CN104151325A - Fluorescent probe with rhodamine fluorophore as matrix and preparation method of fluorescent probe with rhodamine fluorophore as matrix - Google Patents
Fluorescent probe with rhodamine fluorophore as matrix and preparation method of fluorescent probe with rhodamine fluorophore as matrix Download PDFInfo
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- CN104151325A CN104151325A CN201410328897.0A CN201410328897A CN104151325A CN 104151325 A CN104151325 A CN 104151325A CN 201410328897 A CN201410328897 A CN 201410328897A CN 104151325 A CN104151325 A CN 104151325A
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- rhodamine
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000011159 matrix material Substances 0.000 title abstract 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001514 detection method Methods 0.000 claims abstract description 9
- 238000000799 fluorescence microscopy Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000000523 sample Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 10
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229940043267 rhodamine b Drugs 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 238000010898 silica gel chromatography Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 abstract description 22
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 abstract description 7
- 201000010099 disease Diseases 0.000 abstract description 5
- 238000013399 early diagnosis Methods 0.000 abstract description 3
- 230000008506 pathogenesis Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 238000001917 fluorescence detection Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 210000002700 urine Anatomy 0.000 abstract description 2
- 229910001431 copper ion Inorganic materials 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 239000003068 molecular probe Substances 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 238000001636 atomic emission spectroscopy Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 230000003834 intracellular effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000011897 real-time detection Methods 0.000 description 2
- OALHHIHQOFIMEF-UHFFFAOYSA-N 3',6'-dihydroxy-2',4',5',7'-tetraiodo-3h-spiro[2-benzofuran-1,9'-xanthene]-3-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 OALHHIHQOFIMEF-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 206010003210 Arteriosclerosis Diseases 0.000 description 1
- 102000012437 Copper-Transporting ATPases Human genes 0.000 description 1
- 206010058314 Dysplasia Diseases 0.000 description 1
- 208000002972 Hepatolenticular Degeneration Diseases 0.000 description 1
- 208000008948 Menkes Kinky Hair Syndrome Diseases 0.000 description 1
- 208000012583 Menkes disease Diseases 0.000 description 1
- 239000006146 Roswell Park Memorial Institute medium Substances 0.000 description 1
- 208000018839 Wilson disease Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 206010002026 amyotrophic lateral sclerosis Diseases 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 208000011775 arteriosclerosis disease Diseases 0.000 description 1
- 238000001391 atomic fluorescence spectroscopy Methods 0.000 description 1
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012875 competitive assay Methods 0.000 description 1
- 208000029078 coronary artery disease Diseases 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 230000013632 homeostatic process Effects 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 208000000509 infertility Diseases 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 231100000535 infertility Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
- 230000004792 oxidative damage Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- G—PHYSICS
- 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
Abstract
The invention relates to a fluorescent probe with a rhodamine fluorophore as a matrix and a preparation method of the fluorescent probe. The fluorescent probe has a structural formula as shown in the specification. The preparation method of the fluorescent probe is mild in reaction condition and few and simple in synthesis step; the yield of the fluorescent probe is high; and raw materials are cheap and easy to obtain. The fluorescent probe related by the invention can be applied to detection of environmental pollutants and copper ions in urine and has the advantages of strong anti-jamming capability, short response time, high selectivity and sensitivity and the like, and the detection limit can be as low as the nM grade. In addition, the fluorescent probe can be applied to fluorescence imaging of Cu<2+> in living cells and has a potential application value on the aspects of fluorescence detection of Cu<2+> in a life body as well as early diagnosis and pathogenesis research on diseases related to Cu<2+>.
Description
Technical field
The present invention relates to a kind of fluorescent molecular probe and preparation method thereof, particularly a kind ofly take fluorescent probe that rhodamine fluorophore is parent and preparation method thereof.
Background technology
Copper is requisite trace element in human body, at the aspects such as structure of neural system, genetic expression, protein, plays an important role.Lack copper in human body and easily cause and lack copper anaemia, dysplasia of children, hypomnesis, slow in reacting, woman infertility etc., lack for a long time copper also can cause arteriosclerosis, cause the generation of coronary heart disease.On the other hand, excessive copper is taken in also can produce toxicity, and this is because copper catalysis has produced the oxidative damage that active oxygenated species can cause other biological molecule etc.Therefore, in cell, the imbalance of the homeostasis of copper will cause the disorder of its metabolism and growth, even causes serious disease and death.The disease relevant to copper comprises Menkes syndromes, Wilson disease, alzheimer's disease, ALS disease etc.
With respect to detection methods such as atomic emission spectrometry (AES), atomic absorption spectrometry (AAS), atomic fluorescence spectroscopy (AFS) and electrochemical methods, highly sensitive, real-time detection that fluorescence detection has, to advantages such as the basic not damageds of sample, at present the common fluorophore for fluoroscopic examination mainly contains rhodamine fluorophore, naphthalimide fluorescent group, fluoresceins fluorophore etc.Wherein, rhodamine and derivative thereof are good owing to having higher specific absorbance, stronger fluorescence quantum yield and photochemical stability etc., have been widely used in the design of ion probe.
Current already present organic molecular probe mainly also exists following problem: I. to synthesize aspect, and the design of probe molecule is synthetic also exists complex structure, step is more loaded down with trivial details, productive rate is lower deficiency.II. fluoroscopic examination aspect, there is the problems such as detection sensitivity is low, the time of response is long, immunity from interference is low in part organic molecular probe.Therefore, design the fluorescent probe molecule of synthesizing new, realize trace detection and the interior fluorescence imaging of cell of cupric ion, will there is important Research Significance and using value.
Summary of the invention
One of object of the present invention is to overcome the deficiency that existing organic probe molecule exists, and provides a class to take the fluorescent probe that rhodamine fluorophore is parent.
Two of object of the present invention is to provide the preparation method of this fluorescent probe.
For achieving the above object, the present invention adopts following reaction mechanism:
；
Or
According to above-mentioned reaction mechanism, the present invention adopts following technical scheme:
The fluorescent probe that the rhodamine fluorophore of take is parent, is characterized in that the structural formula of this fluorescent probe:
or
.
Prepare an above-mentioned method of take the fluorescent probe that rhodamine fluorophore is parent, it is characterized in that the concrete steps of the method are:
A. salicylic aldehyde and epoxy chloropropane is soluble in water according to the mol ratio of 2:1 ~ 5:1, back flow reaction 4 h, cooled and filtered obtains product, then by the method for recrystallization, purifies and obtains 1,3-bis-(2-carboxaldehyde radicals phenoxy group)-2-propyl alcohol, and its structural formula is:
;
B. rhodamine B or rhodamine 6G and hydrazine hydrate is even according to the mixed in molar ratio of 1:10 ~ 1:40, and be dissolved in ethanol, then reflux 8 h, the product utilization silica gel column chromatography separation obtaining obtains rhodamine B hydrazides or rhodamine 6G hydrazides, and its structural formula is:
or
;
C. by 1 of above-mentioned steps a gained, the rhodamine B hydrazides of 3-bis-(2-carboxaldehyde radicals phenoxy group)-2-propyl alcohol and step b gained is even according to the mixed in molar ratio of 1:3 ~ 1:10, and be dissolved in ethanol, reflux 24 h, rotary evaporation, except desolventizing, utilizes silica gel column chromatography separation to obtain rhodamine B derivative probe molecule.
Application in above-mentioned trace detection of take fluorescent probe cupric ion in determinand that rhodamine fluorophore is parent.
Application in above-mentioned fluorescence imaging of take fluorescent probe cupric ion in realizing viable cell that rhodamine fluorophore is parent.
Fluorescent probe of the present invention, for the trace detection of determinand cupric ion, has following feature: 1. selectivity is good, can realize single cupric ion and detect, and does not have coexisting ion impact; 2. highly sensitive, detectability is low to moderate nmole rank; Time of response fast, reaction completes moment, can realize real-time detection; 4. fluorescence and colour-change naked eyes are visible.
According to the present invention, the determinand that such fluorescent probe detects for cupric ion, includes but not limited to environmental pollutant sample and human urine sample.
According to the present invention, the selected viable cell of such fluorescent probe cupric ion fluorescence imaging, includes but not limited to Hela cell.
A class provided by the present invention be take the preparation method of the fluorescent probe that rhodamine fluorophore is parent, and reaction conditions is gentle, and synthesis step is few, and products collection efficiency is high, and raw material is cheap and easy to get.Fluorescent probe provided by the present invention is short to the cupric ion time of response, selectivity and highly sensitive, and detectability is low to moderate nM rank, and can with the naked eye identify the variation of fluorescence and color, is a kind of fluorescent probe of good detection cupric ion.Fluorescent probe provided by the present invention also can be applicable to Cu in viable cell
2+fluorescence imaging and in life entity Cu
2+fluoroscopic examination, with Cu
2+on the early diagnosis of relative disease and pathogenesis, there is potential using value.
Accompanying drawing explanation
Fig. 1 is the uv-visible absorption spectra of selectivity experiment in embodiment 2.
Fig. 2 is the fluorescence spectrum of titration experiments in embodiment 2.
Fig. 3 is the cell fluorescence imaging of rhodamine B derivative probe molecule in embodiment 3.
Embodiment
For making the present invention easier to understand, below in conjunction with drawings and Examples, describe in detail.These embodiment only play illustrative effect, are not limited to range of application of the present invention.
Embodiment 1: the preparation of rhodamine B derivative probe molecule
(1) salicylic aldehyde and epoxy chloropropane is soluble in water according to the mol ratio of 2:1 ~ 5:1, reacting by heating 4 h, cooled and filtered obtains product, then by the method for recrystallization, purifies and obtains 1,3-bis-(2-carboxaldehyde radicals phenoxy group)-2-propyl alcohol.
(2) rhodamine B and hydrazine hydrate is even according to the mixed in molar ratio of 1:10 ~ 1:40, and be dissolved in ethanol, reflux 8 h then, the product utilization silica gel column chromatography separation obtaining obtains rhodamine B hydrazides.
(3) prepared by above-mentioned steps (1) 1, rhodamine B hydrazides prepared by 3-bis-(2-carboxaldehyde radicals phenoxy group)-2-propyl alcohol and above-mentioned steps (2) is even according to the mixed in molar ratio of 1:3 ~ 1:10, and be dissolved in ethanol, reflux 24 h, rotary evaporation is except desolventizing, utilize silica gel column chromatography separation to obtain rhodamine B derivative probe molecule, then adopt nuclear magnetic resonance analyser (Bruker AVANCE 500MHz type nuclear magnetic resonance analyser, Bruker company, Switzerland) sterling of the rhodamine B derivative making is carried out to nuclear magnetic resonance spectroscopy, concrete analysis result is as follows:
1h NMR: δ (deuterated DMSO) 9.14(s, 2H, N=C-H), 7.90(m, 2H, ArH) and, 7.57(m, 6H, ArH), 7.29(m, 2H, ArH), 6.99(t, 2H, ArH), 6.29-6.50(m, 12H, ArH), 4.30-4.54 (m, 5H, CH
2cHCH
2), 3.35(s, 1H, OH), 3.23 (q, 16H, N
cH 2 cH
3), 1.09 (t, 24H, NCH
2 cH 3 ).
Embodiment 2: the preparation of rhodamine 6G derivative probe molecule
(1) salicylic aldehyde and epoxy chloropropane is soluble in water according to the mol ratio of 2:1 ~ 5:1, reacting by heating 4 h, cooled and filtered obtains product, then by the method for recrystallization, purifies and obtains 1,3-bis-(2-carboxaldehyde radicals phenoxy group)-2-propyl alcohol.
(2) rhodamine 6G and hydrazine hydrate is even according to the mixed in molar ratio of 1:10 ~ 1:40, and be dissolved in ethanol, then reflux 8 h, obtain rhodamine 6G hydrazides by solid with deionized water repetitive scrubbing after cold filtration.
(3) prepared by above-mentioned steps (1) 1, rhodamine 6G hydrazides prepared by 3-bis-(2-carboxaldehyde radicals phenoxy group)-2-propyl alcohol and above-mentioned steps (2) is even according to the mixed in molar ratio of 1:3 ~ 1:10, and be dissolved in ethanol, reflux 24 h, rotary evaporation is except desolventizing, utilize silica gel column chromatography separation to obtain rhodamine 6G derivative probe molecule, then adopt nuclear magnetic resonance analyser (Bruker AVANCE 500MHz type nuclear magnetic resonance analyser, Bruker company, Switzerland) carry out nuclear magnetic resonance spectroscopy, concrete analysis result is as follows:
1h NMR: δ (deuterated DMSO): 9.20(s, 2H, N=C-H), 7.94(m, 2H, ArH), 7.60(m, 6H, ArH), 7.30(m, 2H, ArH), 6.97(t, 2H, ArH), 6.27-6.51(m, 12H, ArH), 4.33-4.56 (m, 5H, CH
2cHCH
2), 3.32(s, 1H, OH), 3.20 (q, 8H, NH
cH 2 cH
3), 1,87 (s, 12H, ArCH
3), 1.12 (t, 12H, NHCH
2 cH 3 ).
Embodiment 3: the rhodamine B derivative of usining detects cupric ion as fluorescent probe molecule
(1) take the rhodamine B derivative probe molecule of preparation in embodiment 1, be made into 1 * 10
-5the ethanolic soln of M.
(2) prepare the strong solution (0.1M) of each metal ion species, comprise that interfering ion is as Na
+, K
+, Mg
2+, Ca
2+, Ba
2+, Zn
2+, Li
+, Mn
2+, Co
2+, Hg
2+deng, and ion Cu to be detected
2+.
(3) in selectivity experiment, each metal ion species of getting respectively certain equivalent joins in the rhodamine B derivative solution of 2.0 mL, then carries out absorption spectrum and fluorescence spectrum test.The results are shown in accompanying drawing 2.
(4) in titration experiments, with pipette, extract 2.0 mL rhodamine B derivatives, be placed in 1.0 cm * 1.0 cm quartz colorimetric utensils, with microsyringe, in solution, add Cu successively
2+solution, often adds and once carries out spectrum test one time.The results are shown in accompanying drawing 3.
(5), in competitive assay, first certain interfering ion is joined in 2.0 mL rhodamine B derivative solution, then add Cu
2+, then carry out spectrum test.
Embodiment 4: rhodamine B derivative is applied to cell imaging
(1) control group, joins 1 * 10
-5the RPMI. 1640 water culture liquid of the rhodamine B derivative probe molecule of M;
(2) Hela cell is cultivated 0.5 hour in above-mentioned nutrient solution;
(3) experimental group, first, with the Cu of 10 μ M
2+water culture Hela cell 0.5 hour, then, then cultivates 0.5 hour with the probe nutrient solution of 10 μ M;
(4) with PBS damping fluid, rinse cell 3 times, will by the nutrient solution of Cell uptake, do not washed away;
(5) cell after cultivating is carried out to imaging on Laser Scanning Confocal Microscope, with the laser excitation of 543 nm, observation of cell fluorescence imaging, result is as Fig. 4.
Fig. 1 carries out the selectivity titration experiments of ultraviolet-visible spectrum with rhodamine B derivative in embodiment 3, can clearly be seen that rhodamine B derivative probe molecule synthetic in the present invention is for Cu from figure
2+there is good selectivity.
Fig. 2 is the fluorometric titration spectrum of rhodamine B derivative in embodiment 3, as can be seen from the figure along with Cu
2+continuous increase, the fluorescence intensity of rhodamine B derivative solution is linear increasing thereupon also.
Fig. 3 is the result that in embodiment 4, rhodamine B derivative is applied to cell imaging.As can be seen from the figure the rhodamine B derivative probe molecule, being synthesized by the present invention can successfully be applied to cell level and detect intracellular Cu
2+.When cultivating with rhodamine B derivative probe molecule after the cell of cultivating with cupric ion in advance, by confocal microscope, can observe cell and send obvious fluorescence, thereby can find out that the synthetic probe molecule of the present invention can successfully detect intracellular cupric ion, this is for studying from now in life entity and Cu
2+early diagnosis and the pathogenesis of relative disease have great importance.
Be only several specific embodiment of the present invention as mentioned above, be not limited to the present invention.Within the spirit and principles in the present invention all, adopt that method same or similar with it is resulting take fluorescent probe that rhodamine fluorophore is parent for cupric ion fluorescence imaging in cell, all in protection domain of the present invention.
Claims (4)
1. the fluorescent probe that the rhodamine fluorophore of take is parent, is characterized in that the structural formula of this fluorescent probe:
or
.
2. prepare a method of take the fluorescent probe that rhodamine fluorophore is parent according to claim 1, it is characterized in that the concrete steps of the method are:
A. salicylic aldehyde and epoxy chloropropane is soluble in water according to the mol ratio of 2:1 ~ 5:1, back flow reaction 4 h, cooled and filtered obtains product, then by the method for recrystallization, purifies and obtains 1,3-bis-(2-carboxaldehyde radicals phenoxy group)-2-propyl alcohol, and its structural formula is:
;
B. rhodamine B or rhodamine 6G and hydrazine hydrate is even according to the mixed in molar ratio of 1:10 ~ 1:40, and be dissolved in ethanol, then reflux 8 h, the product utilization silica gel column chromatography separation obtaining obtains rhodamine B hydrazides or rhodamine 6G hydrazides, and its structural formula is:
or
;
C. by 1 of above-mentioned steps a gained, the rhodamine B hydrazides of 3-bis-(2-carboxaldehyde radicals phenoxy group)-2-propyl alcohol and step b gained is even according to the mixed in molar ratio of 1:3 ~ 1:10, and be dissolved in ethanol, reflux 24 h, rotary evaporation, except desolventizing, utilizes silica gel column chromatography separation to obtain rhodamine B derivative probe molecule.
3. the application in a trace detection of take fluorescent probe cupric ion in determinand that rhodamine fluorophore is parent according to claim 1.
4. one kind according to the application of take in the fluorescence imaging of fluorescent probe cupric ion in realizing viable cell that rhodamine fluorophore is parent described in claim 1.
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496997A (en) * | 2015-01-12 | 2015-04-08 | 济南大学 | Ferric ion fluorescent probe compound as well as preparation method and application thereof |
| CN105754587A (en) * | 2016-03-30 | 2016-07-13 | 泰山医学院 | Imidazo pyridine rhodamine hydrazide type cupric ion ratio fluorescence probe and application thereof |
| CN107417694A (en) * | 2017-05-24 | 2017-12-01 | 延安大学 | A kind of colorimetric and the double response type bismuth ion detection probes of fluorescence and preparation method thereof |
| CN108440548A (en) * | 2018-03-31 | 2018-08-24 | 浙江工业大学 | A kind of rhodamine 6G class fluorescence probe of the group containing hydrazides and its preparation and application |
| CN112920798A (en) * | 2021-01-27 | 2021-06-08 | 大连海事大学 | Near-infrared fluorescent probe and preparation method and application thereof |
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Non-Patent Citations (6)
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496997A (en) * | 2015-01-12 | 2015-04-08 | 济南大学 | Ferric ion fluorescent probe compound as well as preparation method and application thereof |
| CN104496997B (en) * | 2015-01-12 | 2016-04-13 | 济南大学 | A kind of ferric ion fluorescent probe compounds and preparation and application thereof |
| CN105754587A (en) * | 2016-03-30 | 2016-07-13 | 泰山医学院 | Imidazo pyridine rhodamine hydrazide type cupric ion ratio fluorescence probe and application thereof |
| CN107417694A (en) * | 2017-05-24 | 2017-12-01 | 延安大学 | A kind of colorimetric and the double response type bismuth ion detection probes of fluorescence and preparation method thereof |
| CN107417694B (en) * | 2017-05-24 | 2019-04-26 | 延安大学 | A kind of colorimetric and the double response type bismuth ion detection probes of fluorescence and preparation method thereof |
| CN108440548A (en) * | 2018-03-31 | 2018-08-24 | 浙江工业大学 | A kind of rhodamine 6G class fluorescence probe of the group containing hydrazides and its preparation and application |
| CN112920798A (en) * | 2021-01-27 | 2021-06-08 | 大连海事大学 | Near-infrared fluorescent probe and preparation method and application thereof |
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