CN103616357A - Visual biosensor device and preparation method thereof - Google Patents
Visual biosensor device and preparation method thereof Download PDFInfo
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- CN103616357A CN103616357A CN201310626273.2A CN201310626273A CN103616357A CN 103616357 A CN103616357 A CN 103616357A CN 201310626273 A CN201310626273 A CN 201310626273A CN 103616357 A CN103616357 A CN 103616357A
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Abstract
The invention discloses a visual biosensor device and a preparation method thereof. According to the invention, excellent electrical and optical properties and advantages in aspects of biology of GQD (graphene quantum dots) multicolor fluorescence are integrated, GQD samples with different sizes and different luminous colors are prepared by adopting a wet chemistry method, chemical characteristics of the surfaces and the edges of GQDs and assembly of subsequent biomolecules are fully considered, proper chemical groups are selected to perform functional treatment on the surfaces and edges of the GQDs, and different biomolecules are respectively assembled at different fluorescence GQDs to establish a biosensor. The biomolecules have different influences on the GQD fluorescence, a quantitative association exists between the characteristic parameters such as spectral intensity and peak position and the concentrations and types of the biomolecules, visual molecule detection is directly performed on the basis, the preparation method can be applied to biomedicine detection and analysis, and accurate reference is provided for disease diagnosis and treatment. Moreover, multiple biomolecules are conveniently detected.
Description
technical field
The invention belongs to biosensor technique research field, refer in particular to a kind of visual biology sensor building with graphene quantum dot.
background technology
Detection technique of fluorescence is one of important means in biomedical detection always.In recent years, the good characteristic that semiconductor quantum spot size and spectrum are adjustable is more and more subject to biomedical researcher's attention, and at aspects such as molecular labeling, biological detection, medical imagings, has carried out a lot of discussions, has obtained many impressive progresses.Current reported work focuses mostly in CdSe, the semiconductor-quantum-point of the systems such as CdS, and these materials can run into poor stability while applying in biomedical environment, have bio-toxicity, poorly water-soluble, cell membrane penetrate the problems such as level is low.Design stability is luminous, biocompatibility is good, and can make the luminescence system of linear response, develops corresponding optics or spectroscopy detection method, is a research work highly significant.
On the other hand, the good optics and electronics characteristic of Graphene and derivant thereof, has been subject to the attention of people's height.Wherein graphene oxide (GO) has the electron configuration of sp2 and sp3 mixing, and sp2 and sp3 ratio are adjustable, the atom that this is unique and electronic structure, for the regulation and control of the function controlling of this two-dimensional network material, particularly photoelectric characteristic and utilization provide very abundant and physical basis flexibly.Based on this, closely continue to bring out out the report of graphene oxide and graphene quantum dot fluorescence one or two years, people can realize graphene quantum dot and the graphene oxide of different glow colors such as bluish-green grade at present.The quantum mechanics mechanism of further investigation graphene quantum dot multicolor fluorescence and the technology of luminous regulation and control, further expand it in the function and application in the fields such as photoelectron, biological electronics, will be a research topic highly significant.Meanwhile, graphene quantum dot also has very high specific surface, abundant surface state and good biocompatibility, this assembling that is biomolecule with detect the Fundamentals of Material Science that provide good, thereby make it become the important candidate material of bio-sensing.
The features such as enzyme biologic sensor of the prior art can be realized high selectivity and the high sensitivity that enzyme is measured substrate, combines again the fast response time of electrochemica biological sensor, easy and simple to handle, can Fast Measurement sample in a certain given compound concentration.But enzyme biologic sensor also exists many difficult points in development process, as need to find suitable immobilization material enzyme was fixed and is realized the response time of given compound short, the problems such as long service life.The gordian technique of biology sensor research is how biological components is fixed on matrix efficiently and stably.At present, the work such as the quantitative bioanalysis based on graphene quantum dot multicolor fluorescence and visible sensor structure are still rarely found in the world, particularly two-photon fluorescence and time resolution detect will become the visual angle of uniqueness of the present invention, believe the discussion that can carry out a series of novelties, and then the application of expanding the aspects such as biomedicine detection, imaging of Graphene, develop new biological sensing material and technology.
summary of the invention
The object of the present invention is to provide a kind of visual bio-sensing device and preparation method thereof, to find suitable immobilization material, enzyme was fixed and is realized the response time of given compound short, the object of long service life, further to expand the application of the aspect such as biomedicine detection, imaging of Graphene.
In order to solve above technical matters, the good photoelectric characteristic of graphene quantum dot multicolor fluorescence and the advantage of biology aspect thereof are merged in the present invention, analyze regulate and control method and the physical mechanism of yardstick, shape and the characteristics of luminescence of graphene quantum dot, inquire into the assemble method of biomolecule, and based on fluorescence spectrum, time resolved spectroscopy, two-photon fluorescence technology etc. characterization technique, build visual biology sensor, concrete technical scheme is as follows:
A kind of preparation method of visual bio-sensing device, it is characterized in that utilizing the fluorescent characteristic of graphene quantum dot to build visual biology sensor, thereby make visual bio-sensing device utilize visible change in fluorescence directly to obtain the concentration of material to be detected, specifically comprise the following steps:
Step 1, prepares the graphene quantum dot of different size, different fluorescence, and detailed process is as follows
Process one, adopt wet chemical method, take crystalline flake graphite as raw material, adopt Hummers legal system for graphite oxide: in ice-water bath, to assemble reaction bulb, add in the concentrated sulphuric acid of 46ml 98%, under magnetic agitation, add 2g crystalline flake graphite and 1g sodium nitrate solid mixture, slowly add 6g potassium permanganate, control temperature 10-15 ℃, stirring reaction 1.5h; Again beaker is placed in to 35 ℃ of waters bath with thermostatic control, in whipping process, adds deionized water, continue stirring reaction 30min; Control temperature at 95 ℃, reaction 30min obtains reactant liquor one again; With deionized water, reactant liquor one is diluted to 200ml, adds appropriate hydrogen peroxide, stir and to add fast response, with the rotating speed centrifugal treating 10min of 4000rpm, obtain reactant liquor two after waiting reaction to finish; Use hydrogen peroxide, watery hydrochloric acid and deionized water cyclic washing reactant liquor two, make PH=7 again, then be dried 48h under 80 ℃ of conditions, and grinding is sieved, and obtains graphite oxide, is placed in drying box and preserves;
Process two, takes in the water of the quality such as graphite oxide is scattered in, ultrasonic yellowly transparent colloidal solution, then add watery hydrochloric acid, after centrifugal treating, be dried to powder and obtain graphene oxide powder;
Process three, carries out thermal reduction by graphene oxide powder and obtains graphene film, and graphene film is obtained to solution one with 30ml red fuming nitric acid (RFNA) and 10ml concentrated sulphuric acid oxidation ultrasonic decomposition 15h; By solution one centrifugal filtration except disacidify, solution two soluble in water again, by the pH value of NaOH regulator solution two, to being more than or equal to 10, in reactor, 200 ℃ are carried out 10h hydrothermal reduction, with filtering with microporous membrane, obtain liquid graphene quantum dot;
Step 2, selects chemical group to process graphene quantum dot surface and limbic functionization, and the impact of the process of analytic functionization processing on graphene quantum dot fluorescence, and detailed process is as follows:
Process one, gets graphene quantum dot solution described in 20mL, and with HAc, being adjusted to pH value is 5-6;
Process two, then add 50mg alkyl amine and 20mL toluene, after mixing, put into 150 ℃ of reaction 6h of 50mL reactor and obtain solution three;
Process three, the upper toluene solution of draw solution three, under 80 ℃ of conditions, vacuum drying is removed unnecessary alkyl amine, water-soluble graphene quantum dots surface-COO-functional group makes it have good water-solublely, and easily to it, carries out surface-functionalized;
Step 3, builds visual biology sensor, and process is as follows
The assembling of fluorescence graphene quantum dot and biomolecule is built to biology sensor: after graphene quantum dot functionalization with functional group's meeting and biomolecule between produce extraordinary interaction and comprise hydrogen bond, π-πconjugation, thereby combine, fluorescence graphene quantum dot and biomolecule are assembled on electrode, form recognition component, form biology sensor with physics and chemistry transducer, signal amplifying apparatus.
Described biomolecule is glucose oxidase, CEA, CA19-9, any in DNA fragmentation and albumen.
Described chemical group is alkyl amine or lauryl amine.
The concentration of described hydrogen peroxide is 4-6%.
A visual bio-sensing device, is characterized in that: described bio-sensing device is utilize preparation method's preparation of a kind of visual bio-sensing device described in claim 1-4 and obtain.
principle of work of the present invention is:biomolecule in biology sensor can be combined into compound with measured target by identifying, as the combination of antibody and antigen, and the combination of enzyme and matrix, these biomolecule are influential to graphene quantum dot fluorescence.According to the variation of fluorescence, directly can obtain the information of measured target.
the present invention has beneficial effect.The present invention directly utilizes the fluorescence information of graphene quantum dot to carry out detection molecules, can be rapidly and obtain easily the information of target molecule; Utilize graphene quantum dot to build the rule that visual Molecular Detection and biosensor technique contribute to some vital movements of heightened awareness, understand various diseases genesis mechanism, promote the development of Clinics, and then advance and safeguard human health.The present invention will promote the expansion of the exploitation of Graphene photoelectric characteristic and biomedical applications function, and develop Novel visual biological detecting method, thereby provide important references for disease treatment.
Accompanying drawing explanation
Fig. 1 is the TEM figure of graphene quantum dot of the present invention.
Fig. 2 is the structural representation of the material identification original paper of biology sensor of the present invention.
Embodiment
Below in conjunction with specific embodiment, the present invention is more specifically described in detail, but embodiments of the present invention are not limited to this, for being dated especially technological parameter and method, can more solito technology carry out.
embodiment 1: the preparation of graphene quantum dot
The concrete preparation process of the present embodiment graphene quantum dot is as follows: take crystalline flake graphite as starting material, according to Hummer ' s method, prepare graphite oxide, then 25 mg graphite oxides are scattered in 25 mL water, ultrasonicly be dispersed into uniform yellow transparent colloidal solution, solution added to watery hydrochloric acid and be dried to powder after centrifugal.Graphene oxide powder is carried out in tubular furnace to 200 ℃ and carry out 2h thermal reduction graphene oxide sheet, get 30ml red fuming nitric acid (RFNA) and 10ml concentrated sulphuric acid oxidation ultrasonic decomposition 15h for 0.05g thermal reduction graphene film, the pH value of regulator solution is 8, in reactor, 200 ℃ are carried out 10h hydrothermal reduction and make graphene quantum dot, and the TEM figure of the graphene quantum dot obtaining as shown in Figure 1.
embodiment 2: take glucose oxidase as example structure biology sensor
The graphene quantum dot solution of the functionalization of 10 μ L is spun to glass-carbon electrode surface, at room temperature dry one the whole night, then activated electrode is surperficial, finally 10 μ L glucose oxidase suspending liquid are spun to electrode surface, thereby obtain the material identification original paper of enzyme biologic sensor, structure as shown in Figure 2, just can build enzyme biologic sensor.
Claims (5)
1. the preparation method of a visual bio-sensing device, it is characterized in that utilizing the fluorescent characteristic of graphene quantum dot to build visual biology sensor, thereby make visual bio-sensing device utilize visible change in fluorescence directly to obtain the concentration of material to be detected, specifically comprise the following steps:
Step 1, prepares the graphene quantum dot of different size, different fluorescence, and detailed process is as follows
Process one, adopt wet chemical method, take crystalline flake graphite as raw material, adopt Hummers legal system for graphite oxide: in ice-water bath, to assemble reaction bulb, add in the concentrated sulphuric acid of 46ml 98%, under magnetic agitation, add 2g crystalline flake graphite and 1g sodium nitrate solid mixture, slowly add 6g potassium permanganate, control temperature 10-15 ℃, stirring reaction 1.5h; Again beaker is placed in to 35 ℃ of waters bath with thermostatic control, in whipping process, adds deionized water, continue stirring reaction 30min; Control temperature at 95 ℃, reaction 30min obtains reactant liquor one again; With deionized water, reactant liquor one is diluted to 200ml, adds appropriate hydrogen peroxide, stir and to add fast response, with the rotating speed centrifugal treating 10min of 4000rpm, obtain reactant liquor two after waiting reaction to finish; Use hydrogen peroxide, watery hydrochloric acid and deionized water cyclic washing reactant liquor two, make PH=7 again, then be dried 48h under 80 ℃ of conditions, and grinding is sieved, and obtains graphite oxide, is placed in drying box and preserves;
Process two, takes in the water of the quality such as graphite oxide is scattered in, ultrasonic yellowly transparent colloidal solution, then add watery hydrochloric acid, after centrifugal treating, be dried to powder and obtain graphene oxide powder;
Process three, carries out thermal reduction by graphene oxide powder and obtains graphene film, and graphene film is obtained to solution one with 30ml red fuming nitric acid (RFNA) and 10ml concentrated sulphuric acid oxidation ultrasonic decomposition 15h; By solution one centrifugal filtration except disacidify, solution two soluble in water again, by the pH value of NaOH regulator solution two, to being more than or equal to 10, in reactor, 200 ℃ are carried out 10h hydrothermal reduction, with filtering with microporous membrane, obtain liquid graphene quantum dot;
Step 2, selects chemical group to process graphene quantum dot surface and limbic functionization, and the impact of the process of analytic functionization processing on graphene quantum dot fluorescence, and detailed process is as follows:
Process one, gets graphene quantum dot solution described in 20mL, and with HAc, being adjusted to pH value is 5-6;
Process two, then add 50mg alkyl amine and 20mL toluene, after mixing, put into 150 ℃ of reaction 6h of 50mL reactor and obtain solution three;
Process three, the upper toluene solution of draw solution three, under 80 ℃ of conditions, vacuum drying is removed unnecessary alkyl amine, water-soluble graphene quantum dots surface-COO-functional group makes it have good water-solublely, and easily to it, carries out surface-functionalized;
Step 3, builds visual biology sensor, and process is as follows
The assembling of fluorescence graphene quantum dot and biomolecule is built to biology sensor: after graphene quantum dot functionalization with functional group's meeting and biomolecule between produce extraordinary interaction and comprise hydrogen bond, π-πconjugation, thereby combine, fluorescence graphene quantum dot and biomolecule are assembled on electrode, form recognition component, form biology sensor with physics and chemistry transducer, signal amplifying apparatus.
2. the preparation method of a kind of visual bio-sensing device as claimed in claim 1, is characterized in that: described biomolecule is glucose oxidase, CEA, CA19-9, any in DNA fragmentation and albumen.
3. the preparation method of a kind of visual bio-sensing device as claimed in claim 1, is characterized in that: described chemical group is alkyl amine or lauryl amine.
4. the preparation method of a kind of visual bio-sensing device as claimed in claim 1, is characterized in that: the concentration of described hydrogen peroxide is 4-6%.
5. a visual bio-sensing device, is characterized in that: described bio-sensing device is utilize preparation method's preparation of a kind of visual bio-sensing device described in claim 1-4 and obtain.
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| CN104483310A (en) * | 2014-12-03 | 2015-04-01 | 济南大学 | Construction method of visual self-energized glucose biosensor |
| CN106596678A (en) * | 2017-02-16 | 2017-04-26 | 济南大学 | Preparation method of electrochemiluminescent biosensor based on polydopamine nano-microsphere loaded graphene quantum dot |
| CN108020533A (en) * | 2017-12-07 | 2018-05-11 | 广西大学 | Live body quantitative analysis method in situ based on the Fluorimetric Quenching Method of graphene quantum dot to plant roots table absorption polycyclic heteroaryl aromatic hydrocarbon |
| CN111678889A (en) * | 2020-07-13 | 2020-09-18 | 北京碳世纪科技有限公司 | Quantum dot and fluorescent molecule doped graphene biosensor for detecting trace viruses |
| CN113588735A (en) * | 2021-07-21 | 2021-11-02 | 江苏大学 | Construction method of novel photoelectric/visual dual-mode sensor and application of novel photoelectric/visual dual-mode sensor in vomitoxin detection |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104483310A (en) * | 2014-12-03 | 2015-04-01 | 济南大学 | Construction method of visual self-energized glucose biosensor |
| CN104483310B (en) * | 2014-12-03 | 2017-08-11 | 济南大学 | A kind of construction method for visualizing self energizing glucose biological sensor |
| CN106596678A (en) * | 2017-02-16 | 2017-04-26 | 济南大学 | Preparation method of electrochemiluminescent biosensor based on polydopamine nano-microsphere loaded graphene quantum dot |
| CN106596678B (en) * | 2017-02-16 | 2017-11-07 | 济南大学 | A kind of preparation method for the electrochemical luminescence biology sensor that graphene quantum dot is loaded based on poly-dopamine nanoparticle |
| CN108020533A (en) * | 2017-12-07 | 2018-05-11 | 广西大学 | Live body quantitative analysis method in situ based on the Fluorimetric Quenching Method of graphene quantum dot to plant roots table absorption polycyclic heteroaryl aromatic hydrocarbon |
| CN111678889A (en) * | 2020-07-13 | 2020-09-18 | 北京碳世纪科技有限公司 | Quantum dot and fluorescent molecule doped graphene biosensor for detecting trace viruses |
| CN111678889B (en) * | 2020-07-13 | 2023-05-02 | 北京碳世纪科技有限公司 | Quantum dot and fluorescent molecule doped graphene biosensor for detecting trace viruses |
| CN113588735A (en) * | 2021-07-21 | 2021-11-02 | 江苏大学 | Construction method of novel photoelectric/visual dual-mode sensor and application of novel photoelectric/visual dual-mode sensor in vomitoxin detection |
| CN113588735B (en) * | 2021-07-21 | 2023-12-22 | 深圳万知达科技有限公司 | Construction method of photoelectric/visual dual-mode sensor and application of photoelectric/visual dual-mode sensor in vomitoxin detection |
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Application publication date: 20140305 |