CN110156687A - A kind of fluorescence probe and its preparation method and application detecting bivalent cupric ion - Google Patents
A kind of fluorescence probe and its preparation method and application detecting bivalent cupric ion Download PDFInfo
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- CN110156687A CN110156687A CN201910396693.3A CN201910396693A CN110156687A CN 110156687 A CN110156687 A CN 110156687A CN 201910396693 A CN201910396693 A CN 201910396693A CN 110156687 A CN110156687 A CN 110156687A
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- 239000000523 sample Substances 0.000 title claims abstract description 58
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000001514 detection method Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- 229940125904 compound 1 Drugs 0.000 claims description 4
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 7
- 239000003814 drug Substances 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 25
- 210000004027 cell Anatomy 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 229910001431 copper ion Inorganic materials 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 238000002211 ultraviolet spectrum Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 210000004881 tumor cell Anatomy 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N Picolinic acid Natural products OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000004252 FT/ICR mass spectrometry Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 208000029078 coronary artery disease Diseases 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000011132 hemopoiesis Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/06—Ring systems of three rings
- C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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
- 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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- 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
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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- 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
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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Abstract
The invention discloses a kind of fluorescence probes and its preparation method and application for detecting bivalent cupric ion, and wherein the chemical formula of fluorescence probe is C31H27N3O5, it has the following structure:The preparation condition of fluorescence probe of the present invention is simple, which can be to Cu under the conditions of ultraviolet and fluorescence2+There is response, and Cu can be detected in pure water and cell2+, there is huge application potential in terms of biological medicine.
Description
Technical field
The invention belongs to metal ion detection technical fields, and in particular to it is a kind of detect bivalent cupric ion fluorescence probe and
Preparation method and use.
Background technique
With the improvement of living standards, people increasingly pay close attention to the variation of physical fitness, to the micro member in body system
The concern of element is far longer than the past.Common trace elements iron in human body, copper, the content in life entity such as magnesium is to life system
Health it is very important, so the method for inventing the microelement that a kind of method is efficiently able to detect in cell is very heavy
It wants.
Copper plays extremely heavy as essential microelement and nutriment in life system in life system
The help of copper ion is be unable to do without in the effect wanted, such as biological intracorporal hematopoiesis, copper ion participates in a variety of enzymes in heart
Synthesis, copper ion will increase a possibility that coronary heart disease disease is sent out once lacking.If in addition, in life process copper ion not certain
In range, the illness possibility of alzheimer's disease, familial amyotrophic will increase, therefore study in life entity to content of copper ion
Detection have inevitable effect for the normal operation for the system of sustaining life.Meanwhile tumour cell and human normal are thin
Cell phase ratio, copper ion content in tumour cell are obviously greater than normal cell, are primarily due in copper ion in tumour cell
In be easier to be enriched with.
There is an atomic absorption spectrography (AAS) for the monitoring method of general content of copper ion, inductively coupled plasma mass spectrometry method,
Honourable photometry and cyclic voltammetry etc., however that all there is detection process is many and diverse for these methods, testing result is insensitive, cannot
The defects of a large amount of detection and localizations and real-time monitoring.Comparatively, fluorescence probe overcomes the limitation of the above method, it can be quick
, sensitively, specific detection copper ion, method can make probe for cell sheet simply by the structure of transformation probe
Body causes the smallest injury without influencing testing result.Currently, method of the fluorescence probe for cell detection has been obtained extensively
General application.Synthesize a kind of fluorescence probe that is efficient, stable, being capable of copper ion in real-time detection cell have it is important
Meaning.
Summary of the invention
The present invention is intended to provide a kind of fluorescence probe and its preparation method and application for detecting bivalent cupric ion, to be solved
The technical issues of be by MOLECULE DESIGN synthesis be able to detect identification Cu2+Fluorescence probe.The present invention is based on Cu2+It is catalyzed ester group
Hydrolysis principle, fluorescence probe is in Cu2+Under effect, ester group is by Cu2+It is hydrolyzed into hydroxyl and fluorescent quenching occurs, design and synthesize
A kind of novel fluorescent probe compounds.
The present invention detects the fluorescence probe of bivalent cupric ion, chemical formula C31H27N3O5, structural formula is as follows:
The present invention detects the preparation method of the fluorescence probe of bivalent cupric ion, includes the following steps:
Compound 1 (100mg) is added in anhydrous DMSO (5mL) and is heated to 70 DEG C, is cooled to room temperature acquisition solution A；It will
2- pyridine carboxylic acid 30mg) and EDC (90.8mg), DMAP (27.0mg) be added in anhydrous DMSO (5mL), solution B is obtained after dissolution；
The solution A is mixed with the solution B, N2Protection, reacts for 24 hours under room temperature；Product is added dropwise to about after reaction
In the distilled water of 200mL, there is yellow product precipitation, be evaporated under reduced pressure, obtain crude product, depressurizes and take out after being recrystallized with dehydrated alcohol
Filter, can be obtained target product, without just obtaining final fluorescence probe by silica gel column chromatography separating-purifying.
Synthesis process of the present invention is as follows:
The purposes of fluorescence probe of the present invention is in detection Cu2+During use as detection reagent.
Further, fluorescence probe of the present invention can by way of hydrolysis specific recognition Cu2, pass through ultraviolet or fluorescence
Mode is detectable, to Cu2+There is specific recognition.Fluorescence intensity and Cu in fluorescence spectrum2+Concentration is inversely proportional, with
Cu2+The increase of concentration and reduce.
The fluorescence probe can be with the Cu in quantitative detection pure water2+, also may adapt to Cu in living cells2+Detection.
Preparation condition of the invention is simple, which can be to Cu under the conditions of ultraviolet and fluorescence2+There is response, and
Cu can be detected in pure water and cell2+, there is huge application potential in terms of biological medicine.
Detailed description of the invention
Fig. 1 is fluorescence probe of the present invention in using DMSO-d6 as solvent1H-NMR(400MHz)。
Fig. 2 is the mass spectrogram of fluorescence probe of the present invention.
Fig. 3 is the infrared spectrogram of fluorescence probe of the present invention.
Fig. 4 is the UV-Vis absorbance that fluorescence probe of the present invention is added after different metal ions in aqueous solvent.
Fig. 5 is the 0--30 μm of ol/L various concentration Cu of addition into probe solution2+UV-Vis absorbance afterwards.
Fig. 6 is that the fluorescence spectra after different metal ions is added into probe solution.
Fig. 7 is the 0--30 μm of ol/L various concentration Cu of addition into probe solution2+Fluorescent quenching figure afterwards.
Fig. 8 is the 0--10 μm of ol/L various concentration Cu of addition into probe solution2+Linear fit afterwards, linear coefficient R2=
0.96892。
Fig. 9 is that 10 μ L are added into HeLa cell, 10-3Cell and training after the probe solution culture half an hour of mol/L
Cell after supporting half an hour adds 2 times of equivalent Cu2+The two-photon Confocal Images of cell after ion.Wherein, λ ex=
355nm, A are that the confocal fluorescent image after fluorescence probe is added in HeLa cell, and B is bright field image, the merging of C A, B
Image.D is to cultivate half an hour after fluorescence probe is added in HeLa cell, and the Cu of 2 times of equivalents is then added2+Copolymerization coke afterwards is glimmering
Light image, E are bright field image, the merging image of F D, E.
Specific embodiment
Embodiment 1: the synthesis of fluorescence probe
Compound 1 (100mg) is added in anhydrous DMSO (5mL) and is heated to 70 DEG C, is cooled to room temperature acquisition solution A；It will
2- pyridine carboxylic acid 30mg) and EDC (90.8mg), DMAP (27.0mg) be added in anhydrous DMSO (5mL), solution B is obtained after dissolution；
The solution A is mixed with the solution B, N2Protection, reacts for 24 hours under room temperature；Product is added to 200mL after reaction
In distilled water, there is yellow solid precipitation, be evaporated under reduced pressure, obtain crude product, then by being recrystallized twice, most with dehydrated alcohol
It is filtered afterwards by decompression, obtains final fluorescence probe.
1H NMR (400MHz, DMSO) δ 8.90-8.81 (m, 1H), 8.58 (d, J=7.4Hz, 2H), 8.35-8.27 (m,
2H), 8.12 (t, J=8.1Hz, 1H), 7.90 (dd, J=13.0,7.7Hz, 2H), 7.81-7.74 (m, 1H), 7.70 (d, J=
8.2Hz 2H), 7.57 (d, J=8.3Hz, 2H), 4.15 (t, J=6.8Hz, 2H), 3.44 (s, 4H), 3.31 (s, 1H), 2.41
(s, 2H), 2.33 (s, 3H), 1.84 (t, J=6.6Hz, 2H), FTMS:m/z=522.2, theoretical value: 521.52.
Embodiment 2:
1, in order to which can the probe that detect synthesis to Cu in pure water2+With ultraviolet spectra selectivity, by configured 10-5The probe of mol/L pipettes 4mL with liquid-transfering gun, is then separately added into the Ag of 5 times of equivalents again+, Al3+, Ca2+, Cd2+, Co2+, Cu2+,
Fe2+, Hg2+, K+, Li+, Mg2+, Na+, Ni2+, Pb2+Solution after addition, the comparison in ultraviolet spectra is as can be seen that be added Cu2+
Probe obviously have occurred red shift, the position of maximum absorption band is in 374nm, red shift 10nm.This is illustrated can in the probe
To Cu2+Selective ultraviolet spectra response.
2, in order to which can the probe that detect synthesis to Cu in pure water2+With fluorescence selectivity, by configured 10- 5The probe of mol/L pipettes 4mL with liquid-transfering gun, and the Ag of 5 times of equivalents is equally added+, Al3+, Ca2+, Cd2+, Co2+, Cu2+, Fe2+, Hg2 +, K+, Li+, Mg2+, Na+, Ni2+, Pb2+Metal ion detects the response in fluorescence Spectra.It can be seen from fluorescence spectra its
He does not respond to ion pair fluorescence probe, and Cu is added2+Afterwards, apparent quenching has occurred in fluorescence, and maximum emission peak is in 475nm
Place, it was demonstrated that fluorescence probe is in fluorescence spectrum to Cu2+Also selectively response.
3, in order to which can the probe that detect synthesis in water to Cu2+Quantitative detection, by configured 10-5The probe of mol/L
4mL is pipetted respectively with liquid-transfering gun in 4mL centrifuge tube, the Cu for 1-30 μm of ol/L being then separately added into again2+, in ultraviolet spectra
Comparison is as can be seen that with Cu is added2+Red shift gradually has occurred in the increase of concentration, probe, shows the Cu under various concentration2+Energy
Enough make the generation red shift of UV-absorbance maximum.10-5The probe of mol/L is separately added into 1 μm of ol/L, 2 μm of ol/L, 3 μm of ol/L, 4 μ
Mol/L, 5 μm of ol/L, 6 μm of ol/L, 7 μm of ol/L, 8 μm of ol/L, 9 μm of ol/L, the Cu of 10 μm of ol/L2+Fluorescence light under concentration range
Spectrum is as can be seen that with Cu2+The continuous increase of concentration, fluorescence gradually go out to quench, linear coefficient R2=0.96892.This shows glimmering
The detection Cu that light probe can quantify in fluorescence spectrum2+。
4, in order to which can the probe that detect synthesis to Cu in cell2+With good response, 10 μ L are taken, 10-3Mol/L's
Probe is added in the HeLa cell of the culture dish culture of 1mL, is cultivated half an hour, is detected under two-photon Laser Scanning Confocal Microscope
Then fluorescence intensity in cell will add the Cu of 2 times of equivalents with the cell after fluorescence probe culture half an hour2+It is further cultured for half
Hour, the fluorescence intensity of cell is shot under two-photon Laser Scanning Confocal Microscope.Picture can be seen that in cell, and Cu is added2+Later
Than Cu is added2+Fluorescence before is substantially reduced.This explanation, the probe is to Cu in cell2+Also there can be good response, this
For the Cu in detection cell2+Provide an extraordinary detection method.
Claims (6)
1. a kind of fluorescence probe for detecting bivalent cupric ion, it is characterised in that:
The chemical formula of the fluorescence probe is C31H27N3O5, structural formula is as follows:
2. a kind of preparation method of fluorescence probe described in claim 1, it is characterised in that include the following steps:
100mg compound 1 is added in anhydrous DMSO and is heated to 70 DEG C, is cooled to room temperature acquisition solution A；By 30mg 2- pyridine
Formic acid and 90.8mg EDC, 27.0mg DMAP are added in anhydrous DMSO, and solution B is obtained after dissolution；By the solution A with it is described
Solution B mixing, N2Protection, reacts for 24 hours under room temperature；Product is added dropwise in distilled water after reaction, there is yellow product analysis
Out, it is evaporated under reduced pressure later, obtains crude product, depressurize and filter after being recrystallized with dehydrated alcohol, target product can be obtained；
The structural formula of the compound 1 is as follows:
3. a kind of purposes of fluorescence probe described in claim 1, it is characterised in that:
The fluorescence probe is in detection Cu2+During use as detection reagent.
4. purposes according to claim 3, it is characterised in that:
The fluorescence probe can by way of hydrolysis specific recognition Cu2+, it is detectable by ultraviolet or fluorescence mode, it is right
Cu2+There is specific recognition.
5. purposes according to claim 3, it is characterised in that:
Fluorescence probe Cu in detection pure water or living cells2+During use as detection reagent.
6. purposes according to claim 5, it is characterised in that:
The fluorescence probe can be with the Cu in quantitative detection pure water2+Concentration.
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| CN108250188A (en) * | 2018-01-16 | 2018-07-06 | 商丘师范学院 | A kind of long-wavelength fluorescent probe for detecting copper ion and its synthetic method and application |
| CN109320535A (en) * | 2018-09-29 | 2019-02-12 | 江汉大学 | A kind of detection Cu2+Ratiometric fluorescent probe, preparation method and application |
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