CN107513063A - One kind can identify Cu in HL 602+2 Aryimidazoles and phenanthroline probe and preparation method thereof - Google Patents
One kind can identify Cu in HL 602+2 Aryimidazoles and phenanthroline probe and preparation method thereof Download PDFInfo
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- CN107513063A CN107513063A CN201710809887.2A CN201710809887A CN107513063A CN 107513063 A CN107513063 A CN 107513063A CN 201710809887 A CN201710809887 A CN 201710809887A CN 107513063 A CN107513063 A CN 107513063A
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Abstract
The present invention, which discloses one kind, can identify Cu in HL 602+2 Aryimidazoles and phenanthroline probe and preparation method thereof, simultaneously [5,6 f] phenanthroline is applied to 60 intracellular Cu of HL to 2 Aryimidazole provided by the invention2+Detection, to Cu2+High sensitivity, response are high；It is as fluorescence probe in use, to Cu2+With obvious response；For the Cu of various concentrations2+When being detected, good linear relationship is showed；And in HL 60 into the cell to Cu2+There is good selectivity, be infected with the suspension cells of HL 60 of the Aryimidazole of compound 2 simultaneously [5,6 f] phenanthroline after blue light excites, observed in microscope, cell sends green fluorescence, and detection method is reliable；Reaction equation is as follows.
Description
Technical field
The present invention relates to one kind can identify the intracellular Cu of HL-602+2- Aryimidazoles simultaneously [5,6-f] phenanthroline fluorescence visit
Pin and preparation method thereof, belong to the fluorescence probe field of metal ion.
Background technology
Content of the copper in human body is only second to iron and zinc, is one of minor metallic element needed by human.It is present in blood
CER, superoxide dismutase, cytochrome C oxidase are starched, there are a variety of important physiologic functions.When human body copper
It can cause deficiency disease during intake deficiency, but Cu2+The enzyme system of organism can be excessively destroyed, hinders organism normally biochemical
Reaction and metabolism, have very big harm to human body.There are a large amount of copper ions, HL- in more document report HL-60 cells
60 cells are from acute promyelocytic leukemia（APL）Separated in the peripheral blood of patient, APL is acute marrow
Chronic myeloid leukemia（AML）A kind of specific type, be otherwise known as acute myelocytic leukemia M3 types.Be mainly characterized by marrow with it is outer
Marrow cell paraplasm in all blood, the disease account for the 30% of childhood lymphoblastic leukemia, and infant is susceptible to suffer from APL than adult.This be critically ill evil compared with
Greatly, the characteristics of majority of cases all has the state of an illness suddenly weight, and prognosis is dangerous, if treated not in time, threat can be produced to life security.
Therefore the Cu in HL-60 cells is detected in time2+, using highly sensitive technology to Cu2+Micro and quick detection is carried out, for energy
It is enough early to find that disease is particularly important.
It is usually used in detection Cu in active somatic cell at present2+Analyzing detecting method mainly utilize Cu2+(also may be used with indicator
Referred to as chemical molecular probe) between specific chemical reaction or supermolecular mechanism caused by signal intensity come to Cu2+Divided
Analysis detection, these fluorescent probe molecules are to Cu2+There are high selectivity and higher sensitivity.Therefore a kind of fluorescence probe point is prepared
Son is used for detecting the Cu in HL-60 cells2+, micro and quick detection is carried out to it using highly sensitive technology, for can be early
Ground finds that acute promyelocytic leukemia is particularly important.
The invention provides one kind can identify the intracellular Cu of HL-602+Fluorescence probe 2- Aryimidazoles simultaneously [5,6-f] are adjacent
Ferrosin compound and preparation method thereof.
The content of the invention
The purpose of the present invention is that one kind can identify the intracellular Cu of HL-602+2- Aryimidazoles simultaneously [5,6-f] phenanthroline is glimmering
Light probe and its preparation method and application.Fluorescence probe provided by the invention Cu intracellular to HL-602+Recognition result it is accurate,
High sensitivity.
It is provided by the invention to identify the intracellular Cu of HL-602+2- Aryimidazoles simultaneously [5,6-f] phenanthroline compound
Fluorescence probe, have formula (I) shown in
Wherein R be 2,3,4,5,6 substitution methyl, ethyl, propyl group, butyl, nitro, Cl, F, acetyl group, hydroxyl, methoxyl group.
Present invention also offers one kind can identify the intracellular Cu of HL-602+2- Aryimidazoles simultaneously [5,6-f] phenanthroline is glimmering
The preparation method of light probe.It is to synthesize intermediate 1,10- ferrosins -5,6- for raw material with 1,10- ferrosins in more detail
Diketone, then intermediate 2- Aryimidazoles simultaneously [5,6-f] phenanthroline compound is synthesized with aldehyde.
Realize that technical scheme is as follows：
Reactions steps are as follows：
（1）After 1,10- ferrosins, selenium dioxide, the concentrated sulfuric acid, concentrated nitric acid mixture are heated to reflux, reaction obtains thick after terminating
Product, through being recrystallized to give pure compound（Ⅱ）, it is yellow solid.
（2）By compound（Ⅱ）It is dissolved in hydrochloric acid and is heated to reflux with benzaldehyde derivative, ammonium chloride, is obtained after reaction through column chromatography
Compound（I）, it is yellow needle-like crystals；
（Ⅱ）（I）
, according to the invention it is preferred to, step（1）Described 1,10- ferrosins, the mol ratio of selenium dioxide are 1:3；
, according to the invention it is preferred to, step（2）Described compound（Ⅱ）1,10- phenanthroline -5,6- diketone, benzaldehyde-derivative
The mol ratio of thing is 1:2；
, according to the invention it is preferred to, step（1）Described reaction temperature is 100-140 DEG C, more preferably 110-130 DEG C；
, according to the invention it is preferred to, step（2）Described reaction temperature is 100-120 DEG C, more preferably 100-110 DEG C；
In more detail, it is described to identify the intracellular Cu of HL-602+2- Aryimidazoles simultaneously [5,6-f] phenanthroline fluorescence
The preparation method of probe, step are as follows：
（1）1,10- ferrosin 2.0g, selenium dioxide 6.0g are weighed, is well mixed in flask, the 20mL concentrated sulfuric acids, 10 mL are dense
Nitric acid mixes, and ice-water bath is cooled into the mixed acid of cooling.The mixed acid of cooling is slowly added dropwise along flask walls, is added dropwise, adds
Heat is flowed back, and rufous gas is increasingly generated in bottle.Stop heating, obtain rufous clear solution；Rufous clear solution is fallen
Enter into frozen water, acid is slowly neutralized with NaOH, until PH=7 of reactant mixture, this process generates more yellow flocculent deposit,
Yellow mercury oxide is filtered to obtain, with dichloromethane extraction three times, merges organic phase, washing twice, merges organic phase, and organic phase rotation is steamed
It is dry that yellow powder is compound（Ⅱ）, recrystallizing methanol drying, yield 90%.
（2）Weigh Compound（Ⅱ）1,10-Phenanthroline-5,6-Quinone 0.11g, ammonium chloride 1.1667g, benzaldehyde
0.1167g, it is added separately in round-bottomed flask, with dissolving with hydrochloric acid, oil bath heating back flow reaction under magnetic agitation；Solution is by yellow
It is changed into rufous, is cooled to room temperature, reaction solution is poured into frozen water, then ammoniacal liquor is slowly added dropwise, and neutralizes acid until PH=7, during this
There are a large amount of pale yellow precipitates to produce, filter, dry cake to constant weight obtains crude product, crude product silica gel column chromatography, obtained yellowish
Color acicular crystal is compound（I）, yield 55%.
It is an advantage of the invention that：Compared with prior art, the invention provides one kind can identify the intracellular Cu of HL-602+
Fluorescence probe 2- Aryimidazoles simultaneously [5,6-f] phenanthroline compound preparation method, it is provided by the invention to identify HL-
60 intracellular Cu2+Fluorescence probe 2- Aryimidazoles simultaneously [5,6-f] phenanthroline compound has formula（I）Structure, the present invention
Simultaneously [5,6-f] phenanthroline fluorescence probe can be used for the intracellular Cu of HL-60 to described 2- Aryimidazoles2+Detection, to Cu2+Spirit
Sensitivity is high, and response is high；Test result indicates that when compound of the present invention is used in HL-60 cells as fluorescence probe, it is right
Cu2+There is significant response；For the Cu of various concentrations2+In good linear relationship during detection, in HL-60 into the cell to Cu2+Have
Selectivity well, the HL-60 suspension cells for being infected with compound 2- Aryimidazoles simultaneously [5,6-f] phenanthroline excite through blue light
Afterwards, observed in microscope, cell sends green fluorescence, and detection method is reliable.
Brief description of the drawings
Fig. 1 is identification HL-60 intracellular copper ion fluorescence probes 2- (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f]
The UV absorption spectrogram of Phen.
Fig. 1-1 is identification HL-60 intracellular copper ion fluorescence probes 2- (2- hydroxyl-5- nitrobenzophenones) imidazo [5,6-
F] Phen fluorescence spectra.
Fig. 2 is identification HL-60 intracellular copper ion fluorescence probes 2- (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f]
Phen is determined for Cu under 450nm excitation wavelength2+The fluorescence spectra of selectivity.
Fig. 3 is identification HL-60 intracellular copper ion fluorescence probes 2- (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f]
Phen determines the Cu for adding various concentrations under 450nm excitation wavelength2+Front and rear fluorescence spectra.
Fig. 4 is HL-60 suspension cells in copper ion fluorescence probe 2- (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f]
The fluorescence excitation comparison diagram before and after 2h is cultivated in Phen solution, in figure：A is the unexcited image of HL-60 suspension cells；b
To swash in the HL-60 suspension cells for having compound 2- (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f] Phen through blue light
After hair, observed in microscope, cell sends faint green fluorescence；C is HL-60 suspension cells in 2- (2- hydroxyl -5- nitros
Phenyl) imidazo [5,6-f] Phen and Cu2+After being cultivated 2 hours in mixed solution, 2- (2- hydroxyl -5- nitrobenzene is infected with
Base) imidazo [5,6-f] Phen and Cu2+Mixed solution HL-60 suspension cells cell after blue light excites fluorescence
Intensity has enhancing.
Embodiment
It is clearly and completely described below in conjunction with the technical scheme of the embodiment of the present invention, it is clear that described implementation
Example only part of the embodiment of the present invention, rather than whole embodiments.It is common based on the embodiment in the present invention, this area
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
Embodiment 1：The present embodiment is the specific embodiment prepared according to the reaction process of the formula (I) structural compounds.
Phenylimidazole simultaneously [5,6-f] Phen：1,10- ferrosin 2.0g, selenium dioxide 6.0g are weighed, is mixed in flask
Close uniformly, be 18mol L by 20 mL concentration-1The concentrated sulfuric acid, 10 mL concentration are 14mol L-1Concentrated nitric acid mixing, ice-water bath
It is cooled into the mixed acid of cooling.The mixed acid of cooling is slowly added dropwise along flask walls, is added dropwise, is heated to reflux, in bottle gradually
Generate rufous gas.Stop heating, obtain rufous clear solution；Rufous clear solution is poured into frozen water, used
NaOH slowly neutralizes acid, and until PH=7 of reactant mixture, this process generates more yellow flocculent deposit, filter yellow is sunk
Form sediment, with dichloromethane extraction three times, merge organic phase, washing twice, merges organic phase, and organic phase rotation is evaporated to obtain yellow powder
For compound（Ⅱ）, recrystallizing methanol drying, yield 90%.
Weigh Compound（Ⅱ）1,10-Phenanthroline-5,6-Quinone 0.11g, ammonium chloride 1.1667g, benzaldehyde 0.1167g,
It is added separately in round-bottomed flask, is 6mol L with 20 mL concentration-1Dissolving with hydrochloric acid, oil bath heating backflow is anti-under magnetic agitation
Should；Solution is changed into rufous from yellow, is cooled to room temperature, and reaction solution is poured into frozen water, then ammoniacal liquor is slowly added dropwise, neutralize acid until
PH=7, there are during this large amount of pale yellow precipitates to produce, filter, dry cake to constant weight obtains crude product, crude product silicagel column
Chromatography, it is compound to obtain faint yellow acicular crystal（I）, yield 55%.
Embodiment 2：2- (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f] Phen：Preparation method with embodiment 1,
5- nitrosalicylaldehydes are added, obtain faint yellow needle point crystal, yield 57%.Its hydrogen nuclear magnetic resonance spectrogram data is：
1H NMR (500 MHz, DMSO-d6): 9.06 (d, 2H,J=8.2 Hz), 8.98(d, 2H, J= 7.5 Hz),
7.87 (dd, 2H, J = 8.0 Hz), 7.43 (d,1H, J =8.0 Hz), 6.84 (d, 1H, J =8.6 Hz),
6.73—6.75 (m, 1H) 。
Embodiment 3：2- made from embodiment 2 (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f] Phen fluorescence is visited
The UV absorption spectrogram of pin（See Fig. 1）And fluorescence spectra（See Fig. 1-1）.
2- (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f] Phen accurately is weighed, moves it into 10 mL capacity
In bottle, dissolved with absolute ethyl alcohol, the constant volume after sample is completely dissolved, be configured to concentration 1.0 × 10-5 mol L-1Solution, point
Its ultra-violet absorption spectrum and fluorescence excitation spectrum are not determined.Measurement result is as shown in Fig. 1, Fig. 1-1；Fig. 1 visits for copper ion fluorescence
The ultra-violet absorption spectrum of pin 2- (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f] Phen；Fig. 1-1 is copper ion fluorescence
Probe 2- (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f] Phen is for being populated with the glimmering of induced luminescence effect detection
Light spectrogram.
The maximum absorption wavelength of 2- (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f] Phen as can be seen from Figure 1
At 275nm；From Fig. 1-1 it can be seen that the maximum excitation of 2- (2- hydroxyl-5- nitrobenzophenones) imidazo [5,6-f] Phen
Wavelength is at 450nm.Therefore the excitation wavelength for considering decision compound is 450nm.Selection maximum excitation wavelength be in order to
The physical form of high firing rate is obtained, improves sensitivity.
Embodiment 4：2- made from embodiment 2 (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f] Phen fluorescence is visited
Pin is determined for Cu under 450nm excitation wavelength2+Selectivity.
2- (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f] Phen accurately is weighed, is dissolved in chromatographically pure absolute ethyl alcohol
In, concentration is configured to as 1.0 × 10-4 mol•L-1Ligand solution in, respectively choose 10 kinds of different metal ions（Hg2+, Al3+,
Ni2+, Mn2+, Cu2+, Ag+, Ca2+, K+, Na+, Li+）, it is made into ligand concentration 1.0 × 10-5 mol•L-1, concentration of metal ions 1.5
×10-4 mol•L-1Mixed solution, determine solution fluorescence spectrum change.Measurement result is as shown in Figure 2.
Figure it is seen that Cu2+Fluorescence intensity be significantly stronger than other ion fluorescence intensity, illustrate 2- (2- hydroxyls -5-
Nitrobenzophenone) imidazo [5,6-f] Phen fluorescence probe is to Cu2+There is very high selectivity.
Embodiment 5：2- made from embodiment 2 (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f] Phen fluorescence is visited
For the Cu of various concentrations2+Fluoroscopic examination.
2- (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f] Phen accurately is weighed, is dissolved in chromatographically pure absolute ethyl alcohol
In, concentration is configured to as 1.0 × 10-4 mol•L-1Solution, then respectively according to concentration be 0 μM, 50 μM, 100 μM, 150 μM,
200 μM, 250 μM, 300 μM, 350 μM, 400 μM, 450 μM of addition Cu2+, it is made into compound concentration 1.0 × 10-5 mol•L-1, gold
It is respectively 0,0.5 × 10 to belong to ion concentration-5 mol•L-1、1×10-4 mol•L-1、1.5×10-4 mol•L-1、2×10-4 mol•
L-1、2.5×10-4 mol•L-1、3×10-4 mol•L-1、3.5×10-4 mol•L-1、4×10-4 mol•L-1、4.5×10-4
mol•L-110 bottles of mixed solutions, respectively determine solution fluorescence spectrum change.Measurement result is as shown in Figure 3.
As can be seen from Figure 3 the Cu of various concentrations is added2+, the fluorescence spectrum maximum emission peak of solution all never there occurs blue shift or
Red shift, and fluorescence intensity is remarkably reinforced therewith.With the rise of concentration of metal ions, 2- (2- hydroxyl -5- nitrobenzophenones) miaow
The mixed solution fluorescence intensity of azoles simultaneously [5,6-f] Phen is into ascendant trend.
Embodiment 6：HL-60 suspension cells are in 2- made from embodiment 2 (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-
F] fluorescence excitation contrast before and after 2h is cultivated in Phen solution.
It is adjacent luxuriant and rich with fragrance that cultured HL-60 cells are placed in 2- (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f] prepared
In sieve quinoline solution, immersion is washed three times after two hours with phosphate buffered saline (PBS), with indigo plant under inverted fluorescence microscope
Light excites, and takes a picture.
It is adjacent luxuriant and rich with fragrance that cultured HL-60 cells are placed in 2- (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f] prepared
After being soaked two hours in the mixed solution of sieve quinoline and metal ion, take out with phosphate buffered saline (PBS) wash three times,
Blue light is excited and taken a picture under inverted fluorescence microscope.Measurement result is as shown in Figure 4.
From fig. 4, it can be seen that a is the unexcited image of HL-60 suspension cells in figure, compared with a in figure, there is compound
The HL-60 suspension cells of 2- (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f] Phen are after blue light excites, micro-
Observed in mirror, cell sends faint green fluorescence (b in figure), and HL-60 suspension cells are at 2- (2- hydroxyl -5- nitrobenzophenones)
Imidazo [5,6-f] Phen and Cu2+After being cultivated 2 hours in mixed solution, 2- (2- hydroxyl -5- nitrobenzophenones) imidazoles is infected with
And [5,6-f] Phen and Cu2+Mixed solution HL-60 suspension cells after blue light excites the fluorescence intensity of cell have increasing
By force（C in figure）.So as to illustrate that 2- (2- hydroxyl -5- nitrobenzophenones) imidazo [5,6-f] Phen can specificity knowledge
Cu in other HL-60 cells2+, realized into the cell to Cu in HL-602+The Fluorescence Increasing molecular switch of response, this is the system
Larger foundation effect is served applied to more areas such as bio-identifications.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God and any modification made within principle, equivalent substitution and improvement etc., should be included in the scope of the protection.
Claims (8)
1. one kind can identify the intracellular Cu of HL-602+2- Aryimidazoles simultaneously [5,6-f] phenanthroline fluorescence probe, there is formula（I）
Structure,
Formula（I）
Wherein R be 2,3,4,5,6 substitution methyl, ethyl, propyl group, butyl, nitro, Cl, F, acetyl group, hydroxyl, methoxyl group.
2. the intracellular Cu of HL-60 can be identified described in claim 12+2- Aryimidazoles simultaneously [5,6-f] phenanthroline fluorescence visit
The preparation method of pin, comprises the following steps：
（1）After 1,10- ferrosins, selenium dioxide, the concentrated sulfuric acid, concentrated nitric acid mixture are heated to reflux, reaction obtains thick after terminating
Product, through being recrystallized to give pure compound（Ⅱ）, it is yellow solid；
（2）By compound（Ⅱ）It is dissolved in hydrochloric acid and is heated to reflux with benzaldehyde derivative, ammonium chloride, is obtained after reaction through column chromatography
Compound（I）, it is yellow needle-like crystals；
（I）.
3. the intracellular Cu of HL-60 can be identified as claimed in claim 22+2- Aryimidazoles simultaneously [5,6-f] phenanthroline fluorescence
The preparation method of probe,
It is characterized in that step（1）Described 1,10- ferrosins, the mol ratio of selenium dioxide are 1:3.
4. the intracellular Cu of HL-60 can be identified as claimed in claim 22+2- Aryimidazoles simultaneously [5,6-f] phenanthroline fluorescence
The preparation method of probe,
It is characterized in that step（2）Described compound（Ⅱ）1,10- phenanthroline -5,6- diketone, mole of benzaldehyde derivative
Than for 1:2.
5. the intracellular Cu of HL-60 can be identified as claimed in claim 22+2- Aryimidazoles simultaneously [5,6-f] phenanthroline fluorescence
The preparation method of probe, it is characterised in that step（1）The described temperature that is heated to reflux is 100-140 DEG C, more preferably 110-130
℃。
6. the intracellular Cu of HL-60 can be identified as claimed in claim 22+2- Aryimidazoles simultaneously [5,6-f] phenanthroline fluorescence
The preparation method of probe, it is characterised in that step（2）The described temperature that is heated to reflux is 100-120 DEG C, more preferably 100-110
℃。
7. the intracellular Cu of HL-60 can be identified as claimed in claim 22+2- Aryimidazoles simultaneously [5,6-f] phenanthroline fluorescence
The preparation method of probe, it is characterised in that step is as follows：
（1）1,10- ferrosin 2.0g, selenium dioxide 6.0g are weighed, is well mixed in flask, the 20mL concentrated sulfuric acids, 10 mL are dense
Nitric acid mixes, and ice-water bath is cooled into the mixed acid of cooling；The mixed acid of cooling is slowly added dropwise along flask walls, is added dropwise, adds
Heat is flowed back, and rufous gas is increasingly generated in bottle；Stop heating, obtain rufous clear solution；Rufous clear solution is fallen
Enter into frozen water, acid is slowly neutralized with NaOH, until PH=7 of reactant mixture, this process generates more yellow flocculent deposit,
Yellow mercury oxide is filtered to obtain, with dichloromethane extraction three times, merges organic phase, washing twice, merges organic phase, and organic phase rotation is steamed
It is dry that yellow powder is compound（Ⅱ）, recrystallizing methanol drying, yield 90%；
（2）Weigh Compound（Ⅱ）1,10-Phenanthroline-5,6-Quinone 0.11g, ammonium chloride 1.1667g, benzaldehyde 0.1167g, point
It is not added in round-bottomed flask, with dissolving with hydrochloric acid, oil bath heating back flow reaction under magnetic agitation；Solution is changed into reddish brown from yellow
Color, room temperature is cooled to, reaction solution is poured into frozen water, then ammoniacal liquor is slowly added dropwise, and neutralizes acid until PH=7, is had during this large amount of light
Yellow mercury oxide produces, and filters, and dry cake to constant weight obtains crude product, crude product silica gel column chromatography, it is brilliant to obtain faint yellow needle-like
Body is compound（I）, yield 55%.
8. there is formula（I）The compound of structure, applied to the identification intracellular Cu of HL-602+Fluorescence probe
Formula（I）
Wherein R be 2,3,4,5,6 substitution methyl, ethyl, propyl group, butyl, nitro, Cl, F, acetyl group, hydroxyl, methoxyl group.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710809887.2A CN107513063A (en) | 2017-09-09 | 2017-09-09 | One kind can identify Cu in HL 602+2 Aryimidazoles and phenanthroline probe and preparation method thereof |
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| CN201710809887.2A CN107513063A (en) | 2017-09-09 | 2017-09-09 | One kind can identify Cu in HL 602+2 Aryimidazoles and phenanthroline probe and preparation method thereof |
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| CN109776534A (en) * | 2019-02-01 | 2019-05-21 | 山东理工大学 | Ratio sensing type zinc ion fluorescent and its preparation method and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776534A (en) * | 2019-02-01 | 2019-05-21 | 山东理工大学 | Ratio sensing type zinc ion fluorescent and its preparation method and application |
| CN109776534B (en) * | 2019-02-01 | 2020-08-28 | 山东理工大学 | Proportional sensing type zinc ion fluorescent probe and preparation method and application thereof |
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