CN109970762A - It is a kind of based on thiophene-benzene Conjugate macrocycle fluorescence probe and its preparation and application - Google Patents
It is a kind of based on thiophene-benzene Conjugate macrocycle fluorescence probe and its preparation and application Download PDFInfo
- Publication number
- CN109970762A CN109970762A CN201910402657.3A CN201910402657A CN109970762A CN 109970762 A CN109970762 A CN 109970762A CN 201910402657 A CN201910402657 A CN 201910402657A CN 109970762 A CN109970762 A CN 109970762A
- Authority
- CN
- China
- Prior art keywords
- fluorescence probe
- thiophene
- preparation
- benzene
- conjugate macrocycle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D495/18—Bridged systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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"
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The present invention discloses a kind of based on thiophene-benzene Conjugate macrocycle fluorescence probe and its preparation and application, and the general structure of the fluorescence probe isWherein, R is selected from one of the alkyl that carbon atom number is 2~12.It is of the invention based on the S and Hg in thiophene-benzene Conjugate macrocycle fluorescence probe2+Fluorescent quenching occurs after coordination, to realize to Hg2+Fluorescence response, and then can be realized to Hg2+Detection, the fluorescence probe is to Hg2+Selectivity it is good, to Hg2+Detection method it is simple, it is at low cost, it is convenient and efficient.
Description
Technical field
The present invention relates to fluorescent probe technique fields more particularly to a kind of based on thiophene-benzene Conjugate macrocycle fluorescence probe
And its preparation and application.
Background technique
Mercury metal is a kind of one of pollutant that distribution is very wide, has very strong carcinogenicity, even if at much lower concentrations
High risks can be caused to environment and public health.Mercury ion (Hg2+) form existing for nature is very extensive, the nothing in environment
Machine mercury ion can be the methyl mercury of severe toxicity by organism conversion under certain condition.Inorganic mercury mainly influences kidney, and methyl mercury
Nervous system, especially central nervous system are mainly encroached on after into human body.Therefore there is great meaning for the detection of mercury ion
Justice.
Existing Hg2+Detection technique relies on large-scale instrument, including atomic absorption spectrography (AAS), atomic fluorescence spectrometry, inductance
Coupled plasma mass etc.；However above-mentioned Hg2+Detection technique there are expensive equipment, complicated for operation, sample need pre-treatment,
The problems such as time-consuming.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of based on thiophene-benzene Conjugate macrocycle
Fluorescence probe and its preparation and application, it is intended to solve existing Hg2+Expensive equipment existing for detection technique, complicated for operation, sample
Need pre-treatment, the problem of time-consuming.
Technical scheme is as follows:
It is a kind of based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein the general structure of the fluorescence probe isWherein, R is selected from one of the alkyl that carbon atom number is 2~12.
It is described based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein R n-C6H13。
A kind of preparation method as described above based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein comprising steps of
A, under inert gas protection, willTrimethylsilyl acetylene, CuI, Pd (PPh3)4、PPh3、
Organic amine is dissolved in the first organic solvent, is heated to reflux and is stirred to react, room temperature is cooled to after fully reacting, reaction solution is through dense
Contracting, column chromatography for separation obtain the first intermediate；The structural formula of first intermediate is
B, under inert gas protection, the first intermediate, tetrabutyl ammonium fluoride are dissolved in the second organic solvent, under room temperature
It is stirred to react, deionized water quenching reaction is added after fully reacting, is extracted, organic phase is concentrated, column chromatography for separation obtains
Second intermediate；The structural formula of second intermediate is
C, by the second intermediate, CuI, Pd (PPh3)2Cl2It is dissolved in the first in the mixed solvent, stirs 5~10 under room temperature
It, obtains third intermediate through concentration, column chromatography for separation after fully reacting；The structural formula of the third intermediate is
D, under inert gas protection, by third intermediate, Na2S·9H2O is dissolved in the second in the mixed solvent, 130~
It is stirred to react at 170 DEG C, room temperature is cooled to after fully reacting, reaction solution is concentrated, column chromatography for separation obtains fluorescence probe.
The preparation method based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein the inert gas is nitrogen
Or argon gas.
The preparation method based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein in step A, the organic amine
For triethylamine or diisopropylamine；First organic solvent is toluene.
The preparation method based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein described in step ATrimethylsilyl acetylene, CuI, Pd (PPh3)4、PPh3, organic amine molar ratio be 1:2.5~3.5:
0.05~0.15:0.05~0.15:0.1~0.3:1~1.5.
The preparation method based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein in step B, described second has
Solvent is anhydrous THF；First intermediate, tetrabutyl ammonium fluoride molar ratio be 1:2.5~4.
The preparation method based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein in step C, described first is mixed
Bonding solvent is the mixture of the THF that volume ratio is 1:1 and triethylamine；Second intermediate, CuI, Pd (PPh3)2Cl2Mole
Than for 1:0.02~0.05:0.01~0.05.
The preparation method based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein in step D, the second mixing is molten
Agent is the mixture of the toluene that volume ratio is 1:1 and ethylene glycol monomethyl ether；The third intermediate, Na2S·9H2The molar ratio of O is
1:4~7.
A kind of application based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein using as described above based on thiophene
Pheno-benzene Conjugate macrocycle fluorescence probe detects the Hg in solution2+。
The utility model has the advantages that the S and Hg of the invention based in thiophene-benzene Conjugate macrocycle fluorescence probe2+Occur after coordination glimmering
Optical quenching, to realize to Hg2+Fluorescence response, and then can be realized to Hg2+Detection, the fluorescence probe is to Hg2+Selection
Property is good, to Hg2+Detection method it is simple, it is at low cost, it is convenient and efficient.
Detailed description of the invention
Fig. 1 is the THF-H of the different moisture content of fluorescence probe made from the embodiment of the present invention 52The fluorescence emission of O system
Compose comparison diagram, λex=330nm.
Fig. 2 is the THF- of the different metal ions containing equimolar concentration of fluorescence probe made from the embodiment of the present invention 5
H2The fluorescence emission spectrum comparison diagram of O system (water content 90%), λex=330nm.
Fig. 3 is the THF- of the different metal ions containing equimolar concentration of fluorescence probe made from the embodiment of the present invention 5
H2The multiplying power histogram that the fluorescence intensity of O system (water content 90%) changes, λex=330nm.
Specific embodiment
The present invention provide it is a kind of based on thiophene-benzene Conjugate macrocycle fluorescence probe and its preparation and application, to make the present invention
Purpose, technical solution and effect it is clearer, clear, the present invention is described in more detail below.It should be appreciated that this place
The specific embodiment of description is only used to explain the present invention, is not intended to limit the present invention.
The present invention provides a kind of based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein the structure of the fluorescence probe is logical
Formula isWherein, R is selected from one of the alkyl that carbon atom number is 2~12；Preferably, R n-
C6H13。
It is of the invention based on the S and Hg in thiophene-benzene Conjugate macrocycle fluorescence probe2+Fluorescent quenching occurs after coordination, from
And it realizes to Hg2+Fluorescence response, and then can be realized to Hg2+Detection, the fluorescence probe is to Hg2+Selectivity it is good, it is right
Hg2+Detection method it is simple, it is at low cost, it is convenient and efficient.
Preparation method the present invention also provides one kind as described above based on thiophene-benzene Conjugate macrocycle fluorescence probe,
In, comprising steps of
A, under inert gas protection, willTrimethylsilyl acetylene, CuI, Pd (PPh3)4、PPh3、
Organic amine is dissolved in the first organic solvent, is heated to reflux and is stirred to react, room temperature is cooled to after fully reacting, reaction solution is through dense
Contracting, column chromatography for separation obtain the first intermediate；The structural formula of first intermediate is
B, under inert gas protection, the first intermediate, tetrabutyl ammonium fluoride are dissolved in the second organic solvent, under room temperature
It is stirred to react, deionized water quenching reaction is added after fully reacting, is extracted, organic phase is concentrated, column chromatography for separation obtains
Second intermediate；The structural formula of second intermediate is
C, by the second intermediate, CuI, Pd (PPh3)2Cl2Be dissolved in the first in the mixed solvent, stirred under room temperature 5~10 days it is (excellent
Select 7 days), third intermediate is obtained through concentration, column chromatography for separation after fully reacting；The structural formula of the third intermediate is
D, under inert gas protection, by third intermediate, Na2S·9H2O is dissolved in the second in the mixed solvent, 130~
It is stirred to react under 170 DEG C (preferably 150 DEG C), room temperature is cooled to after fully reacting, reaction solution is concentrated, column chromatography for separation obtains
Fluorescence probe.
It should be noted that above-mentioned each reaction step can pass through thin-layer chromatography (Thin layer
Chromatography, TLC) method monitors reaction process and whether determining reaction carries out completely.
Further, the preparation method based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein the indifferent gas
Body is nitrogen or argon gas (preferably nitrogen).
Further, the preparation method based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein in step A, institute
Stating organic amine is triethylamine or diisopropylamine；First organic solvent is toluene；It is describedTrimethyl
Silico acetylene, CuI, Pd (PPh3)4、PPh3, organic amine molar ratio be 1:2.5~3.5:0.05~0.15:0.05~0.15:0.1
~0.3:1~1.5 (preferred molar ratio 1:3:0.1:0.1:0.2:1.3).
Specifically, describedCan be made by following steps: A1, in inert gas, (inert gas can
For nitrogen or argon gas, preferably nitrogen) protection under, willJoin pinacol borate, potassium acetate, [1,1'- bis- (two
Phenylphosphine) ferrocene] palladium chloride, bis- (diphenylphosphine) ferrocene of 1,1'-, it is dissolved in third organic solvent (preferably 1,4- dioxy
Six rings) in, it is heated to reflux and is stirred to react, room temperature is cooled to after fully reacting, reaction solution is concentrated to get through extraction, organic phase
First crude product；Under inert gas (inert gas can be nitrogen or argon gas, preferably nitrogen) protection, then by the first thick production
Object,K2CO3、Pd(PPh3)4Being dissolved in third mixed solvent, (third mixed solvent can be the tetrahydro that volume ratio is 8:1:1
Furans, ethyl alcohol, deionized water mixture) in, be heated to reflux be stirred to react, room temperature is cooled to after fully reacting, react
Liquid is extracted, merges organic phase, concentration, column chromatography for separation, is obtainedA2, in inert gas (inertia
Gas can be nitrogen or argon gas, preferably nitrogen) under protection, it willIt is dissolved in third organic solvent (preferably two
Chloromethanes), it is slowly added to excessive Boron tribromide under the conditions of ice-water bath (preferably 0 DEG C), restores to room temperature to be stirred to react, instead
Deionized water is added after answering completely into reaction solution under ice-water bath, and (purpose is excessive Boron tribromide to be quenched, and then be quenched anti-
Answer), reaction mixture is extracted, merges organic phase, concentration, and the second crude product is obtained；Then by the second crude product, R-Br, carbon
Sour caesium is dissolved in the 4th organic solvent (preferably acetone), be heated to reflux be stirred to react, after fully reacting reaction solution it is concentrated,
Column chromatography for separation obtainsWherein, further, described in step A1Join boric acid
Pinacol ester, potassium acetate, [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride, bis- (diphenylphosphine) ferrocene of 1,1'-,K2CO3、Pd(PPh3)4Molar ratio be 1:4~7:4~7:0.05~0.15:0.05~0.15:4~7:4~7:
0.05~0.15 (preferred molar ratio 1:6:6:0.1:0.1:6:6:0.1)；It is described in step A2
Boron tribromide, R-Br, cesium carbonate molar ratio 1:2.5~3.5:3~7:3~5 (preferred molar ratio 1:3:6:4).
Further, the preparation method based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein in step B, institute
Stating the second organic solvent is anhydrous THF；First intermediate, tetrabutyl ammonium fluoride molar ratio be 1:2.5~4 (preferably rub
You are than being 1:3).
Further, the preparation method based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein in step C, institute
State the mixture that the first mixed solvent is THF and triethylamine that volume ratio is 1:1；Second intermediate, CuI, Pd (PPh3)2Cl2Molar ratio be 1:0.02~0.05:0.01~0.05 (preferred molar ratio 1:0.03:0.025).
Further, the preparation method based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein in step D, the
Two mixed solvents are the mixtures of the toluene that volume ratio is 1:1 and ethylene glycol monomethyl ether；The third intermediate, Na2S·9H2O's
Molar ratio is 1:4~7 (preferred molar ratio 1:6).
Preparation condition based on thiophene-benzene Conjugate macrocycle fluorescence probe of the invention is simple, not harsh, it is easy to accomplish,
Be conducive to production application.
The present invention also provides a kind of applications based on thiophene-benzene Conjugate macrocycle fluorescence probe, wherein using such as above-mentioned institute
That states detects the Hg in solution based on thiophene-benzene Conjugate macrocycle fluorescence probe2+.It is of the invention based on thiophene-benzene Conjugate macrocycle
Fluorescence probe to Hg2+Selectivity it is good, to Hg2+Detection method it is simple, it is at low cost, it is convenient and efficient.
Below by embodiment, the present invention is described in detail.
Embodiment 1
With R=n-C6H13For, shown in preparation route such as following formula (1), acquisition is used to prepare based on thiophene-benzene Conjugate macrocycle
Fluorescence probe substrate 3.
(1) compound 1 (3.00g, 5.45mmol) is added in 250mL round-bottomed flask, connection pinacol borate (8.31g,
32.71mmol), potassium acetate (3.21g, 32.71mmol)；[bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride (Pd (PPh3)2Cl2, 398.90mg, 0.545mmol) and 1, bis- (diphenylphosphine) ferrocene (302.24mg, 0.545mmol) of 1'- are protected in nitrogen
Shield is lower to be added dry Isosorbide-5-Nitrae dioxane 100mL, and being heated to 100 DEG C flows back, and is stirred overnight, and supervises detection reaction by TLC
Process merges organic phase, is spin-dried for decompressor to after reaction, be extracted with water and ethyl acetate, obtains the first thick production
Object.
First crude product is added, potassium carbonate (3.73g, 27.0mmol) is housed, bromo-iodobenzene (3.47mL, 27.0mmol)
With the 250mL twoport flask of tetrakis triphenylphosphine palladium (312mg, 0.27mmol), in N2Lower addition tetrahydrofuran (THF) of protection/
Ethyl alcohol (EtOH)/deionized water (H2O) (v/v/v=80/10/10), 105 DEG C of heating flow back, are stirred overnight, pass through TLC
Reaction process is monitored, after reaction, is extracted with deionized water and DCM, organic phase is collected, decompression removal solvent uses dichloromethane
Alkane/petroleum ether (v/v=2/5) carries out silica gel column chromatography separation as eluant, eluent, obtains 2.00g compound 2, yield is
63.3%.The structural characterization data of compound 2 are as follows:1H NMR(399MHz,CDCl3) δ 7.71 (d, J=2.1Hz, 1H), 7.46
(dd, J=21.7,7.9Hz, 2H), 7.33 (d, J=8.0Hz, 2H), 7.26 (s, 2H), 7.12 (d, J=8.0Hz, 2H), 6.98
(d, J=8.5Hz, 2H), 6.70-6.63 (m, 2H), 3.75 (d, J=1.7Hz, 3H), 1.26 (s, 1H)13C NMR(151MHz,
CDCl3)δ157.23,142.91,141.84,136.07,135.11,131.60,130.96,129.16,128.97,128.89,
125.29,124.41,121.83,112.11,54.09,28.68,-1.02。
(2) in the twoport flask of 250mL, with dry methylene chloride dissolved compound 2 (1.00g, 1.42mmol),
It is slowly added in 0 DEG C Boron tribromide (0.7mL, 7.12mmol), recovery is stirred overnight under nitrogen protection to room temperature, is passed through
TLC monitors reaction process, to after reaction, at 0 DEG C, deionized water 20mL be added, to after reaction, use methylene chloride
It is extracted with water, collects organic phase, decompression removal solvent obtains the second crude product.
Second crude product is dissolved in acetone solvent, adds hexyl bromide 1 bromohexane (1.2mL, 8.54mmol) and cesium carbonate
(1.86g, 5.69mmol) flows back at 80 DEG C, is stirred overnight, and is monitored and is reacted with TLC, mixture is revolved with decompressor
It is dry, it is then that eluant, eluent carries out silica gel column chromatography separation with methylene chloride/petroleum ether (v/v=1/5), obtains 1.12g compound 3
(it is used as substrate of the preparation based on thiophene-benzene Conjugate macrocycle fluorescence probe), yield 93.4%.The structure table of compound 3
Levy data are as follows:1HNMR (399MHz, Chloroform-d) δ 7.72 (d, J=1.9Hz, 1H), 7.52-7.40 (m, 2H), 7.34
(d, J=8.0Hz, 2H), 7.14 (d, J=7.9Hz, 2H), 7.00 (d, J=8.3Hz, 2H), 6.67 (d, J=8.5Hz, 2H),
3.90 (t, J=6.6Hz, 2H), 1.51-1.41 (m, 2H), 1.35 (qd, J=7.2,4.9,3.6Hz, 4H), 0.93 (d, J=
6.3Hz,3H).13C NMR(151MHz,Chloroform-d)δ157.85,144.03,142.87,137.00,135.91,
132.61,132.00,130.16,129.95,129.89,126.28,125.41,122.84,113.62,67.83,31.61,
29.26,25.73,22.59,14.03。
Embodiment 2
With R=n-C6H13For, shown in preparation route such as following formula (2), preparation is visited based on thiophene-benzene Conjugate macrocycle fluorescence
First intermediate 4 of needle.
Compound 3 (4.50g, 5.37mmol) is added in 250mL twoport flask, trimethylsilyl acetylene (1.58g,
16.11mmol), cuprous iodide (CuI, 102.2mg, 0.536mmol), tetrakis triphenylphosphine palladium (Pd (PPh3)4, 620mg,
0.536mmol), triphenylphosphine (PPh3, 281.45mg, 1.07mmol) and diisopropylamine (1mL, 7.13mmol), it is protected in nitrogen
Shield is lower to be added toluene (80mL), is heated to flowing back, be stirred overnight, monitors reaction process with TLC, after reaction, decompression removal
Solvent in reaction solution carries out silica gel column chromatography separation as eluant, eluent with methylene chloride/petroleum ether (v/v=1/5), obtains
The first intermediate of 3.60g 4 is yellow oil, yield 76.8%.The structural characterization data of first intermediate 4 are1H NMR
(399MHz,CDCl3) δ 7.71-7.65 (m, 1H), 7.51 (d, J=7.8Hz, 1H), 7.44-7.34 (m, 3H), 7.37-7.24
(m, 3H), 7.11 (dd, J=8.3,1.6Hz, 3H), 6.97 (d, J=8.7Hz, 3H), 6.69-6.61 (m, 3H), 3.89 (t, J
=6.6Hz, 3H), 1.54 (d, J=1.6Hz, 1H), 1.43 (s, 4H), 1.36-1.30 (m, 6H), 0.94-0.85 (m, 5H),
0.26 (d, J=1.5Hz, 11H), 0.18 (d, J=1.5Hz, 1H)13C NMR (151MHz, Chloroform-d) δ 157.81,
143.78,140.94,140.83,137.88,137.60,136.07,132.64,131.94,131.89,130.51,130.49,
128.59,127.03,126.83,126.34,126.27,126.22,123.45,113.62,105.12,94.18,67.85,
67.81,31.64,31.61,29.30,25.76,22.61,14.06,-2.00。
Embodiment 3
With R=n-C6H13For, shown in preparation route such as following formula (3), preparation is visited based on thiophene-benzene Conjugate macrocycle fluorescence
Second intermediate 5 of needle.
The first intermediate 4 (2.4g, 2.74mmol) is dissolved in the anhydrous THF of 80mL in 250mL twoport flask, in nitrogen
Protection is lower to be added tetrabutyl ammonium fluoride (2.09mL, 8.21mmol), and stirring at normal temperature is overnight, reaction process is monitored with TLC, wait react
Terminate, deionized water quenching reaction is added, extracted with methylene chloride and deionized water, collect organic phase, depressurizes removal solvent, then
It is that eluant, eluent carries out silica gel column chromatography separation with methylene chloride/petroleum ether (v/v=2/5), obtains the second intermediate of 0.943g 5,
Yield is 47.0%.The structural characterization data of second of mesosome 5 are as follows:1H NMR(399MHz,CDCl3)δ7.71(s,1H),7.55
(d, J=7.9Hz, 1H), 7.43 (d, J=7.6Hz, 1H), 7.39-7.32 (m, 2H), 7.26 (s, 1H), 7.12 (d, J=
8.0Hz, 2H), 6.97 (d, J=8.3Hz, 2H), 6.65 (d, J=8.3Hz, 2H), 3.88 (t, J=6.6Hz, 2H), 3.09 (s,
1H), 1.75 (q, J=7.2Hz, 2H), 1.43 (s, 2H), 1.36-1.24 (m, 4H), 0.89 (s, 2H), 0.89 (d, J=
13.0Hz,1H).13C NMR(151MHz,Chloroform-d)δ157.82,143.85,140.94,137.46,136.01,
132.63,131.98,130.66,130.60,128.70,127.33,126.25,122.44,113.62,83.67,77.16,
67.84,31.62,29.28,26.92,25.74,22.60,14.04。
Embodiment 4
With R=n-C6H13For, shown in preparation route such as following formula (4), preparation is visited based on thiophene-benzene Conjugate macrocycle fluorescence
The third intermediate 6 of needle.
By the second intermediate 5 (400mg, 0.545mmol), cuprous iodide (3.12mg, 0.016mmol), triphenylphosphine two
Palladium chloride (9.58mg, 0.014mmol) is added in 1000mL single port bottle, and tetrahydrofuran (THF, 300mL) and triethylamine is added
The mixed solvent of (300mL) stirring at normal temperature 7 days, monitors reaction process by TLC, and to the end of reacting, decompression removal solvent is connect
With methylene chloride/petroleum ether (v/v=1/5) be eluant, eluent carry out silica gel column chromatography separation, obtain 0.15g third intermediate 6,
For green solid, yield 32.1%.The structural characterization data of third intermediate 6 are as follows:1H NMR(600MHz,CDCl3)δ7.74
(d, J=1.7Hz, 1H), 7.53 (dt, J=7.8,1.4Hz, 1H), 7.48 (dt, J=7.7,1.3Hz, 1H), 7.41-7.30
(m, 3H), 7.12 (d, J=8.2Hz, 2H), 7.01-6.96 (m, 2H), 6.69-6.65 (m, 2H), 3.91 (t, J=6.6Hz,
2H), 1.79-1.72 (m, 2H), 1.55 (s, 2H), 1.49-1.41 (m, 2H), 1.34 (pd, J=6.6,4.1Hz, 4H), 1.25
(s,1H),0.93–0.80(m,4H).13C NMR(151MHz,CDCl3)δ157.85,143.85,141.32,137.53,
136.20,132.72,132.13,131.14,130.95,128.78,128.03,126.38,122.12,113.67,81.54,
73.91,67.89,31.65,29.72,29.31,25.78,22.63,14.07。
Embodiment 5
With R=n-C6H13For, shown in preparation route such as following formula (5), preparation is visited based on thiophene-benzene Conjugate macrocycle fluorescence
Needle 7.
Under nitrogen protection, by third intermediate 6 (140.0mg, 0.095mmol), Na2S.9H2O (138.0mg,
0.574mmol) be added in 100mL bottle with two necks, toluene (20mL) and ethylene glycol monomethyl ether (20mL) be added, be heated in 150 DEG C into
Row reflux, is stirred overnight, and monitors reaction process by TLC, to the end of reacting, decompression removal solvent, then with methylene chloride/stone
Oily ether (v/v=1/5) is that eluant, eluent carries out silica gel column chromatography separation, obtains 0.119g based on thiophene-benzene Conjugate macrocycle fluorescence
Probe 7, yield 81.2%.1H NMR (600MHz, CDCl3) δ 7.79 (d, J=3.7Hz, 1H), 7.79 (s, 1H), 7.61
(dt, J=7.5,1.4Hz, 2H), 7.48 (dt, J=7.8,1.4Hz, 2H), 7.47-7.36 (m, 6H), 7.35 (s, 2H),
7.39-7.31 (m, 0H), 7.17-7.08 (m, 4H), 7.05-6.94 (m, 4H), 6.72-6.61 (m, 4H), 3.87 (t, J=
6.6Hz,4H),1.78–1.66(m,4H),1.56(s,11H),1.46–1.36(m,7H),1.35-1.27(m,7H),1.07(s,
0H),0.88(s,7H),0.95–0.81(m,8H),0.07(s,3H),-3.86(s,1H).13C NMR(151MHz,
Chloroform-d)δ156.76,142.82,142.59,140.83,137.18,135.01,133.58,131.62,130.85,
128.16,125.45,125.32,124.88,124.15,122.99,122.50,112.58,66.80,30.91,30.62,
30.59,28.68,28.64,28.28,28.25,24.75,24.71,21.68,21.59,21.56,13.11,13.04,
13.01,-1.02。
Fluorescence probe 7 made from the embodiment is dissolved in THF, preparing several parts of concentration is 1 × 10-5The solution of mol/L, to
Different amounts of deionized water is added in solution, forms the THF-H of different moisture content2O system, the THF-H of different moisture content2O system
Fluorescence emission spectrum is as shown in Figure 1, it is known that with the increase of water content, THF-H2The fluorescence intensity base of fluorescence probe 7 in O system
This is in enhancing trend, and when water content is 90% (volumn concentration), fluorescence intensity reaches maximum value.It is 90% to water content
Fluorescence probe 7 (concentration is 1 × 10-5Mol/L THF-H)2When different metal ions being added in O system, fluorescence is measured
Emission spectrum is as shown in Figure 2, it is known that Hg2+There is apparent fluorescent quenching effect to fluorescence probe 7.With do not add any metal from
(concentration is 1 × 10 to the fluorescence probe 7 that the water content of son is 90%-5Mol/L THF-H)2The fluorescence intensity I of O system0For base
Standard, measure addition equimolar amounts different metal ions caused by fluorescence intensity change multiplying power (1-I/I0, I is containing not
With the THF-H of the fluorescence probe 7 of metal ion2The fluorescence intensity of O system) with situation of change such as Fig. 3 institute of different metal ions
Show, it is known that fluorescence probe 7 is to Hg2+With very strong selectivity.
In conclusion the S and Hg provided by the invention based in thiophene-benzene Conjugate macrocycle fluorescence probe2+It is sent out after coordination
Raw fluorescent quenching, to realize to Hg2+Fluorescence response, and then realize to Hg2+Detection；The fluorescence probe is to Hg2+Selectivity
It is good, to Hg2+Detection method it is simple, it is at low cost, it is convenient and efficient.It is of the invention based on thiophene-benzene Conjugate macrocycle fluorescence probe
Preparation condition it is simple, it is not harsh, it is easy to accomplish, be conducive to production application.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of based on thiophene-benzene Conjugate macrocycle fluorescence probe, which is characterized in that the general structure of the fluorescence probe isWherein, R is selected from one of the alkyl that carbon atom number is 2~12.
2. according to claim 1 based on thiophene-benzene Conjugate macrocycle fluorescence probe, which is characterized in that R n-C6H13。
3. a kind of preparation method as claimed in claim 1 or 2 based on thiophene-benzene Conjugate macrocycle fluorescence probe, feature
It is, comprising steps of
A, under inert gas protection, willTrimethylsilyl acetylene, CuI, Pd (PPh3)4、PPh3, it is organic
Amine is dissolved in the first organic solvent, is heated to reflux and is stirred to react, is cooled to room temperature after fully reacting, and reaction solution is concentrated, column
Chromatography obtains the first intermediate；The structural formula of first intermediate is
B, under inert gas protection, the first intermediate, tetrabutyl ammonium fluoride are dissolved in the second organic solvent, carried out under room temperature
It is stirred to react, deionized water quenching reaction is added after fully reacting, is extracted, organic phase is concentrated, column chromatography for separation obtains second
Intermediate；The structural formula of second intermediate is
C, by the second intermediate, CuI, Pd (PPh3)2Cl2It is dissolved in the first in the mixed solvent, stirs 5~10 under room temperature
It, obtains third intermediate through concentration, column chromatography for separation after fully reacting；The structural formula of the third intermediate is
D, under inert gas protection, by third intermediate, Na2S·9H2O is dissolved in the second in the mixed solvent, at 130~170 DEG C
Under be stirred to react, room temperature is cooled to after fully reacting, reaction solution is concentrated, column chromatography for separation obtains fluorescence probe.
4. the preparation method according to claim 3 based on thiophene-benzene Conjugate macrocycle fluorescence probe, which is characterized in that
The inert gas is nitrogen or argon gas.
5. the preparation method according to claim 3 based on thiophene-benzene Conjugate macrocycle fluorescence probe, which is characterized in that
In step A, the organic amine is triethylamine or diisopropylamine；First organic solvent is toluene.
6. the preparation method according to claim 3 based on thiophene-benzene Conjugate macrocycle fluorescence probe, which is characterized in that
It is described in step ATrimethylsilyl acetylene, CuI, Pd (PPh3)4、PPh3, organic amine molar ratio be 1:
2.5~3.5:0.05~0.15:0.05~0.15:0.1~0.3:1~1.5.
7. the preparation method according to claim 3 based on thiophene-benzene Conjugate macrocycle fluorescence probe, which is characterized in that
In step B, second organic solvent is anhydrous THF；First intermediate, tetrabutyl ammonium fluoride molar ratio be 1:2.5
~4.
8. the preparation method according to claim 3 based on thiophene-benzene Conjugate macrocycle fluorescence probe, which is characterized in that
In step C, first mixed solvent is the mixture of the THF that volume ratio is 1:1 and triethylamine；Second intermediate,
CuI、Pd(PPh3)2Cl2Molar ratio be 1:0.02~0.05:0.01~0.05.
9. the preparation method according to claim 3 based on thiophene-benzene Conjugate macrocycle fluorescence probe, which is characterized in that
In step D, the second mixed solvent is the mixture of the toluene that volume ratio is 1:1 and ethylene glycol monomethyl ether；The third intermediate,
Na2S·9H2The molar ratio of O is 1:4~7.
10. a kind of application based on thiophene-benzene Conjugate macrocycle fluorescence probe, which is characterized in that using such as claims 1 or 2
The Hg detected based on thiophene-benzene Conjugate macrocycle fluorescence probe in solution2+。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910402657.3A CN109970762B (en) | 2019-05-15 | 2019-05-15 | Fluorescent probe based on thiophene-benzene conjugated macrocycle and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910402657.3A CN109970762B (en) | 2019-05-15 | 2019-05-15 | Fluorescent probe based on thiophene-benzene conjugated macrocycle and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109970762A true CN109970762A (en) | 2019-07-05 |
| CN109970762B CN109970762B (en) | 2021-08-17 |
Family
ID=67073597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910402657.3A Active CN109970762B (en) | 2019-05-15 | 2019-05-15 | Fluorescent probe based on thiophene-benzene conjugated macrocycle and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109970762B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014017983A1 (en) * | 2012-07-25 | 2014-01-30 | National University Of Singapore | Highly emissive far-red/near-infrared fluorescent conjugated polymer-based nanoparticles |
| CN106939163A (en) * | 2017-03-13 | 2017-07-11 | 吉林大学 | A kind of preparation method of the fluorescent functional organic clay of height water dispersible |
| CN107652279A (en) * | 2017-10-31 | 2018-02-02 | 华中科技大学 | A kind of diarylethene role in fluorescent molecule switch, its preparation method and application |
-
2019
- 2019-05-15 CN CN201910402657.3A patent/CN109970762B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014017983A1 (en) * | 2012-07-25 | 2014-01-30 | National University Of Singapore | Highly emissive far-red/near-infrared fluorescent conjugated polymer-based nanoparticles |
| CN106939163A (en) * | 2017-03-13 | 2017-07-11 | 吉林大学 | A kind of preparation method of the fluorescent functional organic clay of height water dispersible |
| CN107652279A (en) * | 2017-10-31 | 2018-02-02 | 华中科技大学 | A kind of diarylethene role in fluorescent molecule switch, its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| YOUYONG YUAN 等: "A self-reporting AIE probe with a built-in singlet oxygen sensor for targeted photodynamic ablation of cancer cells", 《CHEM. SCI.》 * |
| ZHIXIANG LU等: "Facile synthesis and separation of E/Z isomers of aromatic-substituted tetraphenylethylene for investigating their fluorescent properties via single crystal analysis", 《J. MATER. CHEM. C》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109970762B (en) | 2021-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103194242A (en) | Liquid crystal compound containing deuterium and preparation method as well as application thereof | |
| CN104559286B (en) | A kind of triphenylamine-boron fluoride complexing dimethyl pyrrole methine derivative organic dyestuff and preparation method thereof | |
| CN102875417A (en) | Liquid crystal compound containing bicyclo (3,3,0) octane and preparation method and application thereof | |
| CN106905169B (en) | A kind of vinyl conjugation tri-arylamine group charge transport materials and preparation method thereof | |
| CN110423217A (en) | A kind of preparation method of conjugated enynes compound | |
| CN106565408A (en) | 1, 5, 9-trisubstituted coronene compound and synthesis method thereof | |
| CN108546229A (en) | It is bent synthon, preparation method and the method for preparing ring penylene class compound | |
| CN109970762A (en) | It is a kind of based on thiophene-benzene Conjugate macrocycle fluorescence probe and its preparation and application | |
| CN105061135B (en) | A kind of synthesis six vast position six benzos and the method for derivative thereof | |
| CN108864143B (en) | Asymmetric seven-element fused thiophene and preparation method and application thereof | |
| CN106632440B (en) | A kind of preparation method of aryl-boric acid ester and ene boric acid ester | |
| CN106146496A (en) | A kind of gulf district cyclization synthetic method of double imide derivative | |
| CN102863391B (en) | Compound containing 4-N-substituted phenyl-benzimidazole and preparation method thereof | |
| CN113185458B (en) | Preparation method and application of trimeric indenyl conjugated 8-benzyloxy quinoline derivative | |
| CN109438487A (en) | Double fluorine boron hyperfluorescence dyestuffs of acyl pyridine hydrazine and preparation method thereof | |
| CN115650951A (en) | Diaryl ethylene organic photochromic material and preparation method thereof | |
| CN111393869A (en) | Fluorescent dye containing phenylethynyl naphthalene, preparation method and application thereof | |
| CN113501817A (en) | Quinolinone derivative containing arylamine group and preparation and application thereof | |
| CN109232169A (en) | A kind of polyaryl replaces fulvalene compound and its synthetic method | |
| CN108586187A (en) | A kind of carbon nano ring and its synthetic method being inserted into anthracene unit in ring is to penylene | |
| CN104628753A (en) | Meso-triphenylamine-substituted 3,5-aryl-modified boron dipyrromethene fluorophore derivatives and preparation method thereof | |
| CN110128231A (en) | A kind of preparation method of diaryl acetylene compound | |
| CN110922988A (en) | Large dielectric anisotropy difluoroethyleneoxy diphenylacetylene type diluent and synthetic method thereof | |
| CN105176517B (en) | A kind of optical oxygen sensing composite material without heavy metal element and preparation method thereof | |
| CN106977536A (en) | A kind of fluorescent chemicals and its production method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |