CN104267088B - Detect electrochemica biological sensor of glutathione and preparation method thereof - Google Patents
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Abstract
The present invention relates to a kind of electrochemica biological sensor for detecting glutathione and preparation method thereof.The sensor is three-electrode system sensor, wherein being platinum electrode to electrode, reference electrode is saturated calomel electrode, and working electrode is gold electrode, it is characterised in that the double-stranded DNA of template can be synthesized as copper nano-cluster by being modified with described gold electrode.The present invention is combined using glutathione with the high-affinity of copper ion, suppresses the synthesis of electrode surface copper nano-cluster, and is characterized by the electrochemical quantitative to copper nano-cluster, realizes the indirect detection to glutathione.The range of linearity of present invention detection glutathione is 1 ~ 1000 nM, and detection limit is about 0.42 nM.The present invention also has the advantages that simple to operate, with low cost, easy to use, selectivity is high, thus with huge potential using value in the field such as Biochemical Research and clinical analysis.
Description
Technical field
The present invention relates to a kind of novel electrochemical Biosensors and preparation method thereof, particularly a kind of detection glutathione
Electrochemica biological sensor and preparation method thereof.
Background of invention
Glutathione is content most abundant small-molecular-weight non-protein sulfhydryl compound in cell, and it is by glutamic acid, half Guang
Propylhomoserin and glycine are formed through peptide bond condensation.Glutathione is the conditioning agent of sulfydryl and sulfide in body, is maintaining albumen mercapto
Play important in terms of the reducing condition and the active, anti-oxidant of enzyme, maintenance living organism internal oxidition reducing environment balance of base
Effect.Some researchs show in recent years, the change of body glutathion inside concentration and alzheimer disease, parkinsonism,
The generation development of many diseases such as diabetes, atherosclerosis is relevant；And the Sensitive Detection of glutathione can be these diseases
The clinical diagnosis and treatment of disease provide many important information.The technology of detection glutathione mainly includes high-efficient liquid phase color now
Spectrometry, ultraviolet-heat amount detection method, capillary electrophoresis, mass spectrometry, spectrofluorimetry etc..These methods are in detection
It is each advantageous in terms of sensitivity, selectivity, detection time and stability, but there is also cumbersome, instrument and equipment is expensive simultaneously
Deng deficiency.Therefore, invent a kind of simple, sensitive glutathione new detecting method and seem very urgent.
Electrochemica biological sensor be a class using electrode as signal adapter, the biology measured with current potential or electric current
Sensor, is mainly combined and is constituted by molecular recognition and information converting member two parts.Electrochemical system realizes electric energy by electrode
Input or output, so as to obtain the electric signal of electrode face finish material.Three-electrode system is commonly used in electrochemical research, including
Working electrode, auxiliary electrode（Also referred to as to electrode）And reference electrode.Electric current flows through working electrode and auxiliary electrode, working electrode institute
The current potential measured is for reference electrode.Electrochemical method is as an alanysis detection method, with equipment is cheap, spirit
Sensitivity is high, it is simple and efficient the advantages of.
The content of the invention
An object of the present invention is to provide a kind of electrochemica biological sensor for detecting glutathione, and the sensor passes through
Quantitative analysis to electrode surface copper nano-cluster, realizes the indirect detection for glutathione.
The second object of the present invention is the preparation method for providing the sensor.
To reach above-mentioned purpose, the present invention uses following mechanism：A single-stranded P1 of DNA is designed, sulfydryl is contained in its 3' end,
Can be by the effect self assembly of gold-mercapto covalent bond in gold electrode surfaces；One and the single-stranded base complete complementaries of P1 are designed in addition
The single-stranded P2 of DNA, both form double-strand at hybridization, the template synthesized as copper nano-cluster in electrode surface.Exist in reducing agent
Under the conditions of, the bivalent cupric ion in solution is reduced into monovalence cuprous ion, the latter occur disproportionated reaction be transformed into cupric from
Son and zeroth order copper atom, and zeroth order copper atom can electrode surface fix double-stranded DNA major groove position occur enrichment and most
End form is into copper nano-cluster.Using hydrochloric acid by the copper nano-cluster oxidation dissolution of synthesis, and detected using electrochemical techniques, can be with
Realize the quantitatively characterizing to electrode surface copper nano-cluster.On the other hand, the copper that glutathione can specifically in binding soln
Ion, so as to suppress the reduction process of copper ion, the quantity for ultimately resulting in the copper nano-cluster of electrode surface synthesis is reduced.Utilize electricity
Chemical technology electrochemical signals resulting when carrying out quantitatively characterizing to copper nano-cluster also accordingly diminish, and are believed by analyzing electrochemistry
Number change number, we can just calculate the concentration of glutathione.
According to above-mentioned mechanism, the present invention is adopted the following technical scheme that：
A kind of electrochemica biological sensor for detecting glutathione, is three-electrode system sensor, wherein being platinum to electrode
Electrode, reference electrode is saturated calomel electrode, and working electrode is gold electrode, it is characterised in that be modified with energy on described gold electrode
Enough DNA double chains that template is synthesized as copper nano-cluster, and the double-strand complementary structure.
Above-mentioned DNA double chain is hybridized by P1, P2 chain to be formed, and the sequence of wherein P1 chains is：5'-TACTCATACGCTCATACG
TTCATCACGACTAAAAA-C6The sequence of-SH-3', P2 chain is：5'- AGTCGTGATGAACGTATGAGCGTATGAGTA-
3'。
The design principle of above-mentioned sequence is that P1-P2 hybridization chain can keep stable pair in electrode surface in experimentation
Chain structure, and no less than 30 bases of double-chain length（The ratio of T-A base-pairs is more than 50%）, to ensure the synthesis of copper nano-cluster
Efficiency.Once DNA sequence is devised, it is prepared or chemical synthesis completes the nucleic acid Synesis Company for transferring to specialty.
The preparation method of a kind of biology sensor according to above-mentioned detection glutathione, it is characterised in that prepare the sensing
The working electrode of device, is concretely comprised the following steps：
A) treated gold electrode is placed in 0.5MH2SO4In, cyclic voltammetry scan is carried out in 0~1.6V voltage ranges,
Sweep speed and be set to 100 mV/s, until reaching stabilization；Drying is stand-by；
B) gold electrode obtained by step a is immersed in into DNA to fix in cushioning liquid, after standing 15 ~ 18 hours at room temperature, then soaked
Not in the 1 mM sulfydryl hexanol aqueous solution, lucifuge is reacted 0.5~2.0 hour, and with ultrapure water, drying obtains first
The gold electrode of chain modification；Described DNA is fixed in cushioning liquid containing first chain, 10 mM Tris- that concentration is 1 μM
HCl, 1 mM EDTA, 10 mM TCEP and 0.1 M NaCl, the pH value of solution is 7.4；
C) gold electrode through first chain modification obtained by step b is immersed in DNA hybridization buffer liquid, 4 DEG C stand 1 ~ 2
Ultrapure water is used after hour, drying obtains the gold electrode of complete double-stranded DNA modification；Described DNA hybridization buffer solution
For 10 mM pH 7.4 phosphate buffer, wherein it is 1 μM of second chain and 1 M NaCl to contain concentration.
The processing method of above-mentioned gold electrode is concretely comprised the following steps：20 μ L Piranhas are dripped in pending gold electrode surfaces
Solution, the i.e. volume ratio of Nong Liu Suan ﹕ hydrogen peroxide are 3 ﹕ 1, are reacted 2 minutes, clean with ultrapure water, nitrogen drying；By gold
It is being respectively 1 μm, 0.3 μm, 0.05 μm of aluminum oxide containing granularity after electrode is polished 2 minutes on 5000 mesh sand paper
Minute surface is polished on the silk of mortar successively, it is then ultrasonic 2 minutes successively in ethanol, ultra-pure water, remove impurity.
A kind of detection method of glutathione, using the biology sensor of above-mentioned glutathione, it is characterised in that the party
Method is concretely comprised the following steps：
A. appropriate ascorbic acid powder is weighed, 10mM is diluted to ultra-pure water, takes 40 μ L and 320 μ L reaction buffers mixed
Close, then toward adding the mixed solution to be measured that 40 μ L contain 10 μM of copper ions and various concentrations glutathione, room temperature in the system
Reaction 20 minutes；Contain MOPS, 300 mM NaCl that concentration is 20 mM and 2 mM MgCl in described reaction buffer2,
The pH value of solution is 7.5.
B. the working electrode gold electrode in biology sensor is put into the mixed solution obtained by step a at once, at room temperature
Reaction 30 minutes.After being dried up with ultrapure water and with nitrogen, working electrode is immersed in the M hydrochloric acid solutions of 200 μ L 0.1
The copper nano-cluster of lysis electrodes surface synthesis.After reaction 2 hours, above-mentioned solution and the M NaAc-HAc of 4.8 mL 0.5 are buffered
Liquid is mixed, and carries out Electrochemical Detection in this, as electrolyte solution.Electrochemical Detection is concretely comprised the following steps：First in -1.2 V electricity
Pressure deposition 8 minutes, then uses differential pulse voltammetry（DPV）Scanning obtains corresponding electrochemical data；Wherein DPV experiments are specific
Parameter is：The V of initial potential 0.1, terminates the V of current potential 0.35, the mV of pulse amplitude 50, the m of pulse period 200.
The present invention constructs a kind of electrochemica biological sensor for detecting glutathione, utilizes glutathione and copper ion parent
With power it is strong the characteristics of, inhibitory action that glutathione is synthesized to copper nano-cluster and Electrochemical Detection are sensitive, convenient Dominant Facies
With reference to, by the quantitatively characterizing for the copper nano-cluster for synthesizing electrode surface, glutathione is carried out quickly, sensitively to detect,
It is with a wide range of applications.
Brief description of the drawings
Fig. 1 is the DPV quantitative tables of the copper nano-cluster of electrode surface synthesis when there is the copper ion of various concentrations in the solution
Levy result.Curve be respectively from a to f 0 M, 1 nM, 10 nM, 100 nM, 1 μM and 10 μM.
Fig. 2 is DPV collection of illustrative plates resulting in 1 μM of glutathione of detection and control experiment.（a）In control group, system not
Containing glutathione；（b）Contain 1 μM of glutathione in experimental group, system.
Fig. 3 is detection various concentrations glutathione（It is respectively 0 nM, 1 nM, 5 nM, 10 nM, 100 nM, 1 μ from a to g
M and 10 μM）When obtained DPV collection of illustrative plates.
Fig. 4 is the relation between DPV peak point currents and glutathione concentrations, and insertion figure is glutathione concentrations in 1-1000
In the range of nM, the linear relationship between DPV peak point currents and glutathione concentrations logarithm value.
The DPV collection of illustrative plates obtained when Fig. 5 is 1 μM of glutathione of detection and 10 μM of interference amino acid.
Specific implementation method
Embodiment one：It is prepared by the gold electrode of double-stranded DNA modification
20 μ L Piranha solution are dripped in pending gold electrode surfaces（The ﹕ 1 of Nong Liu Suan ﹕ hydrogen peroxide=3）Reaction 2 minutes,
It is clean with ultrapure water, nitrogen drying.After gold electrode is polished 5 minutes on 5000 mesh sand paper, containing oxidation respectively
Aluminium（Granularity is respectively 1 μm, 0.3 μm, 0.05 μm）Minute surface is polished on the silk of mortar successively, then in ethanol, ultra-pure water
In successively ultrasound 2 minutes, remove impurity.The gold electrode handled well is placed on 0.5 M H2SO4Middle cyclic voltammetry scan.Set
The V of scanning voltage scope 0~1.6, the mV/s of sweep speed 100, the circle of setting 30 are swept to cyclic voltammetry curve stabilization, are blown with nitrogen
It is dry, obtain being surface-treated clean naked gold electrode, the modification available for sulfydryl DNA.The gold electrode is immersed containing 1 μM of P1 chain
DNA fixes cushioning liquid（10 mM Tris-HCl, 1 mM EDTA, 10 mM TCEP and 0.1 M NaCl, pH 7.4）Middle room
Temperature is lower to stand 15 ~ 18 hours, that is, forms the good P1 chain self assembled monolayers without non-specific adsorption.Use ultrapure water
Gold electrode, and dried up with nitrogen, then gold electrode is immersed into the hybridization buffer containing 1 μM of P2 chain（10 mM pH 7.4 phosphorus
Phthalate buffer, wherein the NaCl containing 1 M）In, 4 DEG C of standings use ultrapure water after 1 ~ 2 hour, and are dried up with nitrogen, i.e.,
Obtain the gold electrode of complete double-stranded DNA modification.
Embodiment two：Copper nano-cluster is synthesized and electrochemical quantitative is characterized
Take the mM ascorbic acid solutions of 40 μ L 10 and 320 μ L reaction buffers（20 mM MOPS, 300 mM NaCl and
2 mM MgCl2, pH 7.5）Mixing, then toward the copper ion solution that 40 μ L various concentrations are added in the system, stand 20 minutes.
The gold electrode that double-stranded DNA is modified is put into above-mentioned mixed solution, is reacted 30 minutes at room temperature.After reaction terminates, ultra-pure water is used
Rinse electrode and dried up with nitrogen, to remove copper ion of the unnecessary absorption in electrode surface.Then, electrode is immersed in 200
The copper nano-cluster that lysis electrodes surface is synthesized in the M hydrochloric acid solutions of μ L 0.1.After 2 hours, by above-mentioned solution and 4.8 mL 0.5
M NaAc-HAc buffer solutions are mixed, and carry out Electrochemical Detection in this, as electrolyte solution.
Associated nucleic acid sequences are as follows：
P1 chain-orderings are：5'-TACTCATACGCTCATACGTTCATCACGACTAAAAA-C6-SH-3'。
P2 chain-orderings are：5'- AGTCGTGATGAACGTATGAGCGTATGAGTA-3'.
Electrochemical Detection specific steps：Deposited first under -1.2 V voltages 8 minutes, then DPV scannings obtain corresponding electricity
Chemical data；DPV tests design parameter：The V of initial potential 0.1, terminates the V of current potential 0.35, the mV of pulse amplitude 50, pulse week
The ms of phase 200.
As shown in Fig. 1 curves a, when copper ion is not present in reaction solution, without obvious in the DPV collection of illustrative plates finally given
Electrochemical response peak, this is due to that now electrode surface does not form copper nano-cluster.And work as in reaction solution and there is copper ion
When, DPV collection of illustrative plates obtains an obvious feature redox peaks near 0.22 V, and the peak current absolute value is with copper ion
Concentration increases and increased（Curve b to f）.Result above shows by a series of steps such as dissolving with hydrochloric acid, electro-deposition and DPV scannings
Suddenly, it is possible to achieve the quantitatively characterizing of the copper nano-cluster synthesized to electrode surface.
Embodiment three：The detection of various concentrations glutathione
Take the mM ascorbic acid solutions of 40 μ L 10 and 320 μ L reaction buffers（20 mM MOPS, 300 mM NaCl and
2 mM MgCl2, pH 7.5）Mixing, then contain 10 μM of copper ions and various concentrations gluathione toward 40 μ L are added in the system
Peptide（0 nM, 1 nM, 5 nM, 10 nM, 100 nM, 1 μM and 10 μM）Mixed solution to be measured, react at room temperature 20 minutes.With
Afterwards, the gold electrode that double-stranded DNA is modified is put into above-mentioned mixed solution, Electrochemical Detection is carried out after reacting 30 minutes at room temperature,
Specific detecting step is identical with embodiment two.
Fig. 2 curves a shows the gold electrode of double-stranded DNA modification in the reaction system of ascorbic acid and copper ion is comprised only
Effect a period of time simultaneously scans obtained DPV collection of illustrative plates after certain processing.There it can be seen that the double-strand that electrode surface is fixed
The template that DNA molecular can be synthesized as copper nano-cluster, and the generation of electrode surface copper nano particles can cause in DPV collection of illustrative plates
There is obvious electrochemical response.And when there is 1 μM of glutathione in system, the obvious decrease of DPV responses finally given
（Fig. 2 curves b）, this is due to that glutathione can be combined with copper ion present in solution, and then inhibits copper nano-cluster to exist
The formation of electrode surface.
As shown in figure 3, with the raising of glutathione concentrations, electrochemical response is gradually reduced in DPV collection of illustrative plates, this explanation with
The increase of glutathione concentrations, increasing copper ion is combined with glutathione, and then cause the copper of electrode surface formation
Nano-cluster is fewer and fewer.
DPV peak point currents and glutathione concentrations mapping are produced into Fig. 4.In addition, Fig. 4 insertion figure is shown, work as gluathione
When peptide concentration changes between 1 ~ 1000 nM, good linear pass is presented in logarithm value and the DPV peak point currents of glutathione concentrations
System, the foundation that can be quantitatively detected as glutathione.The minimum detectability of glutathione is about 0.42 nM.
Example IV：The special Journal of Sex Research of bioelectrochemical sensor
In order to verify the specificity of this bioelectrochemical sensor, we use other amino acid（Alanine, phenylalanine,
Glutamic acid etc.）It is that 10 μM of interference amino acid carry out Electrochemical Detection to concentration respectively according to above-mentioned experimental method as control.
As shown in figure 5, when containing 1 μM of glutathione in solution, the DPV peak currents absolute value of gained is minimum, about 0.16 μ A, and
DPV peak currents absolute value is all larger during containing other interference amino acid, close during with blank control, illustrates this bioelectrochemical sensing
Device has very high selectivity and specificity for glutathione.
Result above shows that this biology sensor has selectivity well and specificity for glutathione, and design is thought
Road is simple, with low cost, convenient experimental operation, testing result are sensitive, has very big in Biochemical Research and clinical analysis field
Potential using value.It is that the sensor on being prepared with double-strand modified gold electrode carries out detection GSH not find patent.
<120>Detect electrochemica biological sensor of glutathione and preparation method thereof
<160> 2
<210> 1
<211> 35
<212> DNA
<213>Artificial sequence
<400> 1
5'-TACTC ATACG CTCAT ACGTT CATCA CGACT AAAAA-C6-SH-3'
<210> 2
<211> 30
<212> DNA
<213>Artificial sequence
<400> 2
5'- AGTCG TGATG AACGT ATGAG CGTAT GAGTA-3'
Claims (4)
1. a kind of electrochemica biological sensor for detecting glutathione, is three-electrode system sensor, wherein being platinum electricity to electrode
Pole, reference electrode is saturated calomel electrode, and working electrode is gold electrode, it is characterised in that being modified with described gold electrode can
The DNA double chain of template is synthesized as copper nano-cluster, and the double-strand is complementary structure；By to working electrode surface copper nano-cluster
Quantitative analysis, realizes the indirect detection to glutathione；
Described DNA double chain is hybridized by P1 chains, P2 chains to be formed, and the sequence of wherein P1 chains is：5'-TACTCATACGCTCATACGTT
CATCACGACTAAAAA-C6The sequence of-SH-3', P2 chain is：5'- AGTCGTGATGAACGTATGAGCGTATGAGTA-3'.
2. a kind of preparation method of biology sensor according to claim 1, it is characterised in that prepare the work of the sensor
Make electrode, concretely comprise the following steps：
A) treated gold electrode is placed in 0.5MH2SO4In, cyclic voltammetry scan is carried out in 0~1.6V voltage ranges, speed is swept
100 mV/s are set to, until reaching stabilization；Drying is stand-by；
B) gold electrode obtained by step a is immersed in into DNA to fix in cushioning liquid, after standing 15 ~ 18 hours at room temperature, then be immersed in
Lucifuge is reacted 0.5~2.0 hour in the 1 mM sulfydryl hexanol aqueous solution, and with ultrapure water, drying obtains the modification of P1 chains
Gold electrode；Described DNA is fixed in cushioning liquid containing the P1 chains, 10 mM Tris-HCl, 1 mM that concentration is 1 μM
EDTA, 10 mM TCEP and 0.1 M NaCl, the pH value of solution is 7.4；
C) gold electrode modified through P1 chains obtained by step b is immersed in DNA hybridization buffer liquid, 4 DEG C of standings are used after 1 ~ 2 hour
Ultrapure water, drying obtains the gold electrode of complete double-stranded DNA modification；Described DNA hybridization buffer solution is 10 mM
PH 7.4 phosphate buffer, wherein being 1 μM of P2 chains and 1 M NaCl containing concentration.
3. method according to claim 2, it is characterised in that the processing method of described gold electrode is concretely comprised the following steps：
Pending gold electrode surfaces drop 20 μ L Piranha solution, the i.e. volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 3:1 solution, instead
Answer 2 minutes, nitrogen drying clean with ultrapure water；After gold electrode is polished 2 minutes on 5000 mesh sand paper, containing
Granularity is respectively 1 μm, 0.3 μm, be polished to minute surface successively on the silk of the mortar of 0.05 μm of aluminum oxide, then ethanol,
It is ultrasonic 2 minutes successively in ultra-pure water, remove impurity.
4. a kind of detection method of glutathione, using biology sensor according to claim 1, it is characterised in that the party
Method is concretely comprised the following steps：
A) appropriate ascorbic acid powder is weighed, 10mM is diluted to ultra-pure water, takes 40 μ L to be mixed with 320 μ L reaction buffers, then
The mixed solution to be measured that 40 μ L contain 10 μM of copper ions and various concentrations glutathione is added into the buffer solution, is reacted at room temperature
20 minutes；Contain MOPS, 300 mM NaCl that concentration is 20 mM and 2 mM MgCl in described reaction buffer2, solution
PH value be 7.5；
B) the working electrode gold electrode in biology sensor is put into the mixed solution obtained by step a at once, reacted at room temperature
30 minutes；After being dried up with ultrapure water and with nitrogen, working electrode is immersed in the M hydrochloric acid solutions of 200 μ L 0.1 and dissolved
The copper nano-cluster of electrode surface synthesis；After reaction 2 hours, reaction resulting solution is buffered with the M NaAc-HAc of 4.8 mL 0.5
Liquid is mixed, and carries out Electrochemical Detection in this, as electrolyte solution；Electrochemical Detection is concretely comprised the following steps：First in -1.2 V electricity
Pressure deposition 8 minutes, then obtains corresponding electrochemical data with differential pulse voltammetry DPV scannings；The specific ginseng of wherein DPV experiments
Number is：The V of initial potential 0.1, terminates the V of current potential 0.35, the mV of pulse amplitude 50, the ms of pulse period 200.
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| CN106282323B (en) * | 2015-05-29 | 2019-08-09 | 南京理工大学 | High-sensitivity DNA fluorescence analysis method for generating copper nanoparticles based on polythymine as template |
| CN105628659A (en) * | 2015-12-21 | 2016-06-01 | 大连理工大学 | Method for detecting lead ions and zinc ions |
| CN106093158B (en) * | 2016-05-07 | 2018-10-23 | 上海大学 | Glutathione detection biosensor, preparation method and its detection method |
| CN106525947B (en) * | 2016-09-21 | 2019-01-11 | 广西师范学院 | The method for detecting solution Glutathione peptide concentration |
| CN109338014B (en) * | 2018-10-19 | 2020-06-02 | 深圳市老年医学研究所 | DNA circulation induction open type DNA fluorescence nano robot construction method |
| CN109253993B (en) * | 2018-10-25 | 2021-03-23 | 中国石油大学(华东) | Nano fluorescent probe and preparation method and application thereof |
| CN109374698A (en) * | 2018-11-06 | 2019-02-22 | 杭州电子科技大学 | A method of based on the 2.5D electrochemistry fingerprint identification fleece-flower root or RADIX POLYGONI MULTIFLORI PREPARATA |
| CN112342272B (en) * | 2020-11-06 | 2022-09-16 | 济南大学 | Biosensor for detecting glutathione based on DNA nano machine |
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