripped the glass-carbon electrode surface that is coated in modified by hydrotalcite nanometer slice, 25 ℃ down dry and with the redistilled water flushing, dry, promptly make the DNA sensitive electrode of modified by hydrotalcite nanometer slice.
With the modified glassy carbon electrode is working electrode, and platinum electrode is to electrode, and the Ag/AgCl electrode is a contrast electrode, and experimental temperature is 25 ± 3 ℃, and experimental system is 20 μ mol/L MB～50mmol/L Tris-HCl buffer solution.The relation explanation that cyclic voltammetry curve current-responsive value and pH change, the DNA sensitive electrode of modified by hydrotalcite nanometer slice has adaptability widely, all can realize Pyrogentisinic Acid's quantitative measurement (see figure 3) in the scope of pH value 5～11; This electrode is preserved to respond after 6 months and is 65% of initial value.
Embodiment 3
(1) preparation of hydrotalcite nano film sol
Take by weighing the Co (NO of 0.12mol
3)
26H
2Al (the NO of O and 0.03mol
3)
39H
2O is dissolved in the 100mL deionized water and is made into salt solusion; The NaOH that takes by weighing 0.29mol is dissolved in proportionaling alkali-forming solution in the 100mL deionized water.It is back-mixing 1 minute in 1000 rev/mins the colloid mill that aqueous slkali and salt solusion are added revolution simultaneously, obtains pink suspending liquid; Be transferred to suspending liquid in the four-hole boiling flask rapidly; under nitrogen protection in 95 ℃ of crystallization 8 hours, suction filtration, wash to filtrate pH value be 7; then filter cake is put into baking oven in 80 ℃ of dryings 12 hours, grinding and promptly getting the Co/Al mol ratio is 4: 1 cobalt aluminum hydrotalcite powder.Get this cobalt aluminum hydrotalcite 0.1g, join in the 50mL formamide, on magnetic stirring apparatus, 70 ℃ of constant temperature stir and can obtain the hydrotalcite nano film sol that concentration is 2g/L in 3 hours.
(2) preparation of the DNA sensitive electrode of modified by hydrotalcite nanometer slice
With concentration is that the hydrotalcite nano film sol 20 μ L of 2g/L drip and are coated in the glass-carbon electrode surface that diameter is the cleaning of 3mm, 35 ℃ of dry down backs with the redistilled water flushing, dry; With salmon sperm ds-DNA is the solution of 1g/L with the redistilled water compound concentration, then this dna solution 30 μ L are dripped the glass-carbon electrode surface that is coated in modified by hydrotalcite nanometer slice, 35 ℃ down dry and with the redistilled water flushing, dry, promptly make the DNA sensitive electrode of modified by hydrotalcite nanometer slice.
With the modified glassy carbon electrode is working electrode, and platinum electrode is to electrode, and the Ag/AgCl electrode is a contrast electrode, and experimental temperature is 25 ± 3 ℃, and test system is 20 μ mol/L MB～50mmol/L Tris-HCl buffer solution of pH=8.5.Cyclic voltammetry detects the DNA sensitive electrode Pyrogentisinic Acid's of modified by hydrotalcite nanometer slice response, and its range of linearity is 4 * 10
-6～2 * 10
-5Mol/L detects and is limited to 2 * 10
-6Mol/L; Is 1 * 10 with this DNA sensitive electrode to concentration
-5The phenol solution of mol/L is carried out 20 tests continuously, and the relative standard deviation of gained data is 2.4%, and operational stability is good; When pyrogallol, resorcinol, β-anthrol, aniline and sodium sulphide were 1: 1 with the phenol ratio, mushing error was all less than 5%.This electrode is preserved to respond after 5 months and is 66% of initial value.
Claims (4)
1, a kind of DNA sensitive electrode of modified by hydrotalcite nanometer slice is characterized in that, is basal electrode with the glass-carbon electrode, constitutes sensitive membrane by double-stranded DNA and cobalt aluminum hydrotalcite nano piece and is modified at the basal electrode surface, and wherein the content of double-stranded DNA is 2.1～4.2 μ g/mm
2, the content of cobalt aluminum hydrotalcite nano piece is 1.4～5.6 μ g/mm
2Described double-stranded DNA is a kind of in herring sperm dna or the salmon sperm dna.
2, a kind of method for preparing the described DNA sensitive electrode of claim 1 is characterized in that, processing step is:
(1) preparation of hydrotalcite nano film sol
According to the Co/Al mol ratio is that 2: 1～4: 1 ratio takes by weighing Co (NO
3)
26H
2O and Al (NO
3)
39H
2O, being dissolved in and being made into metallic ion (Co+Al) total concentration in the deionized water is the salt solusion of 1.5～1.8mol/L; Taking by weighing NaOH is dissolved in and is made into the aqueous slkali that concentration is 2.8～3.5mol/L in the deionized water; It is back-mixing 1～2 minute in 300～1000 rev/mins the colloid mill that above-mentioned salt solusion and aqueous slkali are added revolution simultaneously, obtains pink suspending liquid; With suspending liquid under nitrogen protection in 90～100 ℃ of crystallization 6～8 hours, suction filtration, wash to filtrate pH value be 6～7, then filter cake is put into baking oven in 50～80 ℃ of dryings 12～48 hours, grind cobalt aluminum hydrotalcite powder;
The ratio that according to hydrotalcite quality/formamide volume is 0.5～2g/L joins above-mentioned cobalt aluminum hydrotalcite powder in the formamide, stirs 0.5～3 hour in 70～90 ℃ of constant temperature, obtains settled solution, is the hydrotalcite nano film sol;
(2) preparation of the DNA sensitive electrode of modified by hydrotalcite nanometer slice
By 1.4～5.6 μ g/mm
2Usefulness measure above-mentioned hydrotalcite nano film sol and drip and be applied to clean glass-carbon electrode surface, 20～35 ℃ of dry down backs with the redistilled water flushing, dry; Double-stranded DNA is mixed with the solution that concentration is 0.5～1g/L with redistilled water, again by 2.1～4.2 μ g/mm
2Usefulness measure the double-stranded DNA drips of solution and be coated on the hydrotalcite nano lamella, 20～35 ℃ of dryings and with the redistilled water flushing, dry, the DNA sensitive electrode of modified by hydrotalcite nanometer slice.
According to the preparation method of the described DNA sensitive electrode of claim 2, it is characterized in that 3, the double-stranded DNA described in the step (2) is a kind of in herring sperm dna or the salmon sperm dna.
According to the preparation method of the described DNA sensitive electrode of claim 2, it is characterized in that 4, the redistilled water described in the step (2) is the distilled water through twice distillation.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071460A (en) * | 2010-11-19 | 2011-05-25 | 长春理工大学 | Method for preparing europium-doped lanthanum phosphate porous nanorods on basis of herring sperm DNA template |
| CN102183645A (en) * | 2011-01-24 | 2011-09-14 | 中国科学院合肥物质科学研究院 | Food-borne pathogenic bacteria detection immuno-sensor and preparation method thereof |
| CN103217462A (en) * | 2013-02-22 | 2013-07-24 | 上海大学 | Electrochemical drug sensor used for detecting acetaminophen, and preparation method thereof |
| CN103318977A (en) * | 2013-05-23 | 2013-09-25 | 北京化工大学 | Method for preparing hydrotalcite-based supercapacitor material through amorphous aluminum precursor induction |
| CN104086786A (en) * | 2014-07-17 | 2014-10-08 | 厦门大学 | Preparation method and application of hydrogel electrode |
| CN104449676A (en) * | 2014-12-24 | 2015-03-25 | 北京化工大学 | Preparation method of chiral optical thin film with porphyrin intercalation DNA and hydrotalcite compound |
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| CN1459502A (en) * | 2002-05-23 | 2003-12-03 | 北京化工大学 | Anionic type laminated material immobilized enzyme and its preparation method |
| CN100498323C (en) * | 2007-05-18 | 2009-06-10 | 北京化工大学 | Electrochemical biological sensor sensing film and its preparing method and use |
| CN101140257B (en) * | 2007-10-18 | 2010-04-21 | 北京化工大学 | Biologic sensor enzyme functional susceptivity film containing nickel and aluminum hydrotalcite nano piece and method of producing the same |
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2008
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071460A (en) * | 2010-11-19 | 2011-05-25 | 长春理工大学 | Method for preparing europium-doped lanthanum phosphate porous nanorods on basis of herring sperm DNA template |
| CN102071460B (en) * | 2010-11-19 | 2012-10-31 | 长春理工大学 | Method for preparing europium-doped lanthanum phosphate porous nanorods on basis of herring sperm DNA template |
| CN102183645A (en) * | 2011-01-24 | 2011-09-14 | 中国科学院合肥物质科学研究院 | Food-borne pathogenic bacteria detection immuno-sensor and preparation method thereof |
| CN102183645B (en) * | 2011-01-24 | 2013-12-11 | 中国科学院合肥物质科学研究院 | Food-borne pathogenic bacteria detection immuno-sensor and preparation method thereof |
| CN103217462A (en) * | 2013-02-22 | 2013-07-24 | 上海大学 | Electrochemical drug sensor used for detecting acetaminophen, and preparation method thereof |
| CN103318977A (en) * | 2013-05-23 | 2013-09-25 | 北京化工大学 | Method for preparing hydrotalcite-based supercapacitor material through amorphous aluminum precursor induction |
| CN103318977B (en) * | 2013-05-23 | 2015-02-18 | 北京化工大学 | Method for preparing hydrotalcite-based supercapacitor material through amorphous aluminum precursor induction |
| CN104086786A (en) * | 2014-07-17 | 2014-10-08 | 厦门大学 | Preparation method and application of hydrogel electrode |
| CN104449676A (en) * | 2014-12-24 | 2015-03-25 | 北京化工大学 | Preparation method of chiral optical thin film with porphyrin intercalation DNA and hydrotalcite compound |
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