CN106565728A - Pyridine rhodamine 6G fluorescence probe compound as well as preparation method and application thereof - Google Patents
Pyridine rhodamine 6G fluorescence probe compound as well as preparation method and application thereof Download PDFInfo
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- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6447—Fluorescence; Phosphorescence by visual observation
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- G—PHYSICS
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Abstract
The invention discloses a pyridine rhodamine 6G fluorescence probe compound as well as a preparation method and application thereof. The preparation method comprises the following steps of, in an organic solvent, mixing rhodamine 6G hydrazide and acetylpyridine, after the rhodamine 6G hydrazide and the acetylpyridine are sufficiently dissolved, adding acetic acid as a catalyst into an obtained first mixture, heating and refluxing a mixed system until a reaction is complete, cooling a reaction system to a room temperature, and carrying out post treatment on the cooled reaction system, so as to obtain a target compound I; and further weighing and taking the compound I, dissolving the compound I in dichloromethane, and putting an obtained second mixture at a dark place to culture a signal crystal, so as to obtain a clear crystal after one week, wherein the mole ratio of the rhodamine 6G hydrazide to the acetylpyridine to the catalyst is (1 to 1.2) to 1 to (0.05 to 0.1). The compound I, to which the invention relates, is a cupric ion fluorescence probe, and has better detection sensitivity; and the fluorescence-emission wavelength of the compound I is located in a long-wavelength interval, the compound I is applicable to a wide pH (potential of Hydrogen) range, and therefore, the compound I can be used for the detection of a copper ion in a biological living cell and the fluorescence imaging of the copper ion in the biological living cell.
Description
The present invention is in Tianjin State Scientific and Technological Commission fund（Fund number：14JCYBJC23900）, Tianjin Normal University's fund（Fund number：
53H14040）Subsidy under carry out.
Technical field
The present invention relates to environmental science, chemical sensitisation technology and bioanalysiss application, are related to pyridine rhodamine 6G glimmering
Light probe compound as receptor to specific to metal copper ion, the use of the bore hole of high selectivity colour developing identification and fluorescence identifying
On the way.
Background technology
Metal ion detection has important application in fields such as biology, medical science, environmental sciences, for example, 2010, Zeng Zhengzhi
Et al. synthesized furtural rhodamine B aldehyde hydrazone compound（Dalton Trans., 2010, 39, 7894-7896）, the change
Compound can according to generation color and change in fluorescence recognizing Cu2+, and can be used as Cu in lung carcinoma cell2+Detection.
The detection metal ion method for adopting at present has various, such as colorimetry, indicator method, electrode method and optical pickocff
Deng.But sensitivity is relatively low during colorimetric method for determining, it is impossible to which the metal ion in active somatic cell is measured.Indicate agent method spirit
Sensitivity and selectivity are low.Electrical interference can be produced during determination of electrode or cell is damaged, therefore is not suitable for cell microscopy.
By contrast, these defects are not had based on the photochemical method of fluorescent probe.Fluorescent probe analysis method has selectivity good, clever
Sensitivity is high, sample size is little, it is simple and efficient the features such as.
The content of the invention
The compound I invented by this patent is a kind of Cu based on pyridine rhodamine 6G2+Fluorescent molecular probe, with Luo Dan
The characteristics of bright 6G lactams volution " closure-colourless ", " open loop-coloured generation fluorescence that is stimulated ", with Schiff's base imines C=N
Double bond structure, can carry out high selectivity fluorescence identifying to copper ion by coordination.
The compound with I architectural features of the present inventor's design is the noval chemical compound for having no report.
First purpose of the present invention there is provided the compound with structure Formulas I.
Second object of the present invention there is provided inclusion compound I and know for the bore hole colour developing to copper ion high selectivity
The purposes of other and fluorescence identifying probe.Experiment shows that compound I is recognized and glimmering with the bore hole colour developing to hydrion high selectivity
Light recognizes the purposes of probe, and does not receive metal ion disturbance.
For achieving the above object the invention discloses following technology contents：
Compound with structure Formulas IN'-(2- pyridine radicals)-ethylidene rhodamine 6G hydrazides：
The present invention further discloses compoundN'-(2- pyridine radicals)-ethylidene rhodamine 6G hydrazides preparation method, compound
The preparation of I is carried out as follows：
The synthesis of compound：
Rhodamine 6G hydrazides and acetylpyridine are added in round-bottomed flask, methanol is added, after fully dissolving, a few drop ice is added
Second acid as catalyst, mixed system is heated to reflux complete to reaction.Reaction system is cooled to into room temperature, by the mixing in flask
System is transferred in the beaker for filling mixture of ice and water, with organic base adjust solution ph to show slightly alkalescence when have solid to separate out,
Vacuum filtration, is precipitated with distilled water wash, obtains crude product, dried in vacuum overnight.Gained crude product Jing pillar layer separation (second
Acetoacetic ester:Petroleum ether=4:1, v:V), obtain target compound.
The present invention further discloses compound I is used as to copper ion high selectivity bore hole colour developing identification and fluorescence identifying
Application in terms of probe.
Compound designed by the present inventionMolecular characterization be the lactams spiral shell of rhodamine 6G in the structure of I
Ring is closure state, and solution is colourless, when copper ion and compoundDuring effect, volution is opened and is changed into quinoid structure, now solution
It is changed into orange red and with fluorescent emission from colourless.Therefore, compoundSelectivity fluorescence identifying can be carried out to copper ion.It is real
Test and show, purposes of the compound I with the bore hole colour developing identification to copper ion high selectivity and fluorescence identifying probe.
The good effect that compound I disclosed in this invention has compared with prior art is：
(1) safe preparation process, synthesis are simple；
(2) the advantages of there is high sensitivity, high selectivity and fast reactivity to copper ion；
(3) fluorescent probe does not receive Ba when copper ion is detected2+, Cd2+, Co2+, Fe3+, Mn2+, Zn2+, Bi3+, Ca2+,
Hg2+, Mg2+, Ni2+, Pb2+, Sr2+The interference of plasma；
(4) the pH wide scopes that the fluorescent probe is adapted to, it is adaptable to which biological cell copper ion is recognized.
Description of the drawings：
Structural formulas of the Fig. 1 for compound I；
Mono-crystalline structures figures of the Fig. 2 for compound I；
Fig. 3 is compound I (10μM THF/)tris-HCl (4:7.5) blank solution and 5 times are worked as 6, v/ v, pH=
Measure the ultra-violet absorption spectrum of 14 metal ion species solution；
Fig. 4 is compound I (10μM THF/)tris-HCl (4:7.5) blank solution and 5 times are worked as 6, v/ v, pH=
Measure the fluorescence emission spectrum of 14 metal ion species solution；
Fig. 5 is compound I blank under white light, 13 metal ion species and copper ion (left 1 in figure) recognition imaging contrast；
Fig. 6 is compound I blank under fluorescence, 13 metal ion species and copper ion (left 1 in figure) recognition imaging contrast；
Fig. 7 is compoundMass spectrum；
Fig. 8 is the ELIMINATION OF ITS INTERFERENCE fluorescence emission spectrum of 13 metal ion species when compound I is recognized to copper ion；
Fig. 9 is compound I to copper ion titration fluorescence spectrum；
Figure 10 is compound I uv absorption working curves；
Figure 11 is that compound I recognizes pH fluorescence titration curves to copper ion；
Figure 12 is that compound I is detected to the copper ion in living cells and its fluorescence imaging；Scale in picture is 20 μm.
Specific embodiment：
In order to more fully explain the enforcement of the present invention, there is provided following preparation method embodiments.These embodiments are only
Explain, rather than limit the scope of the present invention.In order to simple and clear, in discussion below to the description of known technical method,
The process for preparation of solution is repeated no more.Raw material rhodamine 6G hydrazides therein and acetylpyridine are commercially available.
Embodiment 1.
CompoundSynthesis：
1.0 g rhodamine 6Gs hydrazides and 0.30 g 2- acetylpyridines are added in 100 mL flasks, plus 10 mL methanol room temperature
Stirring 10 minutes, treats fully dissolving, then adds 0.1 mL glacial acetic acids and make catalyst, mixed system is heated to reflux 2.5 little
It is complete up to reaction, reaction system is cooled to into room temperature, the mixed system in flask is transferred to the burning for filling mixture of ice and water
Cup in, with triethylamine adjust solution to show slightly alkalescence（PH value 7-7.5）, have solid to separate out in beaker immediately, vacuum filtration, with steaming
Distilled water washing precipitation 2-3 time, obtains crude product, dried in vacuum overnight.Gained crude product Jing pillar layer separation (ethyl acetate:
Petroleum ether=4:1, v:V), 0.98 g of target compound, yield 79%, mp are obtained: 266-268 ℃.
1H NMR (400 MHz, DMSO-d6) δ 8.56 (d, J = 4.5 Hz, 1H), 7.88- 7.86 (m,
1H), 7.75 (t, J = 7.7 Hz, 1H), 7.57 (s, 2H), 7.55 (s, 1H), 7.41-7.38 (m, 1H),
7.09 (d, J = 6.6 Hz, 1H), 6.27 (s, 2H), 6.25 (s, 2H), 5.01 (t, J = 5.1 Hz,
2H), 3.11 (dt, J = 13.1, 6.6 Hz, 4H), 1.88 (s, 6H), 1.19 (t, J = 7.0 Hz, 6H);
13C NMR (101 MHz, DMSO-d6) δ 169.41, 159.91, 154.65, 152.07, 151.76,
149.26, 147.98, 137.22, 133.37, 130.37, 129.05, 127.87, 125.56, 124.26,
123.29, 121.29, 118.37, 105.95, 96.14, 66.93, 17.49, 14.65 ppm;
MS (ESI-MS), m/z, 532.7 [M+H]+。
The synthetic route of above course of reaction is as follows：
Weigh 20mg compound I to be dissolved in dichloromethane, be placed in dark place culture monocrystalline.Clear crystal is obtained after one week.Chemical combination
The three-dimensional molecular structure figure of thing I（30% probability level of ellipsoid）：The mono-crystalline structures adopt APEX II CCD single crystal diffractometers, make
With being incident radiation through graphite monochromatised Mok alpha rays (λ=0.71073), withω-2θScan mode collects point diffraction,
Cell parameter is obtained through least square refinement, monocrystalline, structure cell ginseng is solved using software from difference Fourier electron density map
Number is：
Embodiment 2.
CompoundSynthesis：
By 2.5g rhodamine 6Gs hydrazides and 0.7g acetylpyridines, in adding 100mL flasks, and add 15mL methanol that solid is molten
Solve, then Deca 0.2mL glacial acetic acid makees catalyst, mixed system is heated to reflux to reacting completely, reaction system is cooled to room
After temperature, mixed system is transferred in the beaker for filling mixture of ice and water, adjusts solution with triethylamine neutral to alkalescence, beaker is shown slightly
There is solid to separate out, vacuum filtration is precipitated 2-3 time with distilled water wash, obtains crude product, dried in vacuum overnight.Gained is thick to be produced
Product Jing pillar layer separation (ethyl acetate:Petroleum ether=4:1, v:V), target compound 2.2g, yield 71%, mp are obtained:266-268
℃。
Embodiment 3
CompoundSynthesis：
By 5.0 g rhodamine 6Gs hydrazides and 1.5 g acetylpyridines, in adding 100 mL flasks, and 20 mL methanol are added by solid
Dissolve, then 0.5 mL glacial acetic acids of Deca make catalyst, mixed system is heated to reflux to reacting completely, reaction system is cooled to
After room temperature, mixed system is transferred in the beaker for filling mixture of ice and water, with triethylamine adjust solution to show slightly alkalescence, in beaker
There is solid to separate out immediately, vacuum filtration is precipitated 2-3 time with distilled water wash, obtains crude product, dried in vacuum overnight.Gained is thick
Product Jing pillar layer separation (ethyl acetate:Petroleum ether=4:1, v:V), target compound 3.7g, yield 60%, mp are obtained:266-
268℃.Weigh 20mg compound I to be dissolved in dichloromethane, be placed in dark place culture monocrystalline.Clear crystal is obtained after one week.
Embodiment 4.
Compound I to Cu2+Ion recognition character：
Accurately Weigh Compound I, uses tetrahydrofuran in 10mL brown volumetric flasks:tris-HCl=4:6(v:V, pH=7.5）It is slow
Solution constant volume is rushed, 1.0 × 10 are configured to-3The storing solution of M.
Prepare Mg2+、Ca2+、Mn2+、Fe3+、Co2+、Ni2+、Cu2+、Zn2+、Sr2+、Cd2+、Ba2+、Hg2+、Pb2+、Bi3+It is tested
The tetrahydrofuran of examination metal ion:tris-HCl=4:6(v:V), the 1.0 × 10 of pH=7.5-3The storing solution of M.
Prepare THF:Water=4:6(v:V), pH is respectively 1,2,3,4,5,6,7,8,9,10,11,12,13 solution, error
For ± 0.5.
Determine that compound I being capable of high selectivity Cu by ultraviolet spectra, fluorescence spectrum2+Ion.
Concrete operations are：
The 1.0 × 10 of 0.1mL compound I are measured accurately with liquid-transfering gun-3The storing solution of M, moves into 15 10mL brown volumetric flasks
In, first bottle comprises only compound I, and remaining is separately added into 0.5mL metal ion storing solutions, uses tetrahydrofuran:tris-HCl=4:
6(v:V, pH=7.5）Solution constant volume.Compound is determined respectively, compound I and Mg2+、Ca2+、Mn2+、Fe3+、Co2+、Ni2+、
Cu2+、Zn2+、Sr2+、Cd2+、Ba2+、Hg2+、Pb2+、Bi3+The ultraviolet spectra of the metal ion solution for coexisting, fluorescence spectrum.
The ultraviolet spectra of compound I and Action of Metal Ions, fluorescence spectrum are shown in Fig. 3, Fig. 4.
Test shows, compound I (10μM THF/)tris-HCl(4:6, v/v, pH=7.5) blank solution, compound I
5 times of equivalent Mg of middle addition2+、Ca2+、Mn2+、Fe3+、Co2+、Ni2+、Cu2+、Zn2+、Sr2+、Cd2+、Ba2+、Hg2+、Pb2+、Bi3+'s
THF：H2O=4:6(v:V, pH=7.5) in solution, except Cu2+Outside system, the ultra-violet absorption spectrum of remaining solution, fluorescence emission spectrum
Intensity it is very weak.Add Cu2+THF：H2O=4:6(v:V, pH=7.5) solution occur at 520nm ultraviolet absorption peak and
Fluorescence signal is significantly increased at the 550nm.This is due to compound I and Cu2+Produce coordination, acyl in the volution of compound I
There is open loop in amine structure, rhodamine parent oxa- anthracene nucleus generates quinoid structure, system and recovered bigπKey is conjugated, and causes visible
There is color change in light area.Fig. 5, Fig. 6 are we can observe that containing Cu2+Compound I solution respectively under white light and 254nm fluorescence
It is changed into orange red from colourless（Gray scale is represented）.
Embodiment 5.
Compound I is to Cu2+During ion identification, Mg2+、Ca2+、Mn2+、Fe3+、Ni2+、Co2+、Zn2+、Sr2+、Cd2+、Ba2+、Hg2+、
Pb2+、Bi3+The ELIMINATION OF ITS INTERFERENCE of 13 metal ion species：
Compound I, above-mentioned tested metal ion solution are prepared according to 4 method of embodiment.In compound I (10μM THF/)tris-HCl(4:6,v:V, pH=7.5) Cu is added in solution2+(50μM) and other metal ions (100 are separately added intoμM).Root
We can observe that according to Fig. 8, in the presence of having other metal ions, compound I still with Cu2+ Generation is acted on, fluorescent emission
Spectrum is presented significant change and intensity is hardly by other metal ion disturbances.Prove compound I to Cu2+ Show high choosing
Selecting property.
Embodiment 6.
Compound I is to Cu2+During ion identification, Cu2+ Impact of the concentration to fluorescence spectrum：
Compound I, tested Cu are prepared according to 4 method of embodiment2+Solution.
Compound I original state unstressed configuration signals.With Cu2+The increase of solubility, fluorescence signal strengthen therewith, this explanation
Cu2+Rhodamine lactams volution in inducing compounds I is opened.Cu2+ Fig. 9 is shown in impact of the concentration to fluorescence.
Embodiment 7.
Compound I is to Cu2+The fluorescence titration of ion identification pH scope is tested：
We conducted soda acid fluorescence titration to determine compound I to Cu2+The optimum pH scope of identification.Configuration concentration first
For 1.0 × 10-3mol·L-1Storing solution, with the buffer solution of HCl and the NaOH different pH value of configuration as constant volume solution.
It is observed that compound I fluorescence signal occurs in the range of pH 4-13 in Figure 11 fluorescence titration curve charts, as addition Cu2+Afterwards
The expanded range of Fluorescence Increasing is to 1-10.This shows that compound I is can serve as in the range of biological pH（pH 4-10）Detection Cu2+'s
Fluorescent molecular probe.
Embodiment 8.
Compound I detects copper ion and its fluorescence imaging experiments in being applied to living cells：
By 1.5 × 10-5mol·L-1Compound I (takes from concentration for 1.0 × 10-3mol·L-1Storing solution) be added to and cultivate
Mouse macrophage culture dish in, cultivate 3.5 hours at 37 DEG C, suction out solution in culture dish, pure water washes three times, each 2mL.
To in the above-mentioned Tissue Culture Dish containing compound I, Cu is separately added into2+Concentration is 2.0mL 1.5 × 10-5mol·L-1、5.0mL
Cu2+1.5×10-5mol·L-1(concentration is taken from for 1.0 × 10-3mol·L-1Storing solution), enter incubator overnight.Such as Figure 12 institutes
Show, cell is presented rhodamine 6G characteristic fluorescence.Find simultaneously, when concentration of metal ions increases, cell fluorescence intensity also increases therewith
Plus.
Compound can be used for the detection of copper ion in living things system and the copper ion fluorescence imaging in living biological cell.
In sum, compound I involved in the present invention is a kind of copper ion fluorescence probe, with preferably detecting sensitive
Degree, the fluorescence emission wavelengths of compound I are between long wavelength region, it is adaptable to pH wide scopes, therefore, can be used for living biological cell
Copper ion fluorescence imaging in middle copper ion detection and living biological cell.
Claims (5)
1. there is structural formulaCompoundN'-(2- pyridine radicals)-ethylidene rhodamine 6G hydrazides
。
2. compound described in claim 1N'-(2- pyridine radicals)-ethylidene rhodamine 6G hydrazides preparation method, its feature exists
In carrying out by the steps：
In organic solvent, rhodamine 6G hydrazides and acetylpyridine are mixed, acetic acid is added after fully dissolving and be catalyzed
Agent, mixed system is heated to reflux to reaction completely, reaction system being cooled to room temperature, mixed system being transferred to and is filled frozen water
In the beaker of mixture, solution ph is adjusted as 7-7.5 with organic base, vacuum filtration is precipitated with distilled water wash, slightly produced
Product, dried in vacuum overnight, gained crude product Jing pillar layer separation, eluant is v:V ethyl acetate:Petroleum ether=4:
1, obtain target compound；Further Weigh Compound I is dissolved in dichloromethane, is placed in dark place culture monocrystalline, after one week
To clear crystal；Wherein rhodamine 6G hydrazides：Acetylpyridine：The mol ratio of catalyst is 1-1.2：1：0.05-0.1；It is described
Organic solvent be methanol；Described organic base is triethylamine.
3. N ' described in claim 1-(2- pyridine radicals)-ethylidene rhodamine 6G hydrazides monocrystalline, it is characterised in that the mono-crystalline structures
Using APEX II CCD single crystal diffractometers, using through graphite monochromatised Mok alpha rays, λ=0.71073 is incident spoke
Penetrate, withω-2θ is scannedMode collects point diffraction, obtains cell parameter through least square refinement, from difference Fourier electronics
Density map solves monocrystalline using software, and cell parameter is：
。
4. compound described in claim 1N'-(2- pyridine radicals)-ethylidene rhodamine 6G hydrazides prepared as high to copper ion
Application in terms of selectivity bore hole colour developing identification and fluorescence identifying.
5. compound described in claim 1N'-(2- pyridine radicals)-ethylidene rhodamine 6G hydrazides prepare as living biological cell
The application in terms of copper ion fluorescence imaging in middle copper ion detection and living biological cell.
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|---|---|---|---|---|
| CN111307778A (en) * | 2020-03-31 | 2020-06-19 | 西安医学院 | Preparation method and detection method of copper ion semi-quantitative detection test paper |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111307778A (en) * | 2020-03-31 | 2020-06-19 | 西安医学院 | Preparation method and detection method of copper ion semi-quantitative detection test paper |
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Application publication date: 20170419 |