CN106770111A - A kind of cadmiumsulfide quantum dot detects the fluorescence analysis method of zinc ion concentration - Google Patents

A kind of cadmiumsulfide quantum dot detects the fluorescence analysis method of zinc ion concentration Download PDF

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CN106770111A
CN106770111A CN201611174362.8A CN201611174362A CN106770111A CN 106770111 A CN106770111 A CN 106770111A CN 201611174362 A CN201611174362 A CN 201611174362A CN 106770111 A CN106770111 A CN 106770111A
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quantum dot
zinc ion
fluorescence
ion concentration
cys
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田丹碧
甘建红
张凌华
朱杰
吴胜男
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Nanjing Tech University
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Nanjing Tech University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432Quenching

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  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The invention discloses a kind of fluorescence analysis method of cadmiumsulfide quantum dot quick detection zinc ion concentration, its Cleaning Principle is the cadmiumsulfide quantum dot (L Cys@CdS) that used quantum dot is surface modification L cysteines, bipyridyl ruthenium [Ru (bpy)2(dppz)]2+Molecule is adsorbed onto on the surface of quantum dot so that the fluorescence of quantum dot is quenched, due to Zn as quencher by electrostatic attraction2+Only there is enhancement effect of fluorescence to L Cys@CdS QDs, work as Zn2+When there is Competition and the bipyridyl ruthenium of quantum dot surface between, Zn2+Amino and carboxyl with L Cys surfaces form coordinate bond, because the active force of coordinate bond causes [Ru (bpy) more than electrostatic attraction2(dppz)]2+Molecule departs from the surface of quantum dot, so that the fluorescence of quantum dot recovers, the variable quantity and Zn of fluorescence intensity2+Concentration it is relevant, therefore can be used for detect Zn2+Concentration.Zinc ion detection method disclosed in the present invention is simple to operate, with low cost, it is not necessary to special instrument and equipment, and selectivity and sensitivity are significantly increased compared to conventional zinc ion detection means.

Description

A kind of cadmiumsulfide quantum dot detects the fluorescence analysis method of zinc ion concentration
Technical field
The invention belongs to nano biological sensor field, and in particular to a kind of cadmiumsulfide quantum dot detection zinc ion concentration Fluorescence analysis method.
Background technology
Zinc ion is second largest transition metal in human body, and vital effect is played in life system, is both made For the key structure of many protein is constituted, catalytic action is also played in many enzymes, it is also related to many cell processes.This Outward, zinc ion is considered as excessively poisonous in the environment, may cause Plant death, and pollute available soil.Meanwhile, Disorderly also relevant with several mental illnesses, such as Alzheimer's disease, epilepsy and cerebral ischemia etc. of zinc ion.Therefore, zinc ion Trace detection caused and widely paid close attention in chemistry and bio-science field.
The fluorescent optical sensor of many detection zinc ions is disclosed in the prior art, but the fluorescent optical sensor of report is mostly Chemical sensor based on quinoline, fluorescein, cumarin and naphthalimide etc..And these chemical sensors detection zinc from Many problems, such as building-up process complicated and time consumption can be run into subprocess, fluorescent yield is low, and stability is low, poor selectivity, detection limit It is low with sensitivity etc..In recent years, the sensor of the highly sensitive high selectivity of Development of Novel is extremely urgent to detect zinc ion.
The cadmiumsulfide quantum dot (L-Cys@CdS QDs) of Rosenzweig seminars report surface modification Cys is only There is enhancement effect of fluorescence to zinc ion and with good selectivity, such that it is able to realize detecting zinc ion (Anal.Chem., 2002,74 (19):5132-5138).Due to limited in one's ability, this inspection policies sensitivity of Fluorescence Increasing It is not high.
Bipyridyl ruthenium series compound has stronger binding ability to double chain DNA molecule, and scientists are it all the time The situation of change of DNA sequence dna in real-time tracking living cells is gone as molecular probe.Newest research work shows, works as bipyridyl ruthenium (II) when compound and quantum dot are combined by electrostatic attraction, can be by Photo-induced electron transfer effect by quantum dot Fluorescent quenching.In the presence of target analytes, either with quantum dot combine substitution bipyridyl ruthenium (II) compound or and Bipyridyl ruthenium (II) compound combines substitution quantum dot, and bipyridyl ruthenium (II) the distance between compound and quantum dot will all become Far, the fluorescence of quantum dot is recovered, and at this moment fluorescence signal is changed into " turn on " from " turn off ", such that it is able to target Thing carries out quantitative determination.
At present, the metal ions such as mercury ion, copper ion, zinc ion have been successfully applied to as fluorescence probe using quantum dot Detection, and realize having not been reported the detection of zinc ion using the compound that quantum dot and bipyridyl ruthenium are formed.
The content of the invention
It is an object of the invention to provide simple and quick, the highly sensitive zinc ion detection method of one kind.
To realize goal of the invention, the present invention is adopted the following technical scheme that:
(1) with Cys as stabilizer, the cadmiumsulfide quantum dot of Cys modification is obtained;
(2) using bipyridyl ruthenium [Ru (bpy)2(dppz)]2+It is quenched the fluorescence of cadmiumsulfide quantum dot;
(3) pH value of solution is adjusted using Tris-HCl cushioning liquid;
(4) it is right after reaction a period of time to the zinc ion that various concentrations are added in the reaction solution that pH is regulated in step (3) Solution is detected, with zinc ion concentration as abscissa, fluorescence intensity is ordinate, draws standard curve.
The fluorescence analysis method of detection zinc ion concentration of the present invention, Cys, nitre in described step (1) The mol ratio of sour cadmium and vulcanized sodium is 2: 1.5: 1.
The fluorescence analysis method of detection zinc ion concentration of the present invention, bipyridyl ruthenium solution in described step (2) Concentration be 0-170 μm of ol/L, preferably 140 μm ol/L.
The fluorescence analysis method of detection zinc ion concentration of the present invention, described step (3) preferably buffers molten Liquid is Tris-HCl cushioning liquid, and the concentration of the buffer solution and specific consumption are by those skilled in the art understand and grasp.
The fluorescence analysis method of detection zinc ion concentration of the present invention, addition cushioning liquid will in the step (3) The pH of solution is adjusted to 7-9, preferably 7.5.
Present invention utilizes bipyridyl ruthenium as quencher by electrostatic attraction adsorb cadmiumsulfide quantum dot surface so as to The fluorescence of quantum dot, in conjunction with the specific recognition between zinc ion and cadmiumsulfide quantum dot, zinc ion and bipyridyl are fallen in quenching There is the amino on stabilizer Cys of the Competition due to zinc ion with quantum dot surface, carboxyl formation between ruthenium to match somebody with somebody Position key, vulcanization is formed because the active force of coordinate bond causes bipyridyl ruthenium molecule to depart from the surface of quantum dot more than electrostatic attraction Cadmium quantum dot-zinc ion complex compound, so that the fluorescence of the cadmiumsulfide quantum dot being quenched recovers and fluorescence intensity again Variable quantity is relevant with the concentration of zinc ion, therefore can be used for detecting the concentration of zinc ion.Compared with prior art, this hair It is bright to have an advantage in that:The fluorescence analysis method of this zinc ion detection of development is simple to operate quick, with low cost, is not required to Special instrument and equipment is wanted, with good general applicability, selectivity and sensitivity are compared to conventional zinc ion detection means It is significantly increased.
Brief description of the drawings
Fig. 1 is the UV-visible spectrum (UV-Vis) (line style) and fluorescence spectra (FL) (dotted line of cadmiumsulfide quantum dot Type).
The transmission electron microscope picture (TEM) of Fig. 2 cadmiumsulfide quantum dots.
Fig. 3 is the fluorescence spectra of Mechanism Validation:(a) cadmiumsulfide quantum dot;(b) cadmiumsulfide quantum dot+zinc ion;(c) Cadmiumsulfide quantum dot+bipyridyl ruthenium;(d) cadmiumsulfide quantum dot+bipyridyl ruthenium+zinc ion.
Fig. 4 (A) is the zinc that various concentrations are added in the Tris-HCl cushioning liquid of cadmiumsulfide quantum dot-bipyridyl ruthenium The fluorescence spectra of ion (0-1000 μm of ol/L);(B) for zinc ion concentration is linear with fluorescence intensity.
Specific embodiment
The Mechanism Validation of embodiment 1
Respectively to 2mL a, the Tris-HCl of the cadmiumsulfide quantum dot of 80 μ L, 100 μ L is added to delay in 4 centrifuge tubes of b, c, d Solution is rushed, then, to the bipyridyl ruthenium solution that 120 μ L are added in c pipes, is managed to d to the zinc ion solution that 60 μ L are added in b pipes again The bipyridyl ruthenium solution and the zinc ion solution of 60 μ L of 120 μ L of middle addition, others ultra-pure water are settled to 400 μ L, at room temperature After placing 5min, excitation wavelength is 360nm, and launch wavelength scope detects its fluorescence intensity (as shown in Figure 3) in 400-700nm.
Fig. 3 is Mechanism Validation figure, from column diagram a and column diagram b it can be seen that can make cadmium sulfide quantum in the presence of zinc ion The Fluorescence Increasing of point, but the degree of Fluorescence Increasing is not enough to delicately detect zinc ion, and this not only illustrates the sulphur selected by us Cadmium quantum dot has specific recognition for zinc ion, and also explanation has background signal, can interference detection results.Compare Column diagram c and column diagram d, it can be seen that zinc ion can make the fluorescence of the cadmiumsulfide quantum dot for being quenched fluorescence extensive again The fluorescence intensity of zinc ion is high 2 times than being individually added into for the intensity that multiple and fluorescence recovers, and this illustrates the fluorescence constructed by us Analysis method can reduce the interference of background signal, so as to improve the sensitivity of detection zinc ion.
The drafting of the standard curve of the zinc ion of embodiment 2 detection
To bipyridyl ruthenium solution and 100 μ that the cadmiumsulfide quantum dot of 80 μ L, 140 μ L are separately added into the centrifuge tube of 2mL The Tris-HCl buffer solutions of L, after reacting 15min at room temperature, add the zinc ion solution of various concentrations, zinc ion concentration according to It is secondary to be:0 μm of ol/L, 8 μm of ol/L, 24 μm of ol/L, 40 μm of ol/L, 56 μm of ol/L, 72 μm of ol/L, 104 μm of ol/L, 136 μm of ol/L, 168 μm of ol/L, 200 μm of ol/L, 400 μm of ol/L, 600 μm of ol/L, 800 μm of ol/L and 1000 μm of ol/L, are settled to ultra-pure water 400 μ L, its fluorescence intensity is determined after placing 5min at room temperature;As abscissa, fluorescence intensity is ordinate to concentration with zinc ion Mapping, you can draw the canonical plotting (as shown in Figure 4) of zinc ion.
Fig. 4 shows that the fluorescence intensity of solution also gradually strengthens and zinc ion concentration is in 8- with the increase of zinc ion concentration There is good linear relationship between 200 μm of ol/L, detection is limited to 9.20nM.
Although above the present invention is described in detail with a general description of the specific embodiments, On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.

Claims (9)

1. a kind of fluorescent method for detecting zinc ion concentration, it is characterised in that using bipyridyl ruthenium [Ru (bpy)2(dppz)]2+Point Son is adsorbed onto on the surface of the cadmiumsulfide quantum dot that Cys are modified the fluorescence for being quenched quantum dot by electrostatic attraction, due to L-Cys@CdS QDs are only to Zn2+There is enhancement effect of fluorescence, work as Zn2+Its amino and carboxyl with L-Cys surfaces when presence Coordinate bond is formed, because the active force of coordinate bond causes bipyridyl ruthenium molecule to depart from the surface of quantum dot more than electrostatic attraction, from And recover the fluorescence of quantum dot, therefore can be used for detecting Zn2+Concentration.
2. the XRF of detection zinc ion concentration according to claim 1, it is characterised in that specifically include following step Suddenly:
(1) with Cys as stabilizer, the cadmiumsulfide quantum dot of Cys modification is obtained;
(2) using bipyridyl ruthenium [Ru (bpy)2(dppz)]2+It is quenched the fluorescence of cadmiumsulfide quantum dot;
(3) pH value of solution is adjusted using Tris-HCl cushioning liquid;
(4) to the zinc ion that various concentrations are added in the reaction solution that pH is regulated in step (3), to solution after reaction a period of time Detected, with zinc ion concentration as abscissa, fluorescence intensity is ordinate, drawn standard curve.
3. it is according to claim 1 detection zinc ion concentration fluorescence analysis method, it is characterised in that the step (1) In, the stabilizer of quantum dot surface is Cys.
4. it is according to claim 1 detection zinc ion concentration fluorescence analysis method, it is characterised in that described step (1) mol ratio of Cys, cadmium nitrate and vulcanized sodium is 2: 1.5: 1 in.
5. it is according to claim 1 detection zinc ion concentration fluorescence analysis method, it is characterised in that described step (2) concentration of bipyridyl ruthenium solution is 0-170 μm of ol/L, preferably 140 μm ol/L in.
6. it is according to claim 1 detection zinc ion concentration fluorescence analysis method, it is characterised in that the step (3) In, described buffer solution is Tris-HCl cushioning liquid, and the concentration of the buffer solution and specific consumption are those skilled in the art institute Understand and grasp.
7. it is according to claim 1 detection zinc ion concentration fluorescence analysis method, it is characterised in that the step (3) The pH value of solution is adjusted to 7-9, preferably 7.5 by middle addition cushioning liquid.
8. it is according to claim 1 detection zinc ion concentration fluorescence analysis method, it is characterised in that the reaction time is 0- 30min, preferably 15min.
9. it is according to claim 1 detection zinc ion concentration fluorescence analysis method, it is characterised in that the step (4) In, the ultimate density for adding zinc ion to be measured is 0-1000 μm of ol/L.
CN201611174362.8A 2016-12-15 2016-12-15 A kind of cadmiumsulfide quantum dot detects the fluorescence analysis method of zinc ion concentration Pending CN106770111A (en)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN107389639A (en) * 2017-07-26 2017-11-24 广西师范学院 Utilize the method for nitrogen phosphorus doping carbon quantum dot probe in detecting aryl ruthenium
CN110927127A (en) * 2018-09-20 2020-03-27 Tcl集团股份有限公司 Detection method of free cadmium ions
CN110927130A (en) * 2018-09-20 2020-03-27 Tcl集团股份有限公司 Detection method of free zinc ions
CN111359630A (en) * 2018-12-25 2020-07-03 Tcl集团股份有限公司 Composite material and preparation method thereof
CN112028115A (en) * 2020-09-18 2020-12-04 东北林业大学 Cadmium sulfide quantum dot and preparation method thereof

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CN103592276A (en) * 2013-11-19 2014-02-19 东南大学 Quantum dot fluorescence sensor for cadmium ion detection, and detection method of fluorescence sensor
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107389639A (en) * 2017-07-26 2017-11-24 广西师范学院 Utilize the method for nitrogen phosphorus doping carbon quantum dot probe in detecting aryl ruthenium
CN110927127A (en) * 2018-09-20 2020-03-27 Tcl集团股份有限公司 Detection method of free cadmium ions
CN110927130A (en) * 2018-09-20 2020-03-27 Tcl集团股份有限公司 Detection method of free zinc ions
CN110927127B (en) * 2018-09-20 2021-04-02 Tcl科技集团股份有限公司 Detection method of free cadmium ions
CN110927130B (en) * 2018-09-20 2021-07-02 Tcl科技集团股份有限公司 Detection method of free zinc ions
CN111359630A (en) * 2018-12-25 2020-07-03 Tcl集团股份有限公司 Composite material and preparation method thereof
CN112028115A (en) * 2020-09-18 2020-12-04 东北林业大学 Cadmium sulfide quantum dot and preparation method thereof

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