CN108444955A - A kind of fluorescent optical sensor constituted based on DNA combination terbium ions and the application in differentiation and detection metal ion - Google Patents
A kind of fluorescent optical sensor constituted based on DNA combination terbium ions and the application in differentiation and detection metal ion Download PDFInfo
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Abstract
A kind of fluorescent optical sensor constituted based on DNA combination terbium ions Tb of disclosure of the invention and the application on metal ion is being distinguished and detected, is realizing the differentiation and detection of mass metal ion with the method for time-resolved fluorescence.First, what we filtered out three sections of different lengths is rich in guanine（G）And thymidine（T）Single stranded DNA as ligand pass through antenna effect sensitization Tb constitute fluorescent optical sensor（DNA/Tb）；Further we, which are dissolved in DNA/Tb in buffer solution, adds 49 metal ions, including alkali metal ion, alkaline-earth metal ions, transition/late transition metal ion and rare earth ion.Antenna effect is influenced since metal ion and DNA interact so that DNA/Tb obtains different time-resolved fluorescence signals and fluorescence lifetime under the conditions of different metal ions.Finally use principal component analysis（PCA）Method analysis obtain fluorescence signal and fluorescence lifetime, realize the differentiation and detection of metal ion.This method also achieves the metal half-quantitative detection in river water.
Description
Technical field
The invention belongs to fluorescence analysis detection field, more particularly to a kind of fluorescent optical sensor of DNA combinations terbium ion, with exempting from
The time-resolved fluorescence of label and the method for fluorescence lifetime realize the differentiation to mass metal ion and detection.
Background technology
The detection of biochemical species is not only the key in biochemical analysis field, at the same also environmental monitoring, food security,
The fields such as clinical diagnosis play an important role.For this purpose, fluorescent optical sensor because with it is simple and quick, monitor in real time, be easily understood,
High repeatability and other advantages and become effective detection instrument.However most of fluorescent optical sensor can all meet with the dry of background fluorescence
It disturbs, to influence sensitivity and the response range of detection.To effectively eliminate background fluorescence, ideal method is exactly time resolution skill
Art.TIME RESOLVED TECHNIQUE is that short-life self-luminous is distinguished from the fluorescence of long-life using time-domain.Currently, lanthanum
It is that fluorescence probe derived from metal has attracted people widely to pay close attention to, due to its unique optical property, such as grows glimmering
Light service life, narrow emission peak and big Stokes shift.These properties all allow rare earth ion doped fluorescence probe suitable
It is detected for time resolution and background fluorescence is eliminated with this.
In traditional method for sensing, as soon as often analyzing a kind of detectable substance just needs a sensor, and it is intensive to need
Labour develops the sensor of a variety of target specificity responses.In view of this problem, people start to be dedicated to being based on pattern
The sensor array that " chemical nose/tongue " array or differential of identification integrate is realized big by the response of one group of sensing element
Measure the differentiation and detection of target.
Metal ion is inextricably linked with life entity.The detection of metal ion belongs to weight in biochemical species detection
The part wanted.Alkali and alkaline earth metal ions are very active metallic elements, and Each performs its own functions in vivo for these biological elements,
It maintains the normal activity of life entity and pushes the development of life entity.For example, the potassium ion in human body is distributed in intracellular fluid
, the osmotic pressure of intracellular fluid and external solution is maintained, the internal structure of cell is stablized, participates in the transmission of nerve information, maintains the heart
The normal function of vascular system, and activator as certain enzymes participate in many important biochemical reactions etc..Sodium with from
In extracellular fluid, potassium and sodium collective effect adjust the balance of internal water and make heartbeat regularization the formal distribution of son.Lithium from
Son can cause the reduction of the amine amount of adrenaline and nerve endings, can significantly affect the amount of neurotransmitter.And heavy metal such as chromium, lead
The health that life entity can be seriously threatened with the enrichment of mercury plasma in vivo such as causes the loss of memory, learns defect, blindness and ear
Deaf, a series of serious problems such as kidney injury and cancer, such as iron ion is played as the essential trace elements of the human body to pass
Important role is related to the transport of oxygen in blood, DNA synthesis, numerous important life processes such as cellular invasion.Iron ion lacks
Less or it is present in excess the generation of the missing and disease that can all lead to some physiological functions, such as hypoferric anemia, hypertension, infertile
Infertility, apoplexy etc..Rare earth (RE) metal includes that lanthanide series and heavy metal element are more and more used in the industry, by this
The discharge of waste water of a little metal ion pollutions etc. not only can cause destructive injury to the mankind and ecology, can also cause mutation and
Cancer, radioactivity cause destructive injury to the mankind and ecology.Therefore, highly sensitive, highly selective extensive monitoring
It is vital with metal ion is distinguished.
Conventional method is as follows at present：
Atomic absorption spectrography (AAS) (AAS)；Inductively coupled plasma atomic emission spectrometry (ICP-AES)；Inductive coupling
Plasma Mass Spectrometry (ICP-MS)；Colorimetric method；Fluorescence method etc. based on graphene oxide or gold nano grain.
Traditional metal ion is distinguished and the method for detection generally requires expensive large-scale instrument, is completed such as ICP-AES；
And this process needs complicated early-stage preparations, has the destructive loss that will also result in detectable substance simultaneously to sample, real-time
For high-throughput quickly context of detection in situ there is limitation, testing cost is generally higher.It is colorimetric method, glimmering other than large-scale instrument
Light method is also used.But these methods may only distinguish several or more than ten metal ion species simultaneously at present, can not accomplish
The detection distinguished on a large scale, while it being also required to complicated probe preparation work, do not meet the simple and quick trend of method.
Invention content
The purpose of the present invention is to provide a kind of fluorescent optical sensors (DNA/Tb) of DNA combinations terbium ion, use time resolution
The method of fluorescence realizes the differentiation and detection of mass metal ion.It is realized with a kind of economical and practical mode and is almost covered
The detection of entire periodic table of elements range.Early-stage preparations complicated in the existing method distinguished, detect metal ion are overcome, are needed
Want expensive large-scale instrument, it is difficult to realize quickly detection high-throughput in real time in situ, be unfavorable for the defect of large-scale promotion and need
It wants complicated probe to prepare, the deficiency of detection metal ion can not be distinguished on a large scale.
Realizing the specific technical solution of the object of the invention is：
A kind of fluorescent optical sensor constituted based on DNA combination terbium ions, which is characterized in that be rich in guanine using three sections
(G) and the few chain DNA of thymidine (T) deoxyribonucleotide it, is combined, is formed with terbium ion respectively in buffer solution
[G3T]3/Tb、[G3T]5/Tb、[G3T]6/Tb；Wherein, [G3T]3、[G3T]5、[G3T]6For three segment DNA, Tb is terbium ion；
DNA sends out the fluorescence composition fluorescent optical sensor as antenna ligand sensitization Tb and is denoted as DNA/Tb；The three segment DNAs concentration is
1~100 μM；A concentration of 0.5~200 μM of Tb；Buffer solution is tris-HCl, a concentration of 50~200mM, pH value be 7.0~
9.0；Reaction temperature is 10~40 DEG C；Reaction time is 5~20 minutes；The volume ratio of solution is 1: 1: 1.
A kind of preparation method of above-mentioned fluorescent optical sensor, including step in detail below：
Step 1：Prepare DNA/Tb fluorescent optical sensors
The oligonucleotide chain rich in guanine (G) and thymidine (T) deoxyribonucleotide different from ten segment length
[G3T]NIt has screened three sections and has reacted the best [G of fluorescent effect with rare earth terbium ion (Tb)3T]N([G3T]3,[G3T]5,[G3T]6),
Constitute the three parts of fluorescent optical sensor；The fluorescent optical sensor, [G3T]3,[G3T]5,[G3T]6A concentration of 1~100 μM.Terbium
A concentration of 0.5~200 μM of ion, buffer solution used are Tris-HCl, and reaction density is 50~200mM, the buffer solution
PH value be 7.0~9.0；Preferably, pH=7.4.The reaction temperature is room temperature.The volume ratio of solution is 1: 1: 1.
The application on metal ion is being distinguished and detected to a kind of above-mentioned fluorescent optical sensor, specifically includes：
Step 1：The selection of detection method
It is mixed that metal ion standard solution or metal ion to be measured respectively are added into the DNA/Tb optical sensors of acquisition
Liquid is closed, is incubated 5 minutes.Realized to metal ion by the method for Time-resolved fluorescence assay method and detection fluorescence lifetime or
The detection of fluorescence and fluorescence lifetime after metal ion aggregate sample is added；The metal ion be alkali metal, alkaline-earth metal, transition/
Late transition metal, rare earth ion；
Step 2：The processing of detection data
Every group of experiment is repeated 5 times, the fluorescence data and lifetime data obtained with the method analysis of principal component analysis (PCA)
(3DNA/Tb sensing elements × target number × 5 Duplicate Samples), carries out the differentiation and detection of metal ion；Wherein,
The alkali metal is Li, Na, K, Rb and Cs；The alkaline-earth metal is Ca, Sr, Ba and Mg；The transition/rear transition
Metal is Co, Mn, Cu, Cr, Hg, Al, Ni, Cd, Zn, Pb, Ag, Fe II, Fe III, Ti, V, Zr, Mo, Ru, Pd, Ir, Cr VI, Sn
Ⅱ、SnⅣ、Bi；The rare earth metal is Tb, La, Ce, Y, Eu, Pr, Ho, Nd, Er, Yb, Dy, Gd, Sm, Lu, Tm and Sc.
Compared with prior art, advantageous effect of the present invention includes as follows：
The present invention changes the detection pattern of currently used metal ion, without complicated preparation of samples early period, is not required to
Expensive large-scale instrument is used, cost has been saved.The differentiating method for also changing metal ion simultaneously, without complicated probe
Preparation process, required DNA sequence dna can be obtained by commercialized chemical synthesis.Purity is high, at low cost.Expand gold again simultaneously
Belong to the detection range of ion, coverage area is almost the entire periodic table of elements.Metal ion is realized to distinguish and examine on a large scale
It surveys.The present invention is to report a kind of pattern-recognition system of DNA combinations terbium ion (Tb) for the first time at present, using three sections of different lengths
Few chain DNA sensitization rare earth terbium ion form general " chemical nose/tongue " sensor, and utilize unmarked time resolution
Fluorescence analysis method realizes the analysis and detection to its fluorescence.Principal component analytical method and clustering method is finally combined to carry out
The differentiation and detection of metal are realized in the analysis of fluorescence data.Detection method dosage is few, and entire reaction system only needs micro
Grade, has saved the usage amount of probe, has realized the detection of micro low cost.After detection method is using sensitization
The fluorescence of rare earth terbium ion has very long fluorescence lifetime (reaching ms grades) as signal, so as to glimmering using time resolution
The method of light analysis can effectively eliminate the influence of the background fluorescence and scattering fluorescence in detection process, can significantly improve spirit
Sensitivity and signal-to-noise ratio, while invention also demonstrates the pattern-recognitions based on DNA/Tb fluorescence lifetimes can also complete metal ion
Differentiation and detection.
Description of the drawings
Fig. 1 is present invention preparation and overhaul flow chart；
Fig. 2 is three segment DNA the selection result schematic diagrames of the invention；
The concentration that Fig. 3 is the DNA of three sections of different lengths determines figure；
Fig. 4 is the preliminary result figure of the present invention；
Fig. 5 is DNA, the circular dichroism spectrogram result figure of DNA/Tb；
Fig. 6 is interfering ion respectively influences situation map to DNA/Tb；
Fig. 7 is to carry out the result figure that metal ion is distinguished on a large scale with PCA methods；
Fig. 8 is to identify system to the metal ion of various concentration, the area of the metal ion sample mixing of various concentration with DNA/Tb
Divide result figure；
Fig. 9 is the differentiation result figure of the different valence state of same metal；
Figure 10 is the differentiation result figure for the concentration that five kinds of metals distinguish two orders of magnitude；
Figure 11 is the differentiation result figure to metal ion sample mixing in river water with PCA methods.
Specific implementation mode
In conjunction with following specific examples and attached drawing, the present invention is described in further detail, protection content of the invention
It is not limited to following embodiment.Without departing from the spirit and scope of the invention, those skilled in the art it is conceivable that change
Change and advantage is all included in the present invention, and using appended claims as protection domain.The process of the implementation present invention,
Condition, reagent, experimental method etc. are among the general principles and common general knowledge in the art in addition to the following content specially referred to,
Content is not particularly limited in the present invention.
Embodiment 1
It is screened from the DNA of 10 sections of different lengths, 10 μM of [G3T]N(N=1-10) (such as table 1) is added separately to
After 10 μM of Tb solution is incubated 10min, it is detected with the method for Time-resolved fluorescence assay.As shown in Fig. 2, [G3T]3,
[G3T]5[G3T]6Show better sensitization ability.This three segment DNA is selected to constitute fluorescence sense as antenna ligand sensitization Tb
Device DNA/Tb, the stoichiometric ratio then carried out between DNA and Tb is explored, the DNA ([G of various concentration3T]3, [G3T]5With
[G3T]6) be added separately in 10 μM of Tb solution, the DNA sensitizations Tb for obtaining various concentration uses time resolution after being incubated 10min
The method of fluorescence analysis is detected.As a result see Fig. 3.As shown in figure 3, [G3T]3, [G3T]5[G3T]6Antenna be sensitized ratio
([G3T]N/ Tb) it is 4 respectively:5,2:5,1:5.Unless spy explains, in next experiment, [G is selected3T]3, [G3T]5With
[G3T]6Final concentration be respectively 8 μM, 4 μM, 2 μM.Realize sensor of the invention.
Table 1
Embodiment 2
It chooses silver ion (Ag) and chromium ion (Cr) and blank (water) is used as preliminary experiment, take 10 μ L different metal ions to be measured
Solution is added in sensor solution, and 5min is placed at room temperature for after mixing, is then examined with the method for Time-resolved fluorescence assay
It surveys.Realize that as shown in Fig. 4 a-e, Ag can make DNA/Tb Fluorescence Increasings to fluorescence data processing with the method for principal component analysis, and
Cr can cause DNA/Tb fluorescent quenchings.Every group of experiment is repeated 5 times, with method analysis of fluorescence matrix (the 3DNA/Tb sensors of PCA
Composition × target number × 5 Duplicate Samples), as a result as shown in fig. 4f, these three targets (2 kinds of metals and blank) can pass through base
It is distinguished in fluorescent optical sensor DNA/Tb.In order to further probe into the mechanism of action, the DNA/Tb fluorescence in the case of these three is determined
In the service life, as shown in Fig. 4 g-i, the fluorescence lifetime of DNA/Tb fluorescent optical sensors is more than 0.4ms, it was demonstrated that the sensor can be used
Make time resolution (TRL) metal-ion fluorescent analysis detection without background interference.In typical TRL experiments, in pulse excitation
Under, a delay time and acquisition time are set, to eliminate short-life background fluorescence in delay time in acquisition time
In be only collected into the DNA/Tb signals of long-life.And after addition Cr, Ag, fluorescence lifetime changes, such as Fig. 4 j-k
It is shown.Then, PCA also analyzes fluorescence lifetime of the fluorescent optical sensor in the case of blank, Ag, Cr, finds based on glimmering
The pattern-recognition in light service life can also carry out fluorescence differentiation well, as shown in Fig. 4 l.Circular dichroism spectra is widely used for characterizing
DNA structure, as shown in figure 5, simple DNA ([G3T]3, [G3T]5[G3T]6) posivtive spike is shown at 260nm respectively,
And go out negative peak is presented in 240nm or so；After addition Tb is combined with DNA, lead to the change of some peak shapes, it is meant that the spaces DNA
The variation of configuration has different fluorescence intensities and different fluorescence lifetime so as to cause DNA/Tb.
Embodiment 3
In order to widely assess DNA/Tb fluorescent optical sensor separating capacities, 49 metal ion species are separately added into as target
Mark, including alkali metal, alkaline-earth metal, transition/late transition metal and rare earth metal, the shape for selecting its most common or stablizing
State.Since alkali metal has lower charge density, because of it is difficult to be detected and distinguished by fluorescent method, so selection is higher
Concentration.Alkali metal concn is 500 μM, other metals are 5 μM, are separately added into 3 DNA/Tb fluorescent sensing devices, detection side
Method is as described in above-mentioned preliminary experiment.PCA analysis methods assess the DNA/Tb fluorescent optical sensor response conditions of metal ion induction.Such as figure
Shown in 6a, c, e, f, 5 kinds of alkali metal, 4 kinds of alkaline-earth metal, 24 kinds of transition/late transition metals, 16 kinds of rare earth metals can be by very clear
Chu distinguishes and has very high differentiation accuracy.It is worth noting that, although only there are three DNA/Tb fluorescent optical sensor groups
At part, but this simple DNA/Tb fluorescent optical sensor can distinguish the very high rare earth ion of similarity.In addition to above-mentioned
Outside pattern-recognition based on TRL, the pattern-recognition based on fluorescence lifetime can also realize metal ion differentiation (with alkali metal and
For alkaline-earth metal), such as Fig. 6 b, d, this has prodigious similarity (Fig. 6 a, c) with TRL results.Therefore proposed by the present invention
DNA/Tb fluorescent optical sensors can be achieved large-scale metal ion at TRL and fluorescence lifetime both of which and distinguish.As
Control experiment, to some and metal ion counter ion counterionsl gegenions (F-,Cl-,NO3 -,SO4 2-,NH4 +) fluorescence response after addition also carries out
Detection, as shown in fig. 7, even if very little if fluorescence changes final concentration of 100 μM in the case of, and then demonstrate glimmering
The change of optical signal is strictly caused by these metal ions.
Embodiment 4
In order to detect the sensitivity of DNA/Tb fluorescent optical sensors, the present invention has selected four kinds of metal (K, Sr, Pb, Tb) conducts
Alkali metal, alkaline-earth metal, the representative of transition/late transition metal and rare earth metal carry out sensitivity analysis.As shown in figure 8, by
It is less than 40% in second Assessing parameters (PC2), so first Assessing parameters (PC1) can describe fluorescence response situation and gold
Belong to the relationship (Fig. 8 a, c, e, g) of concentration.It can be seen from the figure that fluorescence response element also has in a concentration of sub-micromolar grade
Good response (Fig. 8 b, d, f, h), the range of linearity are 0-0.1mM (K) and 0-5 μM (Sr, Pb, Tb).In rare earth ion it is difficult to area
In the case of point, while successfully having distinguished 16 kinds of rare earth ions, the detection (Fig. 8 h) to Tb sensitivity is also achieved.
Embodiment 5
Carry out the differentiation of mixing sample.K/Rb, Ba/Ca, Ru/Ti, the Lu/La of different molar concentration rates are tested, is such as schemed
Shown in 8i-l, after being analyzed by PCA, what these mixing samples can will be apparent that is distinguished out.As shown in figure 9, various concentration
Fe (the Fe of the different valence state of ratioII,FeIII) can be very good to distinguish by PCA.Simultaneously the fluorescent optical sensor that also demonstrates for
The different valence state of same metal is also very sensitive, and five kinds of metals, two various concentrations are similarly obtained by PCA analyses
Ideal result (Figure 10).In addition, a series of unknown standard metal specimens are added in fluorescence response element, Blind Test is carried out,
49 sample success rates are up to 100% (such as table 2).
Table 2
Embodiment 6
In order to prove that DNA/Tb fluorescent optical sensors can distinguish mixing sample in environment, a series of mixing is prepared
Sample.Cu/Pb solution (the Cu/Pb=1 of different mol ratio is separately added into beautiful baby's river water:0,0.75:0.25,0.4:0.6,
0.25:0.75,0:1, be all μM) and Eu/Ce solution (Eu/Ce=0:1,0.3:0.7,0.4:0.6,0.75:0.25,1:0, all
It is μM) and six groups of detection sample A) 0.8 μM of Cu+0.2 μM of Pb, B) 0.5 μM of Cu+0.5 μM of Pb), C) 0.3 μM of Cu+0.7 μ
M Pb),D)0.8μM Eu+0.2μM Ce,E)0.5μM Eu+0.5μM Ce,and F)0.25μM Eu+0.75μM Ce.It will be upper
It states sample to be added separately to be incubated 5 minutes in fluorescent optical sensor, measures its fluorescence intensity.PCA results are as shown in figure 11.It uses simultaneously
ICP-AES analyzes the tenor of detection group, as shown in table 3, it can be found that the PCA ranges of detection group were measured with ICP-AES
As a result consistent.For example, it is 1 that the PCA points of sample A, which are fallen in Cu/Pb molar ratios,:0 and 0.75:Between 0.25, it was demonstrated that the concentration of Cu
It is 0.75-1 μM, a concentration of 0-0.25 μM of Pb.This is consistent with ICP-AES results.Demonstrating DNA/Tb fluorescent optical sensors can be with
Realize the half-quantitative detection of metal ion in complex environment system.This simple unmarked fluorescence analysis method is in low cost
In the case of realize mixing sample measurement, can compare favourably with highly sensitive ICP-AES.
Table 3
The present invention proposes the extensive differentiation and inspection for using DNA/Tb to realize metal ion as fluorescence sense for the first time
It surveys.And this application is matched dependent on the antenna of the interaction induction between the synergistic effect and metal/DNA of DNA sensitizations Tb
The change of bulk effect.Three segment DNAs sensitization Tb is only needed to may make up fluorescence sense, and the interaction of metal ion and DNA can not
It is realized including alkali metal, alkaline earth with the change antenna ligand effect of degree to generate the mode signal of TRL and fluorescence lifetime
Metal, the differentiation of 49 metal ion species including transition/late transition metal and rare earth metal.
It is only presently preferred embodiments of the present invention in summary, is not used for limiting the scope of the invention.It is all according to the present invention
Equivalent changes and modifications made by content all should be protection category of the present invention.
Claims (4)
1. a kind of fluorescent optical sensor constituted based on DNA combination terbium ions, which is characterized in that be rich in guanine using three sections（G）
And thymidine（T）The few chain DNA of deoxyribonucleotide, is combined with terbium ion respectively in buffer solution, forms [G3T]3/
Tb、[G3T]5/Tb、[G3T]6/Tb；Wherein, [G3T]3、[G3T]5、[G3T]6For three segment DNA, Tb is terbium ion；DNA makees
It is sensitized Tb for antenna ligand and sends out the fluorescence composition fluorescent optical sensor, is denoted as DNA/Tb；The three segment DNAs concentration is 1 ~
100μM；A concentration of 0.5 ~ 200 μM of Tb；Buffer solution is tris-HCl, a concentration of 50 ~ 200 mM, pH value be 7.0~
9.0；Reaction temperature is 10~40 DEG C；Reaction time is 5~20 minutes；The volume ratio of solution is 1: 1: 1.
2. fluorescent optical sensor described in a kind of claim 1 is in the application for distinguishing and detecting metal ion.
3. application according to claim 2, which is characterized in that distinguish and detection metal ion specifically includes：
1）Metal ion solution is separately added into three containing fluorescent optical sensor different composition solution, is incubated 5 minutes, uses the time
The method of resolution carries out fluoroscopic examination, obtains fluorescence signal；Wherein, the concentration of the different composition solution of the sensor three is
1~100μM；A concentration of 0. 001~2 mM of metal ion solution；The condition of the fluorescence measurement：Under room temperature, excitation wavelength
For 260 ~ 300 nm, scanning range is 450~650 nm, 50 μ s of delay time, 2 ms of gate duration；The metal ion is alkali
Metal, alkaline-earth metal, transition/late transition metal, rare earth ion；
2）Every group of experiment is repeated 5 times, and uses principal component analysis（PCA）Fluorescence signal i.e. 3 DNA/Tb that obtain of method analysis pass
Sensing unit × target number × 5 Duplicate Samples, realizes the differentiation and detection of metal ion.
4. application according to claim 3, which is characterized in that the alkali metal is Li, Na, K, Rb and Cs；The alkaline earth
Metal is Ca, Sr, Ba and Mg；Transition/the late transition metal is Co, Mn, Cu, Cr, Hg, Al, Ni, Cd, Zn, Pb, Ag, FeⅡ、
FeⅢ、Ti、V, Zr、Mo、Ru、Pd、Ir、CrⅥ、SnⅡ、SnⅣ、Bi；The rare earth metal be Tb, La, Ce, Y, Eu, Pr, Ho, Nd,
Er, Yb, Dy, Gd, Sm, Lu, Tm and Sc.
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| CN103888135B (en) * | 2012-12-20 | 2018-01-16 | 北京普源精电科技有限公司 | It is a kind of that there is the radio-frequency signal source for reducing spuious function |
| CN104926698A (en) * | 2014-03-18 | 2015-09-23 | 中国科学院大连化学物理研究所 | Tetradentate beta-diketone ligand-europium fluorescent complex and application thereof |
| CN106932564B (en) * | 2015-12-30 | 2018-09-25 | 深圳先进技术研究院 | It is used to detect kit and its application of nucleic acids in samples target based on FRET |
| CN105527264A (en) * | 2016-01-18 | 2016-04-27 | 华东师范大学 | Fluorescent probe based on oligodeoxynucleotide chain-sensitized europium ions, ferric iron ion detection method with fluorescent probe, and application of fluorescent probe |
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2018
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| CN110823851A (en) * | 2019-11-12 | 2020-02-21 | 广州大学 | Mercury ion detection method based on rare earth/nucleotide supramolecular assembly |
| CN110823851B (en) * | 2019-11-12 | 2022-09-30 | 广州大学 | Mercury ion detection method based on rare earth/nucleotide supramolecular assembly |
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