CN109053583A - A kind of preparation method and applications of specific recognition copper ion fluorescence probe - Google Patents

A kind of preparation method and applications of specific recognition copper ion fluorescence probe Download PDF

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CN109053583A
CN109053583A CN201811071781.8A CN201811071781A CN109053583A CN 109053583 A CN109053583 A CN 109053583A CN 201811071781 A CN201811071781 A CN 201811071781A CN 109053583 A CN109053583 A CN 109053583A
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王秋生
王凡
曾旭
余子安
王晨霞
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Tianjin University of Technology
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Abstract

A kind of preparation method and applications of specific recognition copper ion fluorescence probe, the compound name are 4,4', 4 ", 4 " '-tetrahydroxys -3,3', 3 ", 3 " '-four (2- benzo [d] imidazoles) tetraphenyl ethylene, chemical molecular formula C54H36N8O4, preparation method: being raw material first by MacMurray reaction synthesis 4 with 4,4'- dimethylamino benzopheone, 4', 4 ", 4 " '-tetramethoxy tetraphenyl ethylenes, obtain 4,4', 4 " by demethylation reaction again; 4 " '-tetrahydroxy tetraphenyl ethylene, be then passed through Duff reaction synthesis 4,4'; 4 ", 4 " '-tetrahydroxys -3,3'; 3 ", 3 " the aldehyde radical tetraphenyl ethylenes of '-four react to form target compound with o-phenylenediamine.The invention has the advantages that the preparation method simple process, raw material are easy to get, are easy to implement, products obtained therefrom is to metal copper ion selectivity with higher, there is aggregation-induced emission simultaneously and crystallize the characteristic of induced luminescence enhancing, can be used for Biological target therapy and bio-imaging.

Description

A kind of preparation method and applications of specific recognition copper ion fluorescence probe
Technical field
The present invention relates to metal ion detection fields, specifically about one kind have AIE property and specific recognition copper from The synthetic method and its application of the tetraphenyl ethylene benzimidazoles compound of son.
Background technique
Heavy metal copper ion is easy to be enriched in vivo, has characteristic difficult to degrade, if passing through food chain for a long time Into in human body, heavy metal in human body content severe overweight will lead to.
Copper is widely distributed in nature, is indispensable one of element during many vital movements, such as Coenzyme, biosynthesis, biology transport in catalysis reaction.Micro copper can promote animal and plant to grow and animal and people A kind of required microelement, the concentration level of copper will affect its vital movement process, the too low meeting of concentration in organism Carry out these vital movement processes can not.
The compound of copper exists with monovalence or divalent state, and in natural water, the amount of copper of dissolution is dropped with the raising of pH It is low, after accumulating to a certain extent in vivo, certain harm will be generated.When the content of Copper in Body is excessive It waits, is easy to generate harm to internal organ, the hazard ratio of especially liver and gallbladder is more serious.The enrichment of animal can increase the poison of copper Property will accumulate excessive copper in human body, also will appear certain disease after people has eaten these exceeded animal foods Shape, Wilson disease (a kind of autosomal recessive disease) are since the copper ions such as people's intracorporal vitals liver kidney brain deposition is excessive Caused by.Copper ion concentration is excessively high to generate the nocuousness such as inhibiting effect or neurotoxicity to the activity of enzyme during vital movement Effect, the internal copper ion of adult excessively will lead to coronary heart disease, hypertension, and the diseases such as artery sclerosis can seriously endanger human body Health.
The detection method of common copper ion concentration has fluorescence method, electrochemical methods, spectrophotometry and chemiluminescence Method etc., wherein fluorescence method has many advantages, such as that selective good, high sensitivity receives significant attention.
Aggregation-induced emission (AIE) has a great development in last decade, and how glimmering past Many researchers be made Luminescent material has fluorescent quenching (ACQ) effect, when many applications, can generate undesirable effect, with AIE effect Molecule is devised, and AIE molecule refers to when monodisperse state, and fluorescence intensity shows very weak, when state of aggregation, Show very strong fluorescence.The design of AIE molecule is based on RIR, and the mechanism of RIM, AIE molecular application is in Sony ericsson mobile comm ab, life Object imaging, optical dynamic therapy, sensor etc..
Tetraphenyl ethylene benzimidazoles compound has unique structure feature: 1) containing multiple donors that may participate in coordination Atom, thus coordination ability is very strong；2) intramolecular presence-OH ,-NH2There is also receptor=N- ,-C of electronics for isoelectronic donor The distance of=O, two groups are closer, can generate ESIPT process.3) tetraphenyl ethylene structure is easily broken off into singly-bound, singly-bound rotation It is limited, it is easy to produce AIE phenomenon.Therefore, the research of tetraphenyl ethylene benzimidazoles compound becomes chemist and biochemistry Family the important topic studied.
In conjunction with the above analysis, a kind of specific detection copper ion concentration diagnostic reagent that the present invention designs, synthesizes can be incited somebody to action It is applied to Cu2+Analysis detection.The specific detection copper ion concentration diagnostic reagent has high sensitivity, selective good, inspection The features such as at low cost is surveyed, to detect Cu in organism2+It is further research indicate a direction.
Summary of the invention
The purpose of the present invention is there are problem, provided for above-mentioned it is a kind of there is AIE characteristic, while have selectivity high and A kind of preparation method of the good specific recognition copper ion fluorescence probe of sensitivity, while it is provided in targeted therapy and biology The application of aspect is imaged.
Technical solution of the present invention:
A kind of preparation method of specific recognition copper ion fluorescence probe, the opposite sex identify that copper ion fluorescence probe is four benzene Ethylene benzimidazoles compound, entitled 4,4', 4 ", 4 " '-tetrahydroxys -3,3', 3 ", 3 " '-four (2- benzo [d] imidazoles) four Styrene, chemical molecular formula C54H36N8O4, molecular structural formula are as follows:
Preparation step is as follows:
1) under protection of argon gas, zinc powder is added in anhydrous tetrahydro furan, under ice salt bath, TiCl is added dropwise4, it is added dropwise After, restore to room temperature, anhydrous pyridine is added, by raw material 4,4'- dimethoxy-benzophenone is dissolved into tetrahydrofuran, It is added in reaction solution, is refluxed overnight later, TLC detects reaction process, after complete reaction, 10% is added in reaction solution Solution of potassium carbonate, stirring at normal temperature 2 hours, vacuum filtration, methylene chloride extraction, anhydrous magnesium sulfate was dry, with ethyl acetate and stone Oily ether recrystallization, obtains 4,4', 4 ", 4 " '-tetramethoxy tetraphenyl ethylene of white powder solid；
2) 4,4', 4 ", 4 " '-tetramethoxy tetraphenyl ethylenes and methylene chloride under protection of argon gas, is added, by BBr3Dissolution Into methylene chloride, the BBr that will be dissolved into methylene chloride under conditions of -78 DEG C3It is added dropwise, after being added dropwise, -78 Under conditions of DEG C, half an hour is reacted, is restored to room temperature, overnight, TLC monitors reaction process for reaction at room temperature, has reacted At later, distilled water is added dropwise, has the precipitation of aubergine solid, is washed with methylene chloride, obtain violet solid 4,4', 4 ", 4 " '-tetrahydroxy tetraphenyl ethylenes；
3) above-mentioned 4,4', 4 ", 4 " '-tetrahydroxy tetraphenyl ethylenes and methenamine are added in trifluoroacetic acid, are heated to reflux 4 hours, TLC monitor reaction process, after restoring room temperature, ice water to yellow solid are added and is precipitated, and suction filtration obtains yellow solid, With methylene chloride: hexamethylene 5:1 column chromatography, it is dry, obtain yellow solid, 4,4', 4 ", 4 " '-tetrahydroxys -3,3', 3 ", 3 " ' - Four aldehyde radical tetraphenyl ethylenes.
4) above-mentioned 4,4', 4 ", 4 " '-tetrahydroxy -3,3', 3 ", the 3 " aldehyde radical of '-four tetraphenyl ethylenes and sodium hydrogensulfite are added Into dehydrated alcohol, 4 hours are stirred under room temperature, o-phenylenediamine is dissolved into a certain amount of DMF, is added in reaction solution, It being refluxed overnight, TLC detects reaction process and a certain amount of distilled water is added after reaction stops, and yellow solid precipitation is had, is filtered, It is washed with methanol, is dried to obtain 4,4', 4 ", 4 " '-tetrahydroxy -3,3' of yellow solid, 3 ", 3 " '-four (2- benzo [d] imidazoles) four Styrene.
The zinc powder, tetrahydrofuran, titanium tetrachloride and anhydrous pyridine mass ratio be 9:30:4:1；4,4'- dimethoxy The mass ratio of benzophenone and anhydrous tetrahydro furan is 1:4.5.
The mass ratio of the 4,4', 4 ", 4 " '-tetramethoxy tetraphenyl ethylenes, methylene chloride and Boron tribromide are 1:11: 4.4。
The mass ratio of the 4,4', 4 ", 4 " '-tetrahydroxy tetraphenyl ethylenes, methenamine and trifluoroacetic acid are 2:2.3: 107.5。
The 4,4', 4 ", 4 " '-tetrahydroxy -3,3', 3 ", the 3 " aldehyde radical of '-four tetraphenyl ethylenes, sodium hydrogensulfite and anhydrous second The mass ratio of alcohol is that the mass ratio of 2:3:235-240 o-phenylenediamine and DMF are 1:19.
The application of the above prepared specific recognition copper ion fluorescence probe, as the dense of quick detection metal copper ion Degree.
The reagent of this method preparation has the characteristic of aggregation-induced emission, while having the characteristic of crystallization induced luminescence, Targeted therapy can be carried out in biologic applications.
The invention has the advantages that the preparation method simple process, raw material are easy to get, are easy to implement, the reagent of preparation is to metal Copper ion selectivity with higher, while there is the characteristic of aggregation-induced emission, there is very high application value.
Detailed description of the invention
Fig. 1 is that (concentration is 3 × 10 to the specific recognition copper ion fluorescence probe THF solution-5Mol/L) different water content items Fluorescence emission spectrum variation diagram under part.
Fig. 2 is that (concentration is 3 × 10 to the specific recognition copper ion fluorescence probe THF solution-5Mol/L) different water content items Figure of fluorescence intensity changes under part.
Fig. 3 is that (concentration is 1 × 10 to specific recognition copper ion fluorescence probe DMSO solution-5Mol/L) with same concentrations Different metal ions (Al3+、Ca2+、Cd2+、Co2+、Cu2+、Fe3+、Hg2+、K+、Mg2+、Mn2+、Na+、Pb2+、Sn2+、Zn2+) after reaction Fluorescence intensity comparison diagram.
Fig. 4 is that (concentration is 1 × 10 to specific recognition copper ion fluorescence probe DMSO solution-5) and various concentration mol/L CuCl2Solution reaction figure of fluorescence intensity changes.
Fig. 5 is that (concentration is 1 × 10 to specific recognition copper ion fluorescence probe DMSO solution-5)) and various concentration mol/L CuCl2Solution reaction uv absorption spectra.
Specific embodiment
Below by the embodiment specific description present invention, but the present invention is not limited by following embodiments.
Embodiment:
A kind of preparation method of specific recognition copper ion fluorescence probe, probe are tetraphenyl ethylene benzimidazole chemical combination Object, tetraphenyl ethylene benzimidazoles compound entitled 4,4', 4 ", 4 " '-tetrahydroxys -3,3', 3 ", 3 " '-four (2- benzo [d] Imidazoles) tetraphenyl ethylene, chemical molecular formula C54H36N8O4, molecular structural formula are as follows:
Preparation step is as follows:
1) under the protection of argon gas, 10.6g zinc powder is added in the anhydrous tetrahydro furan of 40mL, in the condition of ice salt bath Under 2.7mL titanium tetrachloride is added dropwise, after being added dropwise, reaction solution is restored to room temperature, after being heated to reflux 2h, be added anhydrous pyridine 4,4'- dimethoxy-benzophenone 4.0g is dissolved into anhydrous tetrahydro furan, is added in reaction solution later by 1.2mL, reflux Overnight, after fully reacting, the solution of potassium carbonate of addition 10% in reaction solution, stirring at normal temperature 2 hours, meeting in reaction unit Black solid is precipitated, filters, methylene chloride extraction, anhydrous magnesium sulfate is dry, and filtrate revolving is tied again with ethyl acetate and petroleum ether Crystalline substance, it is dry, obtain 4,4', 4 ", 4 " '-tetramethoxy tetraphenyl ethylene of 3.24g white solid powder, yield: 87.3%.1H NMR (400MHz,CDCl3) δ 6.93 (d, 8H), 6.65 (d, 8H), 3.75 (s, 12H) .MS (EI), M/Z:452.2, analytical calculation: 452.3。
Reaction equation are as follows:
2) under the protective condition of argon gas, above-mentioned 4,4', 4 ", 4 " '-tetramethoxy tetraphenyl ethylene of 3.0g is dissolved in 25mL In methylene chloride, by 5.0mLBBr3It is dissolved in the methylene chloride of 10mL, under conditions of -78 DEG C, by Boron tribromide and dichloromethane The mixed liquor of alkane is added dropwise in reaction unit, after being added dropwise, is stirred 30 minutes under conditions of -78 DEG C, is restored later To room temperature, stirring at normal temperature is overnight, to after the reaction was completed, be added dropwise.30mL distilled water is added, has the solid analysis of aubergine Out, it filters, is washed with methylene chloride, it is dry, obtain 4,4', 4 ", 4 " '-tetrahydroxy tetraphenyl ethylene of 2.3g aubergine solid, yield 88%.1H-NMR(400MHz,DMSO-d6) δ 9.23 (s, 4H), 6.71-6.69 (d, J=8Hz, 8H), 6.49-6.47 (d, J= 8Hz,8H).13C-NMR(100MHz,DMSO-d6)δ114.94,132.41,135.51,138.13,155.81.ESI/MS m/z: 396.1[M]+, analytical calculation: 396.2 [M]+
Reaction equation are as follows:
3) by 1.0g4,4', 4 ", 4 " '-tetrahydroxy tetraphenyl ethylenes and 1.14g methenamine are added to the trifluoroacetic acid of 35mL In, being heated to reflux 4 hours is restored to room temperature after reaction, and ice water is added into reactor, it stirs 3 hours at room temperature, There is yellow solid precipitation, filters, obtain crude product, crude product methylene chloride: hexamethylene 5:1 column Chromatographic purification obtains 0.61g 4,4', 4 ", 4 " '-tetrahydroxy -3,3' of yellow solid, 3 ", 3 " the aldehyde radical tetraphenyl ethylenes of '-four, yield 70%.1H-NMR(400MHz, CDCl3) δ 11.01 (s, 4H), 9.66 (s, 4H), 7.26-7.18 (m, 8H), 6.85-6.83 (d, J=8Hz 4H)13C-NMR (100MHz,CDCl3)δ117.92,120.45,134.20,137.70,139.71,160.75,196.10.ESI/Ms m/z: 508.1158[M]+, analytical calculation: 508.1199 [M]+
Reaction equation:
4) by 0.1g 4,4', 4 ", 4 " '-tetrahydroxy -3,3', 3 ", the 3 " aldehyde radical of '-four tetraphenyl ethylenes and 0.15g bisulfite Sodium is added in 15mL dehydrated alcohol, stirs 4h at room temperature, and later, 0.15g o-phenylenediamine is dissolved into 3mLDMF, by adjacent benzene The mixed liquor of diamines and DMF are added in reaction solution, are refluxed overnight, and after complete reaction, 10mL distilled water are added, has yellow Solid is precipitated, and filters, and filter cake is washed with methanol, dry, obtains 4,4', 4 ", 4 " '-tetrahydroxy -3,3' of 0.15g yellow solid, 3 ", 3 " '-four (2- benzo [d] imidazoles) tetraphenyl ethylene, yield 88%:1H NMR(400MHz,DMSO-d6)δ13.19(s,8H), 7.90 (s, 4H), 7.58 (s, 8H), 7.22 (s, 8H) 7.16-7.14 (d, J=8Hz 4H), 6.86-6.84 (d, J=8Hz 4H),13C NMR(100MHz,DMSO-d6)δ112.89,117.26,123.21,129.15,135.10,135.46,139.09, 145.30,151.82,157.18,174.72.Ms:m/z:861.2938 analytical calculation: 861.2969 [M]+.
Reaction equation are as follows:
Prepared specific recognition copper ion fluorescence probe, the characteristic with aggregation-induced emission (AIE) have simultaneously It is enhanced propertied to crystallize induced luminescence, can be used for Biological target therapy, can be used as quickly detecting metal copper ion.
The AIE of specific recognition copper ion fluorescence probe is tested:
The specific recognition copper ion fluorescence probe of preparation is dissolved in THF, being configured to total concentration is 3 × 10-5Mol/L is not With the solution of water content, its spectrum property is detected.
Fig. 1 is that under conditions of different water contents, specific recognition copper ion fluorescence probe is made into using THF as solvent Total concentration is 3 × 10-5Mol/L, setting excitation wavelength is 350nm, measures fluorescence intensity change spectrum, shows in figure: four benzene second The launch wavelength of alkene benzimidazoles compound is 510nm, and when water content is 85%, fluorescence intensity is maximum.
Fig. 2 is the trend chart of fluorescence intensity under conditions of different water contents, the fluorescence in water content 85% Maximum intensity illustrates that the tetraphenyl ethylene benzimidazoles compound has the characteristic of aggregation-induced emission.
The spectrum test of specific detection copper ion concentration diagnostic reagent
Fig. 3 is the metal ion Al of same concentrations3+、Ca2+、Cd2+、Co2+、Cu2+、Fe3+、Hg2+、K+、Mg2+、Mn2+、Na+、 Pb2+、Sn2+、Zn2+Figure of fluorescence intensity changes spectrum after reacting with specific recognition copper ion fluorescence probe, can from figure Out, in addition to Cu2+Weaken fluorescence intensity outer, other metal ions of addition are to the fluorescence intensity of the compound without obvious shadow It rings, it suffices to say that the bright compound is to Cu2+With selectivity.
Fig. 4 is the CuCl that various concentration is gradually added into the specific recognition copper ion fluorescence probe DMSO solution2It is molten Liquid, the excitation wavelength 350nm of setting, the fluorescence intensity change spectrum of measurement, show in figure: specific detection copper ion concentration is examined The launch wavelength of disconnected reagent is 510nm, and CuCl is continuously added into solution2The fluorescence intensity of the compound gradually subtracts after aqueous solution It is weak.
Fig. 5 is the CuCl that various concentration is gradually added into the specific recognition copper ion fluorescence probe DMSO solution2It is molten Liquid, measures uv absorption spectra, shows in figure: the absorbing wavelength of specific recognition copper ion fluorescence probe at 419nm by Gradually decline, be gradually increasing at 325nm, is added drop-wise to 3.03 × 10 in concentration-4When mol/L, UV absorption intensity no longer enhances.

Claims (6)

1. a kind of preparation method of specific recognition copper ion fluorescence probe, the compound name of the fluorescence probe is 4,4', 4 ", 4 " '-tetrahydroxys -3,3', 3 ", 3 " '-four (2- benzo [d] imidazoles) tetraphenyl ethylene, chemical molecular formula C54H36N8O4, molecule Structural formula are as follows:
Preparation step is as follows:
1) under protection of argon gas, zinc powder is added in anhydrous tetrahydro furan, under ice salt bath, TiCl is added dropwise4, it is added dropwise Afterwards, restore to room temperature, anhydrous pyridine is added, by raw material 4,4'- dimethoxy-benzophenone is dissolved into tetrahydrofuran, later It is added in reaction solution, is refluxed overnight, TLC detects reaction process, after complete reaction, 10% carbonic acid is added in reaction solution Potassium solution, stirring at normal temperature 2 hours, vacuum filtration, methylene chloride extraction, anhydrous magnesium sulfate was dry, with ethyl acetate and petroleum ether Recrystallization, obtains 4,4', 4 ", 4 " '-tetramethoxy tetraphenyl ethylene of white powder solid；
2) 4,4', 4 ", 4 " '-tetramethoxy tetraphenyl ethylenes and methylene chloride under protection of argon gas, is added, by BBr3It is dissolved into dichloro In methane, the BBr that will be dissolved into methylene chloride under conditions of -78 DEG C3It is added dropwise, after being added dropwise, in -78 DEG C of item Under part, half an hour is reacted, is restored to room temperature, overnight, TLC monitors reaction process for reaction at room temperature, after reaction is completed, Distilled water is added dropwise, has the precipitation of aubergine solid, is washed with methylene chloride, obtain 4,4', 4 ", the 4 " hydroxyl of '-four of violet solid Base tetraphenyl ethylene；
3) above-mentioned 4,4', 4 ", 4 " '-tetrahydroxy tetraphenyl ethylenes and methenamine are added in trifluoroacetic acid, are heated to reflux 4 Hour, TLC monitors reaction process, after restoring room temperature, ice water to yellow solid is added and is precipitated, suction filtration obtains yellow solid, uses Methylene chloride: hexamethylene 5:1 column chromatography, it is dry, obtain yellow solid, 4,4', 4 ", 4 " '-tetrahydroxys -3,3', 3 ", 3 " '-four Aldehyde radical tetraphenyl ethylene；
4) by above-mentioned 4,4', 4 ", 4 " '-tetrahydroxy -3,3', 3 ", the 3 " aldehyde radical of '-four tetraphenyl ethylenes and sodium hydrogensulfite are added to nothing In water-ethanol, 4 hours are stirred under room temperature, o-phenylenediamine is dissolved into a certain amount of DMF, is added in reaction solution, flow back Overnight, TLC detects reaction process and a certain amount of distilled water is added after reaction stops, and has yellow solid precipitation, filters, use first Alcohol washing, is dried to obtain 4,4', 4 ", 4 " '-tetrahydroxy -3,3' of yellow solid, 3 ", 3 " '-four (2- benzo [d] imidazoles) four benzene second Alkene.
2. the preparation method of specific recognition copper ion fluorescence probe according to claim 1, it is characterised in that: the zinc Powder, tetrahydrofuran, titanium tetrachloride and anhydrous pyridine mass ratio be 9:30:4:1；4,4'- dimethoxy-benzophenone with it is anhydrous The mass ratio of tetrahydrofuran is 1:4.5.
3. the preparation method of specific recognition copper ion fluorescence probe according to claim 1, it is characterised in that: described 4, 4', the mass ratio of 4 ", 4 " '-tetramethoxy tetraphenyl ethylenes, methylene chloride and Boron tribromide are 1:11:4.4.
4. the preparation method of specific recognition copper ion fluorescence probe according to claim 1, it is characterised in that: described 4, 4', the mass ratio of 4 ", 4 " '-tetrahydroxy tetraphenyl ethylenes, methenamine and trifluoroacetic acid are 2:2.3:107.5.
5. the preparation method of specific recognition copper ion fluorescence probe according to claim 1, it is characterised in that: described 4, The mass ratio of 4', 4 ", 4 " '-tetrahydroxy -3,3', 3 ", the 3 " aldehyde radical of '-four tetraphenyl ethylenes, sodium hydrogensulfite and dehydrated alcohol are 2: The mass ratio of 3:235-240 o-phenylenediamine and DMF are 1:19.
6. a kind of application of specific recognition copper ion fluorescence probe prepared by any one of claim 1-5, it is characterised in that: As quick detection metal copper ion, targeted therapy and bio-imaging are used in biologic applications.
CN201811071781.8A 2018-09-14 2018-09-14 A kind of preparation method and applications of specific recognition copper ion fluorescence probe Pending CN109053583A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113248394A (en) * 2021-06-03 2021-08-13 宝鸡文理学院 Method for identifying and resolving chiral compound by using AIE (aluminum iodide) molecule
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CN116003313A (en) * 2021-10-21 2023-04-25 天津理工大学 Preparation method and application of AIE fluorescent compound for rapidly monitoring ammonia gas

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Publication number Priority date Publication date Assignee Title
CN115403475A (en) * 2021-05-26 2022-11-29 天津理工大学 Preparation method and application of diagnostic reagent for specifically detecting copper ion concentration
CN113248394A (en) * 2021-06-03 2021-08-13 宝鸡文理学院 Method for identifying and resolving chiral compound by using AIE (aluminum iodide) molecule
CN113248394B (en) * 2021-06-03 2023-12-05 宝鸡文理学院 Method for identifying and resolving chiral compound by AIE molecule
CN114891169A (en) * 2021-08-05 2022-08-12 中原工学院 Method for synthesizing zinc complex COFs material in one step
CN114891169B (en) * 2021-08-05 2023-07-21 中原工学院 Method for synthesizing zinc complex COFs material in one step
CN116003313A (en) * 2021-10-21 2023-04-25 天津理工大学 Preparation method and application of AIE fluorescent compound for rapidly monitoring ammonia gas

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