CN106324068A - Novel method for detecting lead ions based on sensitivity of DNA-MOF material - Google Patents
Novel method for detecting lead ions based on sensitivity of DNA-MOF material Download PDFInfo
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- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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Abstract
The invention discloses a novel method for detecting lead ions based on the sensitivity of a DNA-MOF material. The method comprises the following steps: preparing a gold-paper chip working electrode Au-PWE; synthesizing Au-MOF from 5,10,15,20-tetra(4-methoxy phenyl)porphyrin, ferric chloride and nanogold; carrying out functionalization by virtue of GR DNA, so as to synthesize a GR-Au-MOF material; modifying the prepared Au-PWE with HP DNA, and dropwise adding a GR-Au-MOF solution mixed with 3,3',5,5'-tetramethyl benzidine, hydrogen peroxide and a sample solution to HP modified Au-PWE; and connecting the modified chip to an electrochemical working station by virtue of a three-electrode system, and detecting the concentration of lead ions by virtue of a differential pulse voltammetry. The novel method for detecting the lead ions is high in sensitivity and good in selectivity, and the real-time monitoring of samples can be realized.
Description
Technical field
The present invention relates to lead ion detection technique field, be a kind of sensitive inspection based on DNA-MOF material in particular
The new method of sounding lead ion, the invention still further relates to use differential pulse voltammetry Sensitive Detection lead ion.
Background technology
Lead ion content is an index important in environmental monitoring, because lead ion enters human body by food chain, when
Human body can be caused a certain degree of injury when content reaches finite concentration, such as child is dull-witted, brain development slowly, siberian crabapple
System damage, can cause death time serious, it is necessary for therefore seeking the high-sensitive detection method of a kind of high efficiency.Along with research
The most perfect, the sensor of various detection lead ions is established, and by using efficient DNA enzymatic, but this DNA enzymatic is deposited
In the most acidproof shortcoming being weak to alkali of poor stability, and easily inactivate in the environment of temperature is slightly higher.With other abiotic catalysis
Unlike agent, enzyme has the specificity of height, and only catalysis is specifically reacted or produces specific configuration.But, due to mostly
Number enzyme is protein, and to heat, acid, alkali instability, structure changes and makes it lose catalysis activity.It addition, native enzyme is at biology
Internal content is the lowest, is difficult to be obtained in a large number native enzyme by purification, therefore expensive, greatly limit its actual application.
Therefore, synthesize fermentoid all the same with native enzyme on chemical constitution, catalytic efficiency, specificity and selectivity, be still research work
The study hotspot of author.
Metal one organic framework materials (Metal Organic Frameworks, MOF) quickly grows nearly ten years
A kind of coordination polymer, has the pore structure of three-dimensional, and typically with metal ion as junction point, organic ligand supports Special composition
3D extends, and is the important novel porous materials of the another class outside zeolite and CNT, has in catalysis, energy storage and separation
Extensively application.At present, MOF has become the important research direction of multiple chemical branch such as inorganic chemistry, organic chemistry.In this respect
Famous scientist such as kitagawa, Yaghi etc..Metal-organic framework materials refers to that transition metal ions leads to organic ligand
Cross the crystalline porous material with periodic network structure being self-assembly of.It has high porosity, low-density, Large ratio surface
Amass, duct is regular, aperture is adjustable and the advantage such as topological structure multiformity and Scalability.Mainly include two important component:
Node and to couple bridge, i.e. MOF be to be connected the organic ligand of number by difference and frame structure that metal ion node combines.
Class Catalyzed Synthesis By Peroxidase activity and H2O2Concentration has dependency, and the change by color and absorbance can be examined
Survey H2O2, further coupling also can other molecule of indirect determination.Owing to MOF material can be anti-with the oxidoreduction of catalyzing hydrogen peroxide
Should, therefore MOF material replaces traditional enzyme to be a problem being worth research as class peroxidase.And MOF
Class peroxidase to acid, alkali, temperature have preferable stability and catalysis activity is higher, it has also become the phases such as Analytical Chemistry in Life Science
One of the study hotspot in field, pass.MOF class peroxidase as reagent in organic synthesis, bioconversion, enzyme coupling reaction, change
The aspects such as luminesceence analysis, immunoassay, sewage disposal are cut and are appeared.Owing to the catalysis of MOF class peroxidase is active and it
Composition, pattern, particle diameter, modification group, valence state, institute's factor such as electrically charged are closed very much, develop that performance is controlled, catalysis activity is higher, steady
Qualitative nanometer class peroxidase strong, that specificity is good, highly sensitive for analytical chemistry particularly Analytical Chemistry in Life Science and is received
Rice analytical chemistry is highly important.It addition, along with the expansion of biosensor application scope, it is desirable to sensor neither disturbs survey
Determine other related components impact in object and don't tested sufficient object, this requirement will be met, high accuracy can be drawn again simultaneously
Measurement result, a set of integration, the optimization system of miniaturization just can obtain satisfied result.Meanwhile, chip technology also will be more
To enter sensor field, it is achieved detecting system integrated, integrated manyly.
Therefore, we are extremely urgent to seek a kind of new method to lead ion Sensitive Detection, can be by the peroxidizing property of MOF
Carry out the detection of lead ion, the electrochemical sensor of the porphyrin of DNA functionalization-organic backbone lead ion sensitization.The present invention synthesizes
Ferrum-porphyrin MOF structure there is good class peroxide enzyme viability, and above in conjunction with upper nano Au particle and GR
DNA sequence, can specific recognition lead ion, carry out in the solution containing hydrogen peroxide and TMB
The detection of electrochemical signals, thus the detection of lead ion in cell can also be realized.
Summary of the invention
The technical problem to be solved in the present invention there is provided the new of a kind of Sensitive Detection lead ion based on DNA-MOF material
Method.
In order to solve above-mentioned technical problem, the present invention is realized by following measures: a kind of based on DNA-MOF material
The new method of Sensitive Detection lead ion, it comprises the following steps:
(1) gold-paper chip working electrode Au-PWE is prepared；
(2) synthesis ferrum-porphyrin MOF material, and modify with nanometer gold, obtain Au-MOF；
(3) ferrum of synthesis-porphyrin MOF material GR DNA is carried out functionalization, synthesize GR-Au-MOF material；
(4) modify upper HP DNA on the Au-PWE that will prepare, be then blended with TMB, peroxide
The GR-Au-MOF solution changing hydrogen and sample solution drips to be modified with on the Au-PWE of HP；
(5) chip modified obtained is connected on electrochemical workstation by three-electrode system, uses differential pulse volt
Peace method carries out the detection of plumbum ion concentration.
The new method of a kind of Sensitive Detection lead ion based on DNA-MOF material, is characterized in that, described new method include as
Lower step:
(1) method printed by wax prints the working region of required three-electrode system, passes through silk screen on working region
Stamp Ag/AgCl reference electrode and carbon comparison electrode, modify upper gold seeds the most on the working electrode (s, dropping gold chloride and
The mixed solution of sodium borohydride, obtains gold-paper chip working electrode Au-PWE；
(2) preparation of MOF material: take 30.22 mg 5,10,15,20-tetra-(4-methoxyphenyl) porphyrins, 35.45 mg
FeCl3·6H2O and 0.8 mL 0.1 mol L -1 HCl ethanol solution join 3 mL N, N '-dimethyl Methanamide and
Supersound process 10 min in the mixed solution of 6 mL ethanol, is then transferred in the autoclave of 40 mL reacting at 150 DEG C 36
H, prepares ferrum-porphyrin MOF material；
(3) preparation of Au-MOF material: take ferrum-porphyrin MOF material prepared by 4.0 mg steps (2) and be dissolved in 1 mL ethanol,
It is added thereto to 0.20 mL 1.00 mol L -1 Ammonia spirit and the mixed liquor of 11.3 mL ethanol, add 1.5 mL
6.0 mmol·L -1Tetraethyl orthosilicate solution, under room temperature stirring reaction 2 h, by gained mixed liquor ethanol centrifuge washing
Three times, then the solid of gained is joined in 2 mL nano-Au solutions, stirring reaction 12 h, obtain Au-MOF material；
(4) preparation of GR-Au-MOF material: 100 μ L 10 μm ol L will be added in the Au-MOF material of step (3) gained-1 GR DNA, GR DNA be dispersed in 50 mmol L -1With 300 mmol L -1The pH of NaCl is the buffering of 8.2
In solution, obtaining GR-Au-MOF material, above-mentioned described GR DNA sequence is 5 '-
ACAGACATCATCTCTGAAGTAGCGCCGCCGTATAGTGAGAAACTCACTATrAGGAAGA GATGATGTCTGTTTTTT-
3 ', on 3 ', modify-(CH2)6-SH；
(5) modify upper 10 μ L HP DNA on the Au-PWE that will prepare, react 90 min at 37 DEG C, then by 10 μ L
It is mixed with 4 μ L 0.90 mmol L -1 3,3 ', 5,5 '-tetramethyl biphenyl amine aqueous solution, 4 μ L 0.50 mmol L -1's
The GR-Au-MOF solution of the sample solution that hydrogenperoxide steam generator and 2 μ L contain different plumbum ion concentration drips to be modified with HP's
On Au-PWE, above-mentioned described HP DNA sequence is 5 '-ACAGACATCATCTCTTCCTCTGT-3 ', modify 3 '-
(CH2)6-SH；
(6) chip modified obtained is connected on electrochemical workstation by three-electrode system, uses differential pulse volt
Peace method carries out the detection of plumbum ion concentration.
Beneficial effects of the present invention:
(1) utilize ferrum-porphyrin MOF materials synthesis Au-MOF, have that good stability, good biocompatibility, toxicity is little, the scope of application
Wide advantage；
(2) the Au-MOF material synthesized by the present invention is prepared simply, be can be mass, and has good class peroxidase
Characteristic, the susceptiveness of mensuration can be improved；
(3) lead ion in the present invention and GR DNA have specific recognition function, the lead ion in sample can be carried out top collar
Detection；
(4) present invention is based on paper three-electrode system, utilizes differential pulse voltammetry to carry out lead ion and measures operation quickly and easily, instead
Should and result be automatically performed by instrument and record, it is to avoid the impact of subjective factors, and ensure there is good repeatability, it is simple to
Site Detection.
Accompanying drawing explanation
With specific embodiment, the present invention is described in further detail below in conjunction with the accompanying drawings.
The detection process of lead ion in [Fig. 1] sample.
Detailed description of the invention
A kind of new method of Sensitive Detection lead ion based on DNA-MOF material, it comprises the following steps:
(1) gold-paper chip working electrode Au-PWE is prepared；
(2) synthesis ferrum-porphyrin MOF material, and modify with nanometer gold, obtain Au-MOF；
(3) ferrum of synthesis-porphyrin MOF material GR DNA is carried out functionalization, synthesize GR-Au-MOF material；
(4) modify upper HP DNA on the Au-PWE that will prepare, be then blended with TMB, peroxide
The GR-Au-MOF solution changing hydrogen and sample solution drips to be modified with on the Au-PWE of HP；
(5) chip modified obtained is connected on electrochemical workstation by three-electrode system, uses differential pulse volt
Peace method carries out the detection of plumbum ion concentration.
The new method of a kind of Sensitive Detection lead ion based on DNA-MOF material, is characterized in that, described new method include as
Lower step:
(1) method printed by wax prints the working region of required three-electrode system, passes through silk screen on working region
Stamp Ag/AgCl reference electrode and carbon comparison electrode, modify upper gold seeds the most on the working electrode (s, dropping gold chloride and
The mixed solution of sodium borohydride, obtains gold-paper chip working electrode Au-PWE；
(2) preparation of MOF material: take 30.22 mg 5,10,15,20-tetra-(4-methoxyphenyl) porphyrins, 35.45 mg
FeCl3·6H2O and 0.8 mL 0.1 mol L -1 HCl ethanol solution join 3 mL N, N '-dimethyl Methanamide and
Supersound process 10 min in the mixed solution of 6 mL ethanol, is then transferred in the autoclave of 40 mL reacting at 150 DEG C 36
H, prepares ferrum-porphyrin MOF material；
(3) preparation of Au-MOF material: take ferrum-porphyrin MOF material prepared by 4.0 mg steps (2) and be dissolved in 1 mL ethanol,
It is added thereto to 0.20 mL 1.00 mol L -1 Ammonia spirit and the mixed liquor of 11.3 mL ethanol, add 1.5 mL
6.0 mmol·L -1Tetraethyl orthosilicate solution, under room temperature stirring reaction 2 h, by gained mixed liquor ethanol centrifuge washing
Three times, then the solid of gained is joined in 2 mL nano-Au solutions, stirring reaction 12 h, obtain Au-MOF material；
(4) preparation of GR-Au-MOF material: 100 μ L 10 μm ol L will be added in the Au-MOF material of step (3) gained-1 GR DNA, GR DNA be dispersed in 50 mmol L -1With 300 mmol L -1The pH of NaCl is the buffering of 8.2
In solution, obtain GR-Au-MOF material；
(5) modify upper 10 μ L HP DNA on the Au-PWE that will prepare, react 90 min at 37 DEG C, then by 10 μ L
It is mixed with 4 μ L 0.90 mmol L -1 3,3 ', 5,5 '-tetramethyl biphenyl amine aqueous solution, 4 μ L 0.50 mmol L -1's
The GR-Au-MOF solution of the sample solution that hydrogenperoxide steam generator and 2 μ L contain different plumbum ion concentration drips to be modified with HP's
On Au-PWE；
(6) chip modified obtained is connected on electrochemical workstation by three-electrode system, uses differential pulse volt
Peace method carries out the detection of plumbum ion concentration.
Embodiment 1 (industrial wastewater)
(1) method printed by wax prints the working region of required three-electrode system, passes through silk screen on working region
Stamp Ag/AgCl reference electrode and carbon comparison electrode, modify upper gold seeds the most on the working electrode (s, dropping gold chloride and
The mixed solution of sodium borohydride, obtains gold-paper chip working electrode Au-PWE；
(2) preparation of MOF material: take 30.22 mg 5,10,15,20-tetra-(4-methoxyphenyl) porphyrins, 35.45 mg
FeCl3·6H2O and 0.8 mL 0.1 mol L -1 HCl ethanol solution join 3 mL N, N '-dimethyl Methanamide and
Supersound process 10 min in the mixed solution of 6 mL ethanol, is then transferred in the autoclave of 40 mL reacting at 150 DEG C 36
H, prepares ferrum-porphyrin MOF material；
(3) preparation of Au-MOF material: take ferrum-porphyrin MOF material prepared by 4.0 mg steps (2) and be dissolved in 1 mL ethanol,
It is added thereto to 0.20 mL 1.00 mol L -1 Ammonia spirit and the mixed liquor of 11.3 mL ethanol, add 1.5 mL
6.0 mmol·L -1Tetraethyl orthosilicate solution, under room temperature stirring reaction 2 h, by gained mixed liquor ethanol centrifuge washing
Three times, then the solid of gained is joined in 2 mL nano-Au solutions, stirring reaction 12 h, obtain Au-MOF material；
(4) preparation of GR-Au-MOF material: 100 μ L 10 μm ol L will be added in the Au-MOF material of step (3) gained-1 GR DNA, GR DNA be dispersed in 50 mmol L -1With 300 mmol L -1The pH of NaCl is the buffering of 8.2
In solution, obtain GR-Au-MOF material；
(5) industrial wastewater is carried out filtration treatment；
(6) modify upper 10 μ L HP DNA on the Au-PWE that will prepare, react 90 min at 37 DEG C, then 10 μ L are mixed
Conjunction has 4 μ L 0.90 mmol L -1 3,3 ', 5,5 '-tetramethyl biphenyl amine aqueous solution, 4 μ L 0.50 mmol L -1Mistake
Hydrogen peroxide solution and the 2 μ L GR-Au-MOF solution containing the industrial wastewater sample that (5) process in steps drip to be modified with the Au-of HP
On PWE；
(7) chip modified obtained is connected on electrochemical workstation by three-electrode system, uses differential pulse volt
Peace method carries out the detection of plumbum ion concentration.
Embodiment 2 (Sucus Mali pumilae)
(1) method printed by wax prints the working region of required three-electrode system, passes through silk screen on working region
Stamp Ag/AgCl reference electrode and carbon comparison electrode, modify upper gold seeds the most on the working electrode (s, dropping gold chloride and
The mixed solution of sodium borohydride, obtains gold-paper chip working electrode Au-PWE；
(2) preparation of MOF material: take 30.22 mg 5,10,15,20-tetra-(4-methoxyphenyl) porphyrins, 35.45 mg
FeCl3·6H2O and 0.8 mL 0.1 mol L -1 HCl ethanol solution join 3 mL N, N '-dimethyl Methanamide and
Supersound process 10 min in the mixed solution of 6 mL ethanol, is then transferred in the autoclave of 40 mL reacting at 150 DEG C 36
H, prepares ferrum-porphyrin MOF material；
(3) preparation of Au-MOF material: take ferrum-porphyrin MOF material prepared by 4.0 mg steps (2) and be dissolved in 1 mL ethanol,
It is added thereto to 0.20 mL 1.00 mol L -1 Ammonia spirit and the mixed liquor of 11.3 mL ethanol, add 1.5 mL
6.0 mmol·L -1Tetraethyl orthosilicate solution, under room temperature stirring reaction 2 h, by gained mixed liquor ethanol centrifuge washing
Three times, then the solid of gained is joined in 2 mL nano-Au solutions, stirring reaction 12 h, obtain Au-MOF material；
(4) preparation of GR-Au-MOF material: 100 μ L 10 μm ol L will be added in the Au-MOF material of step (3) gained-1 GR DNA, GR DNA be dispersed in 50 mmol L -1With 300 mmol L -1The pH of NaCl is the buffering of 8.2
In solution, obtain GR-Au-MOF material；
(5) Sucus Mali pumilae is carried out filtration treatment；
(6) modify upper 10 μ L HP DNA on the Au-PWE that will prepare, react 90 min at 37 DEG C, then by 10 μ L
It is mixed with 4 μ L 0.90 mmol L -1 3,3 ', 5,5 '-tetramethyl biphenyl amine aqueous solution, 4 μ L 0.50 mmol L -1's
Hydrogenperoxide steam generator and the 2 μ L GR-Au-MOF solution containing the Sucus Mali pumilae that (5) process in steps drip to be modified with the Au-PWE of HP
On；
(7) chip modified obtained is connected on electrochemical workstation by three-electrode system, uses differential pulse volt
Peace method carries out the detection of plumbum ion concentration.
Embodiment 3 (river)
(1) method printed by wax prints the working region of required three-electrode system, passes through silk screen on working region
Stamp Ag/AgCl reference electrode and carbon comparison electrode, modify upper gold seeds the most on the working electrode (s, dropping gold chloride and
The mixed solution of sodium borohydride, obtains gold-paper chip working electrode Au-PWE；
(2) preparation of MOF material: take 30.22 mg 5,10,15,20-tetra-(4-methoxyphenyl) porphyrins, 35.45 mg
FeCl3·6H2O and 0.8 mL 0.1 mol L -1 HCl ethanol solution join 3 mL N, N '-dimethyl Methanamide and
Supersound process 10 min in the mixed solution of 6 mL ethanol, is then transferred in the autoclave of 40 mL reacting at 150 DEG C 36
H, prepares ferrum-porphyrin MOF material；
(3) preparation of Au-MOF material: take ferrum-porphyrin MOF material prepared by 4.0 mg steps (2) and be dissolved in 1 mL ethanol,
It is added thereto to 0.20 mL 1.00 mol L -1 Ammonia spirit and the mixed liquor of 11.3 mL ethanol, add 1.5 mL
6.0 mmol·L -1Tetraethyl orthosilicate solution, under room temperature stirring reaction 2 h, by gained mixed liquor ethanol centrifuge washing
Three times, then the solid of gained is joined in 2 mL nano-Au solutions, stirring reaction 12 h, obtain Au-MOF material；
(4) preparation of GR-Au-MOF material: 100 μ L 10 μm ol L will be added in the Au-MOF material of step (3) gained-1 GR DNA, GR DNA be dispersed in 50 mmol L -1With 300 mmol L -1The pH of NaCl is the buffering of 8.2
In solution, obtain GR-Au-MOF material；
(5) river is carried out filtration treatment；
(6) modify upper 10 μ L HP DNA on the Au-PWE that will prepare, react 90 min at 37 DEG C, then 10 μ L are mixed
Conjunction has 4 μ L 0.90 mmol L -1 3,3 ', 5,5 '-tetramethyl biphenyl amine aqueous solution, 4 μ L 0.50 mmol L -1Mistake
Hydrogen peroxide solution and the 2 μ L GR-Au-MOF solution containing the river that (5) process in steps drip to be modified with on the Au-PWE of HP；
(7) chip modified obtained is connected on electrochemical workstation by three-electrode system, uses differential pulse volt
Peace method carries out the detection of plumbum ion concentration.
Embodiment 4 (soil)
(1) method printed by wax prints the working region of required three-electrode system, passes through silk screen on working region
Stamp Ag/AgCl reference electrode and carbon comparison electrode, modify upper gold seeds the most on the working electrode (s, dropping gold chloride and
The mixed solution of sodium borohydride, obtains gold-paper chip working electrode Au-PWE；
(2) preparation of MOF material: take 30.22 mg 5,10,15,20-tetra-(4-methoxyphenyl) porphyrins, 35.45 mg
FeCl3·6H2O and 0.8 mL 0.1 mol L -1 HCl ethanol solution join 3 mL N, N '-dimethyl Methanamide and
Supersound process 10 min in the mixed solution of 6 mL ethanol, is then transferred in the autoclave of 40 mL reacting at 150 DEG C 36
H, prepares ferrum-porphyrin MOF material；
(3) preparation of Au-MOF material: take ferrum-porphyrin MOF material prepared by 4.0 mg steps (2) and be dissolved in 1 mL ethanol,
It is added thereto to 0.20 mL 1.00 mol L -1 Ammonia spirit and the mixed liquor of 11.3 mL ethanol, add 1.5 mL
6.0 mmol·L -1Tetraethyl orthosilicate solution, under room temperature stirring reaction 2 h, by gained mixed liquor ethanol centrifuge washing
Three times, then the solid of gained is joined in 2 mL nano-Au solutions, stirring reaction 12 h, obtain Au-MOF material；
(4) preparation of GR-Au-MOF material: 100 μ L 10 μm ol L will be added in the Au-MOF material of step (3) gained-1 GR DNA, GR DNA be dispersed in 50 mmol L -1With 300 mmol L -1The pH of NaCl is the buffering of 8.2
In solution, obtain GR-Au-MOF material；
(5) by soil dispersion to 10 mL redistilled waters, filtration treatment is then carried out；
(6) modify upper 10 μ L HP DNA on the Au-PWE that will prepare, react 90 min at 37 DEG C, then 10 μ L are mixed
Conjunction has 4 μ L 0.90 mmol L -1 3,3 ', 5,5 '-tetramethyl biphenyl amine aqueous solution, 4 μ L 0.50 mmol L -1Mistake
Hydrogen peroxide solution and the 2 μ L GR-Au-MOF solution containing the pedotheque that (5) process in steps drip to be modified with the Au-PWE of HP
On；
(7) chip modified obtained is connected on electrochemical workstation by three-electrode system, uses differential pulse volt
Peace method carries out the detection of plumbum ion concentration.
Embodiment 5 (serum)
(1) method printed by wax prints the working region of required three-electrode system, passes through silk screen on working region
Stamp Ag/AgCl reference electrode and carbon comparison electrode, modify upper gold seeds the most on the working electrode (s, dropping gold chloride and
The mixed solution of sodium borohydride, obtains gold-paper chip working electrode Au-PWE；
(2) preparation of MOF material: take 30.22 mg 5,10,15,20-tetra-(4-methoxyphenyl) porphyrins, 35.45 mg
FeCl3·6H2O and 0.8 mL 0.1 mol L -1 HCl ethanol solution join 3 mL N, N '-dimethyl Methanamide and
Supersound process 10 min in the mixed solution of 6 mL ethanol, is then transferred in the autoclave of 40 mL reacting at 150 DEG C 36
H, prepares ferrum-porphyrin MOF material；
(3) preparation of Au-MOF material: take ferrum-porphyrin MOF material prepared by 4.0 mg steps (2) and be dissolved in 1 mL ethanol,
It is added thereto to 0.20 mL 1.00 mol L -1 Ammonia spirit and the mixed liquor of 11.3 mL ethanol, add 1.5 mL
6.0 mmol·L -1Tetraethyl orthosilicate solution, under room temperature stirring reaction 2 h, by gained mixed liquor ethanol centrifuge washing
Three times, then the solid of gained is joined in 2 mL nano-Au solutions, stirring reaction 12 h, obtain Au-MOF material；
(4) preparation of GR-Au-MOF material: 100 μ L 10 μm ol L will be added in the Au-MOF material of step (3) gained-1 GR DNA, GR DNA be dispersed in 50 mmol L -1With 300 mmol L -1The pH of NaCl is the buffering of 8.2
In solution, obtain GR-Au-MOF material；
(5) modify upper 10 μ L HP DNA on the Au-PWE that will prepare, react 90 min at 37 DEG C, then by 10 μ L
It is mixed with 4 μ L 0.90 mmol L -1 3,3 ', 5,5 '-tetramethyl biphenyl amine aqueous solution, 4 μ L 0.50 mmol L -1's
The GR-Au-MOF solution that hydrogenperoxide steam generator and 2 μ L contain serum drips to be modified with on the Au-PWE of HP；
(6) chip modified obtained is connected on electrochemical workstation by three-electrode system, uses differential pulse volt
Peace method carries out the detection of plumbum ion concentration.
SEQUENCE LISTING
<110>University Of Ji'nan
<120>new method of a kind of Sensitive Detection lead ion based on DNA-MOF material
<130> 2016
<160> 2
<170> PatentIn version 3.3
<210> 1
<211> 75
<212> DNA
<213>artificial sequence
<400> 1
acagacatca tctctgaagt agcgccgccg tatagtgaga aactcactat raggaagaga 60
tgatgtctgt ttttt 75
<210> 2
<211> 23
<212> DNA
<213>artificial sequence
<400> 2
acagacatca tctcttcctc tgt 23
Claims (2)
1. a new method for Sensitive Detection lead ion based on DNA-MOF material, it comprises the following steps:
(1) gold-paper chip working electrode Au-PWE is prepared；
(2) synthesis ferrum-porphyrin MOF material, and modify with nanometer gold, obtain Au-MOF；
(3) ferrum of synthesis-porphyrin MOF material GR DNA is carried out functionalization, synthesize GR-Au-MOF material；
(4) modify upper HP DNA on the Au-PWE that will prepare, be then blended with 3,3', 5,5-tetramethyl benzidines, peroxide
The GR-Au-MOF solution changing hydrogen and sample solution drips to be modified with on the Au-PWE of HP；
(5) chip modified obtained is connected on electrochemical workstation by three-electrode system, uses differential pulse volt
Peace method carries out the detection of plumbum ion concentration.
The new method of a kind of Sensitive Detection lead ion based on DNA-MOF material the most according to claim 1, its feature
It is that described new method comprises the steps:
(1) method printed by wax prints the working region of required three-electrode system, passes through silk screen on working region
Stamp Ag/AgCl reference electrode and carbon comparison electrode, modify upper gold seeds the most on the working electrode (s, dropping gold chloride and
The mixed solution of sodium borohydride, obtains gold-paper chip working electrode Au-PWE；
(2) preparation of MOF material: take 30.22 mg 5,10,15,20-tetra-(4-methoxyphenyl) porphyrins, 35.45 mg
FeCl3·6H2O and 0.8 mL 0.1 mol L -1 HCl ethanol solution join 3 mL N, N '-dimethyl Methanamide and
Supersound process 10 min in the mixed solution of 6 mL ethanol, is then transferred in the autoclave of 40 mL reacting at 150 DEG C 36
H, prepares ferrum-porphyrin MOF material；
(3) preparation of Au-MOF material: take ferrum-porphyrin MOF material prepared by 4.0 mg steps (2) and be dissolved in 1 mL ethanol,
It is added thereto to 0.20 mL 1.00 mol L -1 Ammonia spirit and the mixed liquor of 11.3 mL ethanol, add 1.5 mL
6.0 mmol·L -1Tetraethyl orthosilicate solution, under room temperature stirring reaction 2 h, by gained mixed liquor ethanol centrifuge washing
Three times, then the solid of gained is joined in 2 mL nano-Au solutions, stirring reaction 12 h, obtain Au-MOF material；
(4) preparation of GR-Au-MOF material: 100 μ L 10 μm ol L will be added in the Au-MOF material of step (3) gained -1
GR DNA, GR DNA be dispersed in 50 mmol L -1With 300 mmol L -1The pH of NaCl be 8.2 buffering molten
In liquid, obtaining GR-Au-MOF material, above-mentioned described GR DNA sequence is 5 '-
ACAGACATCATCTCTGAAGTAGCGCCGCCGTATAGTGAGAAACT CACTATrAGGAAGAGATGATGTCTGTTTTTT-
3 ', on 3 ', modify-(CH2)6-SH；
(5) modify upper 10 μ L HP DNA on the Au-PWE that will prepare, react 90 min at 37 DEG C, then 10 μ L are mixed
Conjunction has 4 μ L 0.90 mmol L -13,3 ', 5,5 '-tetramethyl biphenyl amine aqueous solution, 4 μ L 0.50 mmol L -1Peroxide
The GR-Au-MOF solution of the sample solution that change hydrogen solution and 2 μ L contain different plumbum ion concentration drips to be modified with the Au-PWE of HP
On, above-mentioned described HP DNA sequence is 5 '-ACAGACATCATCTCTTC CTCTGT-3 ', modifies upper-(CH 3 '2)6-SH；
(6) chip modified obtained is connected on electrochemical workstation by three-electrode system, uses differential pulse volt
Peace method carries out the detection of plumbum ion concentration.
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