CN118146263A - Dinitrile ethylene and triphenylphosphine end capped quinoid compound and preparation method and application thereof - Google Patents
Dinitrile ethylene and triphenylphosphine end capped quinoid compound and preparation method and application thereof Download PDFInfo
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- CN118146263A CN118146263A CN202211562614.XA CN202211562614A CN118146263A CN 118146263 A CN118146263 A CN 118146263A CN 202211562614 A CN202211562614 A CN 202211562614A CN 118146263 A CN118146263 A CN 118146263A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 79
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000005977 Ethylene Substances 0.000 title abstract description 4
- 238000003384 imaging method Methods 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 238000005859 coupling reaction Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012312 sodium hydride Substances 0.000 claims description 4
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 210000004027 cell Anatomy 0.000 abstract description 20
- 210000004881 tumor cell Anatomy 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 210000000265 leukocyte Anatomy 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 102000009027 Albumins Human genes 0.000 description 5
- 108010088751 Albumins Proteins 0.000 description 5
- 206010006187 Breast cancer Diseases 0.000 description 4
- 208000026310 Breast neoplasm Diseases 0.000 description 4
- 210000003292 kidney cell Anatomy 0.000 description 4
- 201000007270 liver cancer Diseases 0.000 description 4
- 208000014018 liver neoplasm Diseases 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- -1 quinone compound Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- AZOZOHCZAFSZIG-UHFFFAOYSA-N 2,4-dibromo-1,3-benzothiazole Chemical compound C1=CC=C2SC(Br)=NC2=C1Br AZOZOHCZAFSZIG-UHFFFAOYSA-N 0.000 description 1
- GBXBSLXFJIVISJ-UHFFFAOYSA-N 4,5-dibromo-2h-benzotriazole Chemical compound BrC1=CC=C2NN=NC2=C1Br GBXBSLXFJIVISJ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000007080 aromatic substitution reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
- C07F9/6518—Five-membered rings
- C07F9/65188—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
- C07F9/6539—Five-membered rings
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- 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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- 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
- G01N21/645—Specially adapted constructive features of fluorimeters
- G01N21/6456—Spatial resolved fluorescence measurements; Imaging
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Abstract
The invention discloses a dinitrile ethylene and triphenylphosphine end-capped quinoid compound, a preparation method and application thereof. The quinoid compound has good thermal stability and fluorescence property, can be combined with white blood cells for fluorescence enhancement, can distinguish tumor cells from normal cells, has certain selectivity, and has good application prospect and higher application value in the field of cell imaging; meanwhile, the preparation method of the compound is relatively simple and reasonable in cost, and is more beneficial to industrial production.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric functional materials, and particularly relates to a novel quinone compound with dinitrile vinyl and triphenylphosphine as end caps, and a preparation method and application thereof.
Background
Organic photoelectric functional materials are receiving attention because of the advantages of various types, adjustable structure, light flexibility, large-area preparation and the like. Among them, the quinoid compound is a system which has been studied more intensively in recent years, and its special single double bond alternating structure makes it have the following characteristics: rigid pi plane skeleton, strong electron accepting capacity, narrow band gap, large light absorption coefficient, etc. In addition, as the conjugated length of the quinoid structure extends, the non-aromatic quinoid structure can form an open-shell diradical molecule by recovering the aromaticity, so that the quinoid compound has great development potential in the research fields of organic electronics, near infrared absorption, nonlinear optics, magnetic materials and the like.
Although various quinoid compounds have been synthesized by researchers, most of the quinoid compounds still have dicyanovinyl groups as both side-capping units, and the properties thereof have been limited. Therefore, development of quinoid compounds with different end capping groups provides a new opportunity for research of organic photoelectric materials and has very important significance.
Disclosure of Invention
The invention aims to provide a dinitrile ethylene and triphenylphosphine end capped quinoid compound, a preparation method and application thereof. The quinoid compound has good thermal stability and fluorescence property, can be combined with white blood cells for fluorescence enhancement, can distinguish tumor cells from normal cells, has certain selectivity, and has good application prospect and high application value in the field of cell imaging. Meanwhile, the preparation method of the compound is relatively simple and reasonable in cost, and is more beneficial to industrial production.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
a quinoid compound has a structural formula shown in formula I:
In the formula I, the compound (I),
R is H, C 1～30 alkyl substituted or unsubstituted by nitrogen atom, C 6～20 aromatic hydrocarbon substituted or unsubstituted by nitrogen atom;
X is S or N.
Further, the compound shown in the formula I is a compound shown in the following formula I-a or a compound shown in the formula I-b:
in the formula I-a, R is defined as in the formula I.
Further, in the compound shown in the formula I-a, R is C 5～7 alkyl substituted or unsubstituted by nitrogen atom.
Preferably, the compound of formula I-a is a compound of formula I-a 1:
The invention also provides a preparation method of the quinoid compound, which comprises the following steps:
under the condition of a metal catalyst taking triphenylphosphine as a ligand and alkaline conditions, performing a coupling reaction on a compound shown in a formula II and malononitrile to obtain a compound shown in a formula I;
In formula II, X, R is as defined in formula I.
Further, in the compound shown in the formula II, R is C 5～7 alkyl substituted or unsubstituted by nitrogen atom.
Further, the compound shown in the formula II is dibromobenzotriazol or dibromobenzothiazole.
Further, the molar ratio of malononitrile to the compound of formula II is (1-3): 1, preferably 2:1.
The metal catalyst is tetra (triphenylphosphine) palladium or di (triphenylphosphine) palladium dichloride.
The molar ratio of the metal catalyst to the compound shown in the formula II is (0.05-1): 1.
The alkali is at least one of sodium hydride, sodium hydroxide, potassium carbonate and sodium carbonate.
The molar ratio of the alkali to the compound shown in the formula II is (1-3): 1.
The solvent used in the coupling reaction is at least one of toluene, tetrahydrofuran, chloroform, 1, 2-dimethoxyethane, N-dimethylformamide, chlorobenzene, o-dichlorobenzene, benzene and mesitylene.
The coupling reaction is carried out under the inert gas environment; the inert gas is nitrogen or argon.
Further, the temperature of the reaction is 25-140 ℃, preferably 80-90 ℃; the time is 5-24h, preferably 12h.
The invention also provides application of the quinoid compound as a biological detection material or a biological cell imaging material.
The biological detection material is albumin fluorescent detection.
The biological cell imaging material is a material in tumor cell imaging.
The tumor cells comprise liver cancer cells, breast cancer cells or embryonic kidney cells.
The invention has the following beneficial effects:
The invention synthesizes the quinoid compound based on dinitrile vinyl and triphenylphosphine as two side end sealing groups for the first time, and the compound has good thermal stability and fluorescence property, enhanced fluorescence combined with leucocytes, and can distinguish tumor cells from normal cells, has certain selectivity, and has good application prospect and higher application value in the field of cell imaging. Meanwhile, the preparation method of the compound is relatively simple and reasonable in cost, and is more beneficial to industrial production.
Drawings
FIG. 1 is a synthetic scheme of the quinoid compound of formula I provided by the present invention.
FIG. 2 is a synthetic scheme for the compound of formula I-a 1 of example 1.
FIG. 3 is a synthetic scheme for the compounds of formula I-b in example 2.
FIG. 4 is a thermogravimetric analysis of a compound of formula I-a 1, a compound of formula I-b.
FIG. 5 is a graph showing the UV-visible absorption spectra of a compound of formula I-a 1 and a compound of formula I-b in different solvents.
FIG. 6 shows fluorescence spectra of a compound of formula I-a 1, a compound of formula I-b before and after albumin binding.
FIG. 7 is a photograph showing the cell image of the compound of formula I-a 1 in liver cancer cells, breast cancer cells and embryonic kidney cells
FIG. 8 is a diagram showing the cell imaging of the compound shown in the formula I-b in liver cancer cells, breast cancer cells and embryonic kidney cells.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof.
Example 1
The preparation method of the compound shown in the formula I-a1, as shown in figure 2, specifically comprises the following steps:
(1) Malononitrile (7.9 mg,2.4 eq) and 10mL of 1, 2-methoxyethane were added to the reaction flask under nitrogen, followed by slow addition of sodium hydride (2.9 mg,2.4 eq) at 0deg.C and stirring of the reaction for 30 min.
(2) Then, II-a1 (18 mg,0.05 mmol) and tetrakis (triphenylphosphine) palladium (29 mg,0.5 eq) were added to the system, and the reaction was carried out at 85℃for 12h.
(3) Isolation by thin layer chromatography gave 19mg of yellow solid I-a1 (72% yield).
1 H NMR (300 MHz, deuterated dichloromethane ):δ7.71–7.66(m,3H),7.57-7.50(m,12H),6.80(dd,J＝14.4,8.7Hz,1H),6.66(dd,J＝8.4,3.0Hz,1H),4.40(t,J＝6.9Hz,2H),1.76-1.67(m,2H),1.13–1.02(m,6H),0.75(t,J＝6.3Hz,3H).31P(400MHz,, deuterated dichloromethane, H 3PO4): delta 18.35.HRMS (ESI): m/z theory was C 33H30N5NaP[M+Na+: 550.2131, actual: 550.2131.
Example 2
The preparation method of the compound shown in the formula I-b, as shown in figure 3, specifically comprises the following steps:
(1) Malononitrile (7.9 mg,2.4 eq) and 10mL of 1, 2-methoxyethane were added to the reaction flask under nitrogen, followed by slow addition of sodium hydride (2.9 mg,2.4 eq) at 0deg.C and stirring of the reaction for 30 min.
(2) II-b (15 mg,0.05 mmol) and tetrakis (triphenylphosphine) palladium (29 mg,0.5 eq) were then added to the system and the reaction was allowed to react for 12h at 85 ℃.
(3) Isolation by thin layer chromatography and recrystallisation from tetrahydrofuran/n-hexane gives 19mg of red solid I-b (84% yield).
1 H NMR (700 MHz, deuterated dichloromethane ):δ7.76(m,3H),7.61–7.55(m,12H),7.00(dd,J＝14.2,8.5Hz,1H),6.81(dd,J＝8.5,3.1Hz,1H).13C NMR(175MHz, deuterated dichloromethane ):δ156.4,156.4,150.1,145.9,140.0,139.9,134.3,134.1,134.1,129.8,129.7,120.9,120.6,120.5,120.0,111.0,110.9,83.3,82.7.31P(400MHz,Methylene Chloride-d2,H3PO4):δ18.57.HRMS(ESI):m/z theory C 27H17N4NaPS[M+Na+: 483.0803, actual 483.0800).
Performance test:
1. molecular stability test
Thermogravimetric analysis (TGA) experiments were performed under nitrogen protection (fig. 4) and showed that the temperature was 288 ℃ at 5% weight loss of compound I-a1 and 266 ℃ at 5% weight loss of compound I-b. Experimental data indicate that both compounds I-a1 and I-b have good thermal stability.
2. Ultraviolet-visible absorption spectrum test
The target compounds I-a 1 and I-b were dissolved in methanol, N-dimethylformamide, chloroform, tetrahydrofuran and toluene, respectively, at a concentration of 5X10 -6 mol/L, and subjected to ultraviolet-visible absorption spectroscopy (FIG. 5).
As can be seen from the figure, the maximum absorption peaks of the target compound of formula I-a 1 in methanol, N-dimethylformamide, chloroform, tetrahydrofuran and toluene are 433, 447, 455, 461 and 469nm, respectively, and the maximum absorption peaks of the target compound of formula I-b in methanol, N-dimethylformamide, chloroform, tetrahydrofuran and toluene are 530, 546, 554, 558 and 563nm, respectively. The results show that with the increase of polarity, the absorption spectra of the solutions of the target compounds of the formulas I-a 1 and I-b all have a certain blue shift phenomenon.
3. Fluorescence spectra of the compounds of the formula I-a 1, I-b before and after binding to albumin
As shown in FIG. 6, both the compounds I-a 1 and I-b had weak fluorescence, but after albumin was added, the fluorescence of both the compounds I-a 1 and I-b was greatly enhanced by 14-fold and 250-fold, respectively, accompanied by a blue shift in fluorescence emission, indicating that the compounds I-a 1 and I-b had the ability to detect albumin.
4. Application of compound I-a 1 and compound I-b in biological cell imaging
The compounds I-a 1 and I-b were prepared into 1mM stock solution with DMSO, diluted to 10. Mu.M (containing 1% DMSO) with cell culture solution, and the two probe solutions were added to HepG2 (liver cancer cell), MCF-7 (breast cancer cell), and normal human embryo kidney cell HEK293, respectively, and incubated for 1.5 hours in an incubator protected from light, and observed with confocal laser scanning microscope.
As shown in FIGS. 7 and 8, compounds I-a 1 and I-b light tumor cells well with good signal to noise ratio. Furthermore, these two compounds have a certain selectivity for tumor cell imaging, especially for compound I-b. As shown in FIG. 8, I-b showed a better selectivity with weaker fluorescence in normal cells.
Furthermore, the substitution of II-a1 in example 1 with other compounds of formula II gives the corresponding compounds of formula I-a; the nitrogen atom substitution in R or the aromatic substitution does not affect the progress of the coupling reaction.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. A quinoid compound has a structural formula shown in formula I:
In the formula I, the compound (I),
R is H, C 1～30 alkyl substituted or unsubstituted by nitrogen atom, C 6～20 aromatic hydrocarbon substituted or unsubstituted by nitrogen atom;
X is S or N.
2. The quinoid compound according to claim 1, wherein: the compound shown in the formula I is a compound shown in the formula I-a or a compound shown in the formula I-b:
in formula I-a, R is as defined in claim 1.
3. The quinoid compound according to claim 2, wherein: in the compound shown in the formula I-a, R is C 5～7 alkyl substituted or unsubstituted by nitrogen atom.
4. A process for the preparation of a quinoid compound as claimed in any one of claims 1 to 3 comprising the steps of:
under the condition of a metal catalyst taking triphenylphosphine as a ligand and alkaline conditions, performing a coupling reaction on a compound shown in a formula II and malononitrile to obtain a compound shown in a formula I;
in formula II X, R is as defined in any one of claims 1 to 3.
5. The method of manufacturing according to claim 4, wherein: the molar ratio of the malononitrile to the compound shown in the formula II is (1-3): 1.
6. The method of claim 4 or 5, wherein: the metal catalyst is tetra (triphenylphosphine) palladium or di (triphenylphosphine) palladium dichloride;
the molar ratio of the metal catalyst to the compound shown in the formula II is (0.05-1): 1.
7. The method of any one of claims 4-6, wherein: the alkali is at least one of sodium hydride, sodium hydroxide, potassium carbonate and sodium carbonate;
the molar ratio of the alkali to the compound shown in the formula II is (1-3): 1.
8. The method of any one of claims 4-7, wherein: the solvent used in the coupling reaction is at least one of toluene, tetrahydrofuran, chloroform, 1, 2-dimethoxyethane, N-dimethylformamide, chlorobenzene, o-dichlorobenzene, benzene and mesitylene;
The coupling reaction is carried out under the inert gas environment; the inert gas is nitrogen or argon.
9. The method of any one of claims 5-8, wherein: the temperature of the coupling reaction is 25-140 ℃ and the time is 5-24h.
10. Use of a quinoid compound as claimed in any one of claims 1 to 3 as a biological detection material or biological cell imaging material.
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