CN103439319B - Carbon nano-particles modified electrode electrochemiluminescence measures the method for bleomycin - Google Patents
Carbon nano-particles modified electrode electrochemiluminescence measures the method for bleomycin Download PDFInfo
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- CN103439319B CN103439319B CN201310396240.3A CN201310396240A CN103439319B CN 103439319 B CN103439319 B CN 103439319B CN 201310396240 A CN201310396240 A CN 201310396240A CN 103439319 B CN103439319 B CN 103439319B
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Abstract
A kind of detection method of bleomycin (BLMs) content, belongs to electrochemiluminescence and sensor technical field.Electrochemiluminescence reagent marker DNA is utilized to prepare DNA probe (Ru-DNA), by carboxylated carbon nano-particles modified electrode, by the Competition between electrostatic repulsion and pi-pi accumulation effect, DNA and carbon nano-particles non-covalent bond self assembly principle is utilized to construct carbon nano-particles modified electrode electrochemiluminescence biology sensor.By object bleomycin and DNA probe effect, cause DNA to be cut, be adsorbed on DNA probe on carbon nano-particles modified electrode and reduce, the weak electrochemical luminescence signals of generation, realizes the mensuration to bleomycin with this.This method has simply, advantage fast.
Description
Technical field
The invention belongs to analytical chemistry and electrochemical luminous sensor field, being specially a kind of preparation method of the carbon nano-particles modified electrode electrochemiluminescence biology sensor for measuring bleomycin, and measure method and the application of bleomycin.
Technical background
For modern times biochemical subject and biomedical research, sensitive, the Measurement accuracy protein relevant with disease is vital in a lot, particularly for cancer early sign albumen detection and precisely prediction have great importance.Immune detection is a kind of strong analysis determining technology, and it has been widely used in the detection analysis of tumor marker.Because antibody has high specific and strong recognition reaction, be thus used as recognition element.But due to the defect of antibody in the stability and clinical manipulation of its production, product, people are seeking its substitute.
DNA biosensor a kind ofly detectablely optical, electrically can wait be transformed into the interactional object of DNA for the sensing device of signal, utilizes the interaction of DNA and object can set up many detection techniques for life science.DNA biosensor is a kind of strong analysis test method, can substitute traditional analytical approach set up based on antigen-antibody in many aspects.DNA biosensor is the brand-new biology sensor developed rapidly, open molecular biology and galvanochemistry, the recent studies on field of the subjects such as spectroscopy, the research for life science provides new technology, new method, has profound significance to the research of clinical medicine and genetic engineering.
Electrochemiluminescence (electrogenerated chemiluminescence), be called for short ECL, that the system containing chemiluminescent substance by electrode pair applies certain voltage or by certain electric current, there is chemical reaction between anodizing reduzate or between anodizing reduzate and other coexisting substances of system and generate the intermediate state material of certain instability, this substance decomposition and the chemiluminescence phenomenon produced.Electrochemiluminescence technology is the detection technique that galvanochemistry combines with chemiluminescence, this technology had both been integrated with advantage that is luminous and electrochemical analysis techniques, have again the two combine produce controllability, selectivity, favorable reproducibility, highly sensitive, detectability is low and the new advantage such as dynamic response wide ranges.
Bleomycin (Bleomycins, BLMs, BLM) is a class glycopeptide antibiotics.It is that Japanese Scientists Mei Ze shore was separated first in 1996 and obtains from the nutrient solution of streptomyces verticillatus.Thin bleomycin at oxygen and redox metal ion (as Fe
2+deng) existence under optionally can cut off single stranded DNA or double-stranded DNA, thus cancer cell to be killed.Based on this mechanism, the compound of thin bleomycin and metallic ion is widely used in the supplemental treatment of the kinds cancers such as cutaneum carcinoma, lung cancer, the cancer of the esophagus, the cancer of the brain.The assay method of the bleomycin reported at present has fluorescence method (Feng Li, Yan Feng, Can Zhao, Peng Li and Bo Tang, A sensitive graphene oxide – DNA based sensing platform for fluorescence " turn-on " detection of bleomycin, Chem.Comm., 2012,48:127; Yoshitsugu Akiyama, Qian Ma, Erin Edgar, Andrei Laikhter and Sidney M Hecht, A novel DNA hairpin substrate for bleomycin, Org.Lett., 2008,10:2127) and (Honglan Qi, Xiaoying Qiu, the Chen Wang such as Electrochemiluminescince, Qiang Gaoand Chengxiao Zhang, Anal.Methods, 2013,5:612).The present invention establishes a kind of carboxylated carbon nano-particles modified gold electrode electrochemiluminescence biology sensor, and measures bleomycin with it.Provide a kind of simple and sensitive electrochemiluminescence sensing technology, utilize and present invention achieves the mensuration of bleomycin.
Summary of the invention
For the demand of the deficiencies in the prior art and this area investigation and application, the object of this invention is to provide a kind of simple and sensitive electrochemiluminescence sensing technology, utilize the mensuration that present invention achieves bleomycin; The present invention simultaneously also may be used on other have cutting action protein-based antibiotic mensuration to DNA, also can expand to multi-functional instant pick-up unit easily.
Object of the present invention is achieved through the following technical solutions: the method for carbon nano-particles modified electrode electrochemiluminescence biosensor assay bleomycin, specifically comprises the following steps:
The foundation of carbon nano-particles modified electrode electrochemiluminescence biology sensor, is characterized in that specifically comprising the following steps:
Prepared by carboxylated carbon nano-particles (cCNP): by 0.1 ~ 1.0g polyvinyl alcohol dissolution obtained homogeneous phase solution in 10ml water, then puts into micro-wave oven (600W) and heats 9.5 minutes (min) and change to solution colour.Above-mentioned solution is removed impurity with the centrifugal 30min of 13000rpm, obtains carbon nano-particles;
React 8 hours (h) under 100 degrees Celsius after the nitric acid of 0.1 ~ 2.0 gram of carbon nano-particles and 0.5mL 63% and 0.5mL dimethyl formamide are mixed, obtain carboxylated carbon nano-particles;
Described electrochemiluminescence probe, concrete preparation process is as follows:
Preferably, 200 μ L 2 OD DNA are joined 200 μ L 1.0 × 10
-3mol/L Ru (bpy)
2(dcbpy) in NHS.Vibrate under room temperature 6 ~ 18h.Subsequently, add 100 μ L 3mol/L sodium acetates and the cold absolute ethyl alcohol of 2.0mL in this solution, solution is at-16 DEG C of cooling 24h.Then centrifugal 30min at 12000 rotating speeds and-4 DEG C.The cold ethanol purge of sediment 1mL three times, removes unreacted Ru (bpy)
2(dcbpy) NHS.Obtain Ru (bpy)
2(dcbpy) DNA probe (electrochemiluminescence probe) of NHS mark dissolves with 1.0mL 0.10mol/L phosphate buffer solution, is stored in-18 DEG C for subsequent use;
Preferably, described aminated dna Sequence is: 5'-CGCTTTAAAAAAAGTG-(CH
2)
6-NH
2-3'(DNA, SEQ ID NO:1).
Prepared by modified electrode, concrete preparation process is as follows:
Gold electrode through 1.0 μm, 0.3 μm, the α-A1 of 0.05 μm
2o
3after burnishing powder polishing, rinse well with redistilled water, and in ultrasound bath ultrasonic 5min, dry up with high pure nitrogen, for subsequent use;
The gold electrode handled well is immersed 100 μ L (10
-4m) in mercaptoethylmaine, after fixing 2 ~ 8h (37 DEG C), secondary is rinsed with phosphate buffer solution, get the carboxylated carbon nano-particles solution of 1mL, add NHS 3.6mg, EDC 7.2mg, at 37 DEG C, activate 1h, more above-mentioned electrode is immersed, reaction is spent the night, obtained carbon nano-particles modified electrode;
Utilize the Competition between electrostatic repulsion and pi-pi accumulation effect, obtain carbon nano-particles modified electrode electrochemiluminescence biology sensor.
The method of carbon nano-particles modified electrode electrochemiluminescence biosensor assay bleomycin, is characterized in that specifically comprising the following steps:
Preferably, in 100 μ L electrochemiluminescence probes, the bleomycin sample solution of variable concentrations and the Fe of 0.1mM is added
2+, then modified electrode is immersed reaction a period of time, takes out electrode and measure electrochemical luminescence signals according to a conventional method, according to electrochemical luminescence signals, bleomycin is quantitatively detected.
Compared with prior art, tool has the following advantages and beneficial effect in the present invention:
By the Competition between electrostatic repulsion and pi-pi accumulation effect, DNA and carbon nano-particles non-covalent bond self assembly principle is utilized to construct carbon nano-particles modified electrode electrochemiluminescence biology sensor;
The carbon nano-particles modified electrode electrochemiluminescence biology sensor built is utilized to establish a kind of new method detecting bleomycin.The method that this design adopts has simply, advantage fast.Therefore, the electrochemical luminous sensor that the present invention relates to embodies good development prospect in the research method building detection object.
Accompanying drawing explanation
Fig. 1 is carbon nano-particles modified electrode electrochemiluminescence biology sensor and measures bleomycin schematic diagram.
Fig. 2 is that modified electrode is at bleomycin and probe, Fe
2+in solution after effect, soak time is to electrochemical luminescence signals (Δ I
eCL) interact relation figure.
Fig. 3 is the canonical plotting of electrochemiluminescence intensity and bleomycin concentration.
Embodiment
Be below the specific embodiment that the present invention relates to, technical scheme of the present invention is done to describing further, but protection scope of the present invention be not limited to these embodiments.Every do not deviate from the present invention's design change or equivalent substituting include within protection scope of the present invention.
Embodiment
1. experimental section
1.1 instruments and reagent
1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC), N-hydroxy-succinamide (NHS), be purchased from Tianjin BASF Chemical Co., Ltd.; Ru (bpy)
2(dcbpy) NHS, HS-(CH
2)
6-NH
2be purchased from Sigma-Aldrich.
DNA artificial sequence synthetic used (match Parkson, Beijing bioengineering company limited buys) is as follows:
5'-CGCTTTAAAAAAAGTG-(CH
2)
6-NH
2-3'(DNA，SEQ ID NO：1)。
CHI660B electrochemical workstation (Shanghai Chen Hua instrument company); Anke-TGL-16C flies father-in-law's board supercentrifuge (Shanghai City An Ting scientific instrument factory); Experiment adopts three-electrode system: gold electrode and modified gold electrode are working electrode, and Ag/AgC1 (saturated KCl) electrode is contrast electrode, and platinum electrode is to electrode.
1.2 experimental procedure
1.2.1 the preparation of electrochemiluminescence probe
200 μ L 2OD DNA add 200 μ L 1.0 × 10
-3mol/L Ru (bpy)
2(dcbpy) NHS.Vibrate under room temperature 6 ~ 18h.Subsequently, add 100 μ L 3mol/L sodium acetates and the cold absolute ethyl alcohol of 2.0mL in this solution, solution is at-16 DEG C of cooling 24h.Then centrifugal 30min at 12000 rotating speeds and-4 DEG C.The cold ethanol purge of sediment 1mL three times, removes unreacted Ru (bpy)
2(dcbpy) NHS.Obtain Ru (bpy)
2(dcbpy) DNA probe (electrochemiluminescence probe) of NHS mark dissolves with 1.0mL 0.10mol/L phosphate buffer solution, is stored in-18 DEG C for subsequent use.
1.2.2 the preparation of carboxylated carbon nano-particles
(1) preparation of carbon nano-particles: by 0.5g polyvinyl alcohol dissolution obtained homogeneous phase solution in 10ml water, then puts into micro-wave oven (600W) and heats 9.5min and change to solution colour.Above-mentioned solution is removed impurity with the centrifugal 30min of 13000rpm, then uses dialysis membrane (molecular cut off 2000) to dialyse to it in pure water, continue 4 days to remove residual polyethylene alcohol, obtain carbon nano-particles.
(2) carbon nano-particles is utilized to prepare carboxylated carbon nano-particles: after the nitric acid of 1 gram of carbon nano-particles and 0.5mL 63% and 0.5mL dimethyl formamide being mixed, under 100 degrees Celsius, to react 8h.Then, product utilization 0.22 μM of ultra filtration membrane is filtered, by centrifugal for filtrate 10min (under 14000rmp condition), and with second distillation water washing three times, obtain carboxylated carbon nano-particles, being then dispersed in redistilled water and being prepared into concentration is 2.0mg/mL solution.
1.2.3 the preparation of carbon nano-particles modified electrode
(1) pre-service of gold electrode
Gold electrode through 1.0 μm, 0.3 μm, the α-A1 of 0.05 μm
2o
3after burnishing powder polishing, rinse well with redistilled water, and in ultrasound bath ultrasonic 5min, dry up with high pure nitrogen.Employing three-electrode system detects, and working electrode is gold electrode, and be platinum electrode to electrode, contrast electrode is Ag/AgCl electrode, at K
3[Fe (CN)
6] in solution, arranging voltage is 0 ~ 0.8V, carries out cyclic voltammetric (CV) scanning to gold electrode.If redox current peak is in 0 ~ 100mV, then illustrate that electrode surface is processed.Otherwise again process, till meeting the requirements.After having surveyed, rinse electrode with intermediate water, dry up electrode surface, for subsequent use.
(2) preparation of modified electrode
The above-mentioned gold electrode handled well is immersed 100 μ L (10
-4m) in mercaptoethylmaine, after fixing 4h (37 DEG C), secondary is rinsed with phosphate buffer solution, get the carboxylated carbon nano-particles solution of 1mL, add NHS 3.6mg, EDC 7.2mg, 1h is activated at 37 DEG C, be immersed by above-mentioned electrode, reaction is spent the night again, obtained carbon nano-particles modified electrode.
1.2.4 the detection of bleomycin
Bleomycin solution and the 0.1mM Fe of variable concentrations is added in 100 μ L electrochemiluminescence probes
2+, reaction 30min.Then carbon nano-particles modified electrode is immersed, at 37 DEG C, reacts 7min.Electrode is rinsed three times with the phosphate buffer solution (pH 7.4) of 10mM.Using this electrode as working electrode, be platinum electrode to electrode, contrast electrode is Ag/AgCl electrode, take electrochemical luminescence signals as analytic signal, carries out the mensuration of bleomycin.Optimum configurations is: high pressure 800V, and number of stages of amplification is 3, and controlling potential is 0-1.30V.
1.3 results and discussion
Experimental principle
As shown in Figure 1, in the invention, utilize the cutting action after molecular recognition, thus produce signal intensity, establish the electrochemiluminescence biology sensor measuring bleomycin accordingly.Utilizing single stranded DNA for molecular recognition element, is analyze determination object, to this invention as described checking with bleomycin.
Devise DNA partial sequence (5'-CGCTTTAAAAAAAGTG-(CH
2)
6-NH
2-3'), by an end with Ru (bpy)
2(dcbpy) NHS carries out marking as electrochemical luminescence signals probe.When bleomycin exists, Ru-DNA is cut, formation sheet segment DNA, and it reduces at carbon nano-particles modified electrode surface excess, and electrochemical luminescence signals is weak.When bleomycin does not exist, Ru-DNA in solution is not cut, and due to electrostatic repulsion and the pi-pi accumulation effect of carbon nano-particles and DNA, Ru-DNA is attracted to carbon nano-particles modified electrode surface, electrochemical luminescence signals is strong, realizes the mensuration to bleomycin accordingly.
As shown in Figure 2, carbon nano-particles modified electrode is immersed in DNA probe, Fe
2+, after bleomycin sample effect solution min to electrochemical luminescence signals (Δ I
eCL) there is impact.Within the scope of 1 ~ 5min, the increase of electrochemical luminescence signals intensity soak time and strengthening, after 5min, electrochemical luminescence signals intensity slowly increases, until reach maximal value during 7min, after being greater than 7min, change is little.Therefore determine that carbon nano-particles modified electrode is immersed in DNA probe, Fe
2+, the Best Times of solution is 7min after bleomycin sample effect.
The impact that metallic ion reacts bleomycin cutting DNA is have studied in the present embodiment.Fe is added respectively in reaction system
2+, Co
2+, Zn
2+, Ba
2+, Mg
2+, Ca
2+, Mn
2+during metallic ion, experiment discovery only has Fe
2+have obvious effect, other metallic ion is then inoperative to bleomycin cutting DNA.This shows that the oxidation cutting action of bleomycin and DNA needs Fe
2+ion forms compound as accessory factor thus DNA chain is ruptured.
The range of linearity and the detection limit of the present embodiment are as follows: preferred, in optimal conditions, test the relation investigated between variable concentrations bleomycin and electrochemiluminescence intensity, obtain the typical curve, the range of linearity and the linear equation that detect bleomycin.When the concentration of bleomycin is 1.0 × 10
-10~ 3.0 × 10
-7time between M, the electrochemiluminescence intensity of system increases (as shown in Figure 3) along with the increase of bleomycin concentration.Nonlinear regression equation is Δ I
eCL=-5618.44*exp (-C/79.05)-1156.30*exp (-C/3.67)+6933.49 (Δ I
eCLfor the electrochemiluminescence intensity of system; C is the concentration of bleomycin, 10
-9m; N=7, R=0.9980).The range of linearity of bleomycin is 1.0 × 10
-10~ 3.0 × 10
-8m, equation of linear regression is Δ I
eCL=198.75C+120.72.The method detects and is limited to 4.0 × 10
-11m (3 σ).To concentration 5.0 × 10
-9the RSD that the bleomycin of M carries out 7 parallel replications is 3.5%, shows that the present invention has good reappearance.
Claims (5)
1., for measuring the preparation method of the carbon nano-particles modified electrode electrochemiluminescence biology sensor of bleomycin, it is characterized in that, comprise the following steps:
A, by 0.1 ~ 1.0g polyvinyl alcohol dissolution obtained homogeneous phase solution in 10ml water, then puts into micro-wave oven and heats 15min(minute) change to solution colour, above-mentioned solution is removed impurity with the centrifugal 30min of 13000rpm, obtains carbon nano-particles; React 8 hours (h) under 100 degrees Celsius after the nitric acid of 0.1 ~ 2.0 gram of carbon nano-particles and 0.5mL 63% and 0.5mL dimethyl formamide are mixed;
200 μ L 2OD DNA are joined 200 μ L 1.0 × 10 by b
-3mol/L Ru (bpy)
2(dcbpy) in NHS, vibrate under room temperature 6 ~ 18h, subsequently, 100 μ L 3mol/L sodium acetates and the cold absolute ethyl alcohol of 2.0mL is added in this solution, solution is at-16 DEG C of cooling 24h, then the cold ethanol purge of centrifugal 30min, sediment 1mL three times at 12000 rotating speeds and-4 DEG C, removes unreacted Ru (bpy)
2(dcbpy) NHS, obtains Ru (bpy)
2(dcbpy) the electrochemiluminescence probe of NHS mark, then dissolves with 1.0mL0.10mol/L phosphate buffer solution;
C gold electrode through 1.0 μm, 0.3 μm, the α-A1 of 0.05 μm
2o
3after burnishing powder polishing, rinse well with redistilled water, and in ultrasound bath ultrasonic 5min, dry up with high pure nitrogen, for subsequent use, the gold electrode handled well is immersed 100 μ L 10
-4in the mercaptoethylmaine of M, fix 2 ~ 8h at 37 DEG C after, secondary is rinsed with phosphate buffer solution, get the carboxylated carbon nano-particles solution of 1mL, add N-hydroxy-succinamide (NHS) 3.6mg, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) 7.2mg, 1h is activated at 37 DEG C, again above-mentioned electrode is immersed, reaction is spent the night, obtained carbon nano-particles modified electrode, utilize the Competition between electrostatic repulsion between electrochemiluminescence probe and carbon nano-particles modified electrode and pi-pi accumulation effect, obtain carbon nano-particles modified electrode electrochemiluminescence biology sensor.
2. the method for the electrochemiluminescence biosensor assay bleomycin utilizing the preparation method described in claim 1 to prepare, is characterized in that, comprise the following steps:
Bleomycin solution and the 0.1mM Fe of variable concentrations is added in 100 μ L electrochemiluminescence probes
2+then modified electrode is immersed reaction 7min, rinses electrode three times with the phosphate buffer solution of pH 7.4 10mM, then carry out electrochemiluminescence mensuration, according to effect rear electrode surface electrochemistry electrochemical luminescence signals that luminescence probe produces, bleomycin is quantitatively detected.
3. the method measuring bleomycin as claimed in claim 2, described electrochemiluminescence measures and is specially: adopt three-electrode system to detect, working electrode is gold electrode, be platinum electrode to electrode, contrast electrode is Ag/AgCl electrode, optimum configurations is: high pressure 800V, and number of stages of amplification is 3, and controlling potential is 0-1.30V.
4. preparation method as claimed in claim 1, is characterized in that described DNA partial sequence is 5'-CGCTTTAAAAAAAGTG-(CH
2)
6-NH
2-3'.
5. preparation method as claimed in claim 1, is characterized in that described DNA partial sequence be 3' end is amido modified.
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| CN104007152B (en) * | 2014-06-18 | 2016-05-25 | 青岛科技大学 | Measure the method for electrochemical sensor and the mensuration DNA of DNA based on nano platinum particle catalytic electrochemical cycle signal amplifying technique |
| CN105385770B (en) * | 2015-12-18 | 2018-09-28 | 山东大学 | The Dual-ring hairpin probe for detecting bleomycin mediates label-free strand displacement amplification method |
| CN105950757B (en) * | 2016-06-17 | 2019-11-22 | 山东大学 | Method based on the cascade amplification strategy detection bleomycin that Dual-ring hairpin probe and enzyme mediate |
| CN110426440B (en) * | 2019-07-16 | 2022-02-01 | 曲阜师范大学 | Photoelectrochemistry biosensor and detection method of photoelectrochemistry biosensor for BLM |
| CN114487066A (en) * | 2022-01-27 | 2022-05-13 | 上海市肿瘤研究所 | Ultrasensitive DNA-biomacromolecule sensor, construction and application thereof |
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