CN114907249B - Cyclic chain isomerism stilbene fluorescent molecule, preparation method and application - Google Patents
Cyclic chain isomerism stilbene fluorescent molecule, preparation method and application Download PDFInfo
- Publication number
- CN114907249B CN114907249B CN202110184903.XA CN202110184903A CN114907249B CN 114907249 B CN114907249 B CN 114907249B CN 202110184903 A CN202110184903 A CN 202110184903A CN 114907249 B CN114907249 B CN 114907249B
- Authority
- CN
- China
- Prior art keywords
- fluorescent molecule
- formula
- isomerism
- chain
- cyclic
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
- C07D207/38—2-Pyrrolones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/58—[b]- or [c]-condensed
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- 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
-
- 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
- C09K11/07—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials having chemically interreactive components, e.g. reactive chemiluminescent compositions
-
- 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
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
-
- 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"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Luminescent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a cyclic-chain-isomerism stilbene fluorescent molecule I, a cyclic-chain-isomerism stilbene fluorescent molecule II, a cyclic-chain-isomerism stilbene fluorescent molecule III and a cyclic-chain-isomerism stilbene fluorescent molecule IV. The invention is based on a luminescent system with multiple stimulus responsivity, and utilizes dynamic covalent reaction, pH, redox reaction and illumination to regulate and control the cyclic chain fluorescent molecules of the luminescent system, thus obtaining a regulatable luminescent system.
Description
Technical Field
The application relates to a ring chain isomerism stilbene fluorescent molecule, a preparation method and application thereof, belonging to the technical field of organic fluorescent materials.
Background
Organic luminescent small molecules are used as an important luminescent material, and have wide application in biological imaging, photodynamic therapy, organic light emitting diodes and organic field effect transistors. Conventional luminescent molecules have difficulty avoiding aggregation quenching, thus limiting their use. In 2001 Tang Benzhong et al, a series of molecules with aggregation-induced emission (AIE) phenomenon have been reported, of which more tetraphenyl ethylene molecules have been studied, and researchers have found that a series of functional molecules based on the molecules can be applied to the fields of biological imaging, chemical sensing, smart materials, optical displays, etc. The molecule has an important structural characteristic that each benzene ring is distributed in a propeller shape, so that fluorescence quenching caused by pi-pi accumulation is avoided, and luminescence in an aggregation state is shown.
A molecular switch refers to a molecule that can be reversibly switched in two or more stable states. The molecule may be converted from one stable structure to another under the influence of the stimulus of the applied conditions. Such external environmental stimuli include, for example, pH, temperature, light, current, redox agents, and the like. Because many complex functional regulation in living beings is based on biomolecular switches, molecular switches also play a vital role in the fields of life sciences and medicine. The fluorescent switch is used as a common molecular switch and has important functions in the aspects of sensing detection, chiral screening, signal cascade, intelligent materials and the like.
The molecular switch generates optical responses such as fluorescence and color under external stimulus, and the combined use of multiple stimulus can enrich signal changes so as to increase the complexity of regulation, however, the realization of efficient and multi-level regulation of a system is still challenging. In addition, the molecular switch is required to have good stimulus response and high fatigue resistance so as to achieve good application effect. Some switch molecular structures are relatively special and difficult to modify into molecular structures with universality, and the application of the switch molecular structures is limited. The invention combines the stilbene element with the ring chain isomerism site, and provides a general strategy of fluorescent switch with various stimulus responsivity such as pH, oxidation reduction, illumination and the like. The fluorescent molecule has simple structure, is easy to reform and modify, has good reactivity with amine compounds, and can realize reversible labeling and stimulus response release of the amine compounds. Because amine compounds widely exist in living bodies and drug molecules, the molecular switch has wide application prospect.
Disclosure of Invention
According to one aspect of the application, a cyclic-chain-isomerism stilbene fluorescent molecule I, a cyclic-chain-isomerism stilbene fluorescent molecule II and a cyclic-chain-isomerism stilbene fluorescent molecule III are provided.
A cyclic-chain isomerism stilbene fluorescent molecule I, which is selected from any one of substances with a structural formula shown in a formula I,
in the formula I, ar is selected from any one of C8-C12 aryl, C6-C10 substituted aryl I and C4-C9 heteroaryl I;
x is selected fromAny one of them;
r1 is selected from any one of C1-C8 alkyl, C6-C12 aryl, C6-C10 substituted aryl II and C4-C9 heteroaryl II;
the hetero atom in the C4-C9 heteroaryl I and the C4-C9 heteroaryl II is independently selected from at least one of S, N.
The invention discloses an organic fluorescent molecule with multiple stimulus responsivity and a preparation method thereof. The system diarylethene-based fluorescent switch has a structure shown in formula I. The five-membered cyclic lactone part has the isomerism balance of aldehyde-hemiacetal switching ring, so that the luminescence of the molecules has stimulus responsiveness, and the fluorescence can be regulated and controlled by utilizing alkali ring opening and dynamic covalent reaction of aldehyde and amine; the hydroxyl groups of the five-membered cyclic lactone and lactam moiety can also effect a change in the intensity and wavelength of the fluorescent signal by redox reactions; in addition, the diphenylethylene part in the molecule is a light responsive group, and the conjugated structure of the molecule is changed through photocyclization/oxidation reaction, so that the fluorescence signal and the chemical reactivity are changed. Besides realizing the regulation and control of pH, amine and redox, the molecules show stronger fluorescence change in water after illumination, so that the molecular can be used for amino reversible labeling of biomolecules such as amino acid, polypeptide, protein and the like. In addition, the molecules have aggregation-induced luminescence property in a solid state, and have good application prospects in the field of stimulus-responsive luminescent materials.
Optionally, the substituent in the C6-C10 substituted aryl is selected from any one of halogen, alkoxy, haloalkyl, tertiary amino, nitro, hydroxyl and a group shown in a formula a;
in the formula a, the value range of n1 is more than or equal to 2 and less than or equal to 6.
Optionally, the alkoxy is selected from any one of the groups having the structural formula shown in formula b;
in the formula b, R2 is selected from any one of C1-C5 alkyl.
Optionally, the haloalkyl is a group formed by substitution of at least one H atom in a C1-C5 alkyl group with halogen.
Optionally, the tertiary amine group is selected from any one of the groups having the structural formula shown in formula d;
in the formula C, R4 and R5 are independently selected from any one of C1-C5 alkyl.
Optionally, the ring chain isomerism stilbene fluorescent molecule I has any one of structural formulas shown in a formula I-1,
in formula I-1, ar is selected from
Any one of them;
x is selected fromAny one of them;
R 1 selected from the group consisting of
Any one of them.
According to a second aspect of the present application, there is also provided a preparation method of the above-mentioned cyclic-chain-isomerised stilbene fluorescent molecule i, the preparation method comprising:
s100, obtaining diaryl maleimide;
s200, under the condition that a reducing agent exists, reacting and quenching a solution containing the diaryl maleimide to obtain the ring chain isomerism stilbene fluorescent molecule I;
Wherein the diaryl maleimide is selected from any one of compounds with structural formulas shown in a formula II;
in formula II, ar is selected from C 8 ～C 12 Aryl, C 6 ～C 10 Substituted aryl I, C 4 ～C 9 Any one of heteroaryl I;
r1 is selected from C 1 ～C 8 Alkyl, C 6 ～C 12 Aryl, C 6 ～C 10 Substituted aryl II, C 4 ～C 9 Any one of heteroaryl II;
the C is 4 ～C 9 Heteroaryl I, C 4 ～C 9 In heteroaryl IIThe heteroatoms are independently selected from at least one of S, N;
the product of the ring chain isomerism stilbene fluorescent molecule I is selected from any one of structural formulas shown in the formula I, wherein X is selected fromAny one of them.
In the case of formula I, X isThe cyclic chain isomerism stilbene fluorescent molecule I is diaryl vinyl lactone compound. The preparation method of the diaryl vinyl lactone compound is a method in the prior art.
In another aspect, in formula I, X isThe cyclic chain isomerism stilbene fluorescent molecule I is a diarylethene lactam compound. The preparation method of the diarylethene lactam compound comprises the following steps: firstly, diaryl maleimide is obtained; and then reacting the solution containing the diaryl maleimide in the presence of a reducing agent to obtain the diaryl vinyl lactam compound.
Specifically, the preparation method of the diaryl maleimide comprises the following steps:
s100-1, reacting a mixture containing maleic anhydride, bromine and aluminum chloride at 120-150 ℃ to obtain dibromomaleic anhydride;
s100-2, reacting a mixture containing dibromomaleic anhydride and amine compounds at 110-140 ℃ to obtain a reaction product containing dibromomaleimide, and performing post-treatment on the reaction product to obtain purified dibromomaleimide;
s100-3, dibromomaleimide, aromatic boric acid, pdCl 3 Adding 1, 4-dioxane and sodium carbonate aqueous solution into the mixture of sodium carbonate, heating and reacting to obtain a reaction solution containing diaryl maleimide, and carrying out post-treatment on the reaction solutionAnd (3) treating to obtain the purified diaryl maleimide.
In the step S100-2, the structural formula of the amine compound is R 1 NH 2 ，R 1 Is selected from the group consisting of R in formula I 1 The selection ranges of (2) are consistent and will not be described in detail herein; in step S100-3, the aromatic boric acid has the structural formula ArB (OH) 2 The selection range of Ar is identical to that of Ar in the formula I, and is not described herein.
Optionally, the reducing agent comprises sodium borohydride.
Optionally, in step S200, the reaction is stopped via quenching, including quenching with a quencher comprising an inorganic acid compound.
Specifically, the quencher includes any one of dilute hydrochloric acid, saturated ammonium chloride aqueous solution.
Alternatively, the reaction conditions are a reaction temperature of 0 to 10 ℃.
Optionally, after the quenching, a post-treatment step is further included; the post-treatment step comprises the following steps: extracting the quenched solution to obtain an extract; and then removing the solvent in the extract liquid, and performing chromatography to obtain the ring chain isomerism stilbene fluorescent molecule I.
Specifically, the quenched solution is extracted multiple times by ethyl acetate, then the extract is dried by anhydrous sodium sulfate, the solvent (namely ethyl acetate) is removed by a rotary evaporator, the solvent is separated by a chromatographic column (SiO 2), the eluent is a mixture of petroleum ether and ethyl tetroxide, and the ratio relationship of petroleum ether and ethyl tetroxide can be selected by a person skilled in the art according to actual needs, for example, 10:1.
The application of the cyclic-chain-isomerism stilbene fluorescent molecule I obtained by the preparation method of any one of the above to a fluorescent switch.
According to a third aspect of the present application, there is also provided a method of modulating a fluorescent switch, the method comprising: regulating and controlling the loop chain fluorescent molecules in a preset regulation mode to isomerize the loop chain fluorescent molecules, so that conversion between fluorescence and fluorescence quenching or weakening is realized; wherein the preset regulation mode comprises any one of amine regulation, acid-base regulation, redox regulation and light regulation; the cyclic chain fluorescent molecule is selected from any one of the cyclic chain isomerism stilbene fluorescent molecule I and the cyclic chain isomerism stilbene fluorescent molecule I obtained by any one of the preparation methods.
The conversion between fluorescence emission and fluorescence quenching or weakening refers to the conversion between fluorescence emission and fluorescence quenching or the conversion between fluorescence emission and fluorescence weakening.
Optionally, when the preset regulation mode is amine regulation, the method comprises the following steps: and adding alkylamine into the solution containing the ring chain isomerism stilbene fluorescent molecule I to react with the I, thereby realizing the conversion between fluorescence and fluorescence reduction.
The reaction equation of the reaction I is as follows:
the structural formula of the alkylamine is R 6 NH 2 ；
Wherein R is 6 Is C 1～ C 5 An alkyl group.
Specifically, the reaction I condition is room temperature. For example 15 to 35 ℃.
Optionally, when the preset regulation mode is acid-base regulation, the method includes: adding an acid regulator or an alkali regulator into a solution containing the ring chain isomerism stilbene fluorescent molecule I to react II, thereby realizing the conversion between fluorescence and fluorescence quenching;
the reaction equation of the reaction II is as follows:
wherein the alkali regulator comprises any one of 1, 8-diazabicyclo undec-7-ene and sodium hydroxide;
the acid regulator comprises any one of methanesulfonic acid, trifluoroacetic acid and hydrochloric acid.
Specifically, the reaction II condition is room temperature. For example 15 to 35 ℃.
Optionally, when the preset regulation mode is redox regulation, the method includes: adding an oxidizing reagent or a reducing reagent into a solution containing the ring chain isomerism stilbene fluorescent molecule I to react III, thereby realizing conversion between fluorescence luminescence and fluorescence quenching;
the reaction equation of the reaction III is as follows:
wherein the oxidizing agent comprises MnO 2 、H 2 O 2 Any one of them;
the reducing agent comprises NaBH 4 。
Specifically, the reaction III conditions were room temperature. For example 15 to 35 ℃.
Optionally, when the preset regulation mode is light regulation, the method includes:
reacting IV to a solution containing the ring chain isomerism stilbene fluorescent molecule I under the irradiation of ultraviolet light, so as to realize the conversion between fluorescence and fluorescence quenching;
the reaction equation of the reaction IV is as follows:
optionally, the wavelength of the ultraviolet light is 300-350 nm.
Optionally, the solvent in the solution containing the ring-chain-isomerised stilbene fluorescent molecule i comprises a deuterating agent; the deuterated reagent comprises any one of deuterated acetonitrile, deuterated chloroform and deuterated dichloromethane.
Optionally, the solvent in the solution containing the cyclochain isomerism stilbene fluorescent molecule I also comprises a reagent A; the reagent A is selected from any one of normal hexane, toluene, tetrahydrofuran, chloroform, acetonitrile, methanol and water.
According to a fourth aspect of the present application, there is also provided a cyclic isomerism stilbene fluorescent molecule ii selected from any one of the compounds having the structural formula shown in formula iii;
in the formula III, A' is selected from any one of C8-C12 arylene, C6-C10 substituted arylene I and C4-C9 heteroarylene I;
X is selected fromAny one of them;
R 1 selected from C 1 ～C 8 Alkyl, C 6 ～C 12 Aryl, C 6 ～C 10 Substituted aryl II, C 4 ～C 9 Any one of heteroaryl II;
the C is 4 ～C 9 Heteroarylenes I, C 4 ～C 9 The heteroatoms in heteroaryl ii are independently selected from at least one of S, N.
Alternatively, in formula III, the C 6 ～C 10 Substituted arylene I, C 6 ～C 10 The substituent in the substituted aryl II is selected from any one of halogen, alkoxy, halogenated alkyl, tertiary amino, nitro, hydroxyl and a group shown in a formula a;
in the formula a, the value range of n1 is 2-6;
the alkoxy is selected from any one of groups with a structural formula shown in a formula b;
in formula b, R 2 Selected from C 1 ～C 5 Any one of alkyl groups;
the haloalkyl is C 1 ～C 5 A group formed by substitution of at least one H atom in the alkyl group with halogen;
the tertiary amine group is selected from any one of groups with a structural formula shown in a formula d;
in formula d, R 4 、R 5 Independently selected from C 1 ～C 5 Any one of alkyl groups.
Optionally, the ring chain isomerism stilbene fluorescent molecule II has any one of structural formulas shown in a formula II-1,
in formula III-1, A' is selected from
Any one of them;
x is selected fromAny one of them;
R 1 selected from the group consisting of
Any one of them.
According to a fifth aspect of the present application, there is also provided a method for preparing the cyclic-chain-isomerised stilbene fluorescent molecule ii, the method comprising:
And (3) reacting IV to a solution containing the ring-chain isomerism stilbene fluorescent molecule I under ultraviolet irradiation, so as to obtain the ring-chain isomerism stilbene fluorescent molecule II.
Optionally, the wavelength of the ultraviolet light is 300-350 nm.
According to a sixth aspect of the present application, there is also provided a method of modulating a fluorescent switch, the method comprising: regulating and controlling the ring chain isomerism stilbene fluorescent molecule II in a preset regulation and control mode to isomerize the ring chain isomerism stilbene fluorescent molecule II, so that the conversion between fluorescence and fluorescence quenching or weakening is realized; the preset regulation mode comprises any one of amine regulation, acid-base regulation and redox regulation.
Specifically, the regulation and control mode of the ring-chain isomerism stilbene fluorescent molecule II is similar to that of the ring-chain isomerism stilbene fluorescent molecule I. When amine is regulated, the conversion is between fluorescence luminescence and fluorescence reduction; in the case of acid-base regulation or redox regulation, the conversion between fluorescence and fluorescence quenching is achieved.
According to a seventh aspect of the present application, there is also provided a cyclic isomerism stilbene fluorescent molecule iii selected from any one of the compounds having the structural formula shown in formula iv;
In the formula IV, ar is selected from any one of C8-C12 aryl, C6-C10 substituted aryl I and C4-C9 heteroaryl I;
x is selected fromAny one of them;
r1 is selected from any one of C1-C8 alkyl, C6-C12 aryl, C6-C10 substituted aryl II and C4-C9 heteroaryl II;
the hetero atoms in the C4-C9 heteroaryl I and the C4-C9 heteroaryl II are independently selected from at least one of S, N;
r6 is selected from any one of C1-C5 alkyl.
Optionally, in the formula IV, the substituent groups in the C6-C10 substituted aryl I and the C6-C10 substituted aryl II are selected from any one of halogen, alkoxy, haloalkyl, tertiary amino, nitro, hydroxyl and a group shown in a formula a;
in the formula a, the value range of n1 is 2-6;
the alkoxy is selected from any one of groups with a structural formula shown in a formula b;
in the formula b, R2 is selected from any one of C1-C5 alkyl;
the haloalkyl is a group formed by substituting at least one H atom in C1-C5 alkyl with halogen;
the tertiary amine group is selected from any one of groups with a structural formula shown in a formula d;
in formula d, R 4 、R 5 Independently selected from C 1 ～C 5 Any one of alkyl groups.
Optionally, the ring chain isomerism stilbene fluorescent molecule III has any one of structural formulas shown in the formula IV-1,
In formula IV-1, ar is selected from Any one of them;
x is selected fromAny one of them;
R 1 selected from the group consisting of
Any one of them.
According to an eighth aspect of the present application, there is also provided a method for preparing the cyclic-chain-isomerised stilbene fluorescent molecule iii, the method comprising:
and adding alkylamine into the solution containing the ring-chain isomerism stilbene fluorescent molecule I, and reacting V to obtain the ring-chain isomerism stilbene fluorescent molecule III.
Specifically, the alkylamine has the structural formula R 6 NH 2 ；
Wherein R is 6 Selected from C 1 ～C 5 Any one of alkyl groups.
Alternatively, the conditions of reaction v are: stirring at 15-30 ℃.
According to a ninth aspect of the present application, there is also provided a method of modulating a fluorescent switch, the method comprising: the method comprises the steps of regulating and controlling the ring chain isomerism stilbene fluorescent molecule III in an acid-base regulation mode, so that the ring chain isomerism stilbene fluorescent molecule III is isomerized, and the conversion between fluorescence and fluorescence quenching is realized.
Specifically, the acid-base regulation and control mode of the ring-chain isomerism stilbene fluorescent molecule III is similar to that of the ring-chain isomerism stilbene fluorescent molecule I.
According to a tenth aspect of the present application, there is also provided a cyclic isomerism stilbene fluorescent molecule iv selected from any one of the compounds having the structural formula shown in formula v;
In formula V, A', X are the same as in formula III, R 6 The same as in formula IV.
According to the eleventh aspect of the application, the preparation method of the ring-chain isomerism stilbene fluorescent molecule IV is used for regulating and controlling amine of the ring-chain isomerism stilbene fluorescent molecule II, so that the ring-chain isomerism stilbene fluorescent molecule IV can be obtained.
In this application, "Nu" means amine modulation.
C 1 ～C 8 The number of carbon atoms contained in the group is 1 to 8.
"alkyl" is a radical formed by the loss of any one of the hydrogen atoms from the molecule of an alkane compound, including straight chain alkanes, branched alkanes, cycloalkanes, branched cycloalkanes;
"aryl" is a radical of an aromatic compound molecule that is formed by the loss of any one of the hydrogen atoms on the aromatic ring;
"heteroaryl" refers to a group formed by the loss of any one hydrogen atom from an aromatic ring in an aromatic compound molecule having a heterocyclic aromatic ring;
"substituted aryl" refers to a group on an aryl group wherein any hydrogen atom is replaced with a substituent;
"arylene" refers to a group in an aromatic compound molecule that is formed by the loss of two hydrogen atoms from two adjacent C atoms of an aromatic ring;
"heteroarylene" refers to a group formed by the loss of two hydrogen atoms from two adjacent C atoms from an aromatic ring in an aromatic compound molecule having a heterocyclic aromatic ring;
"substituted arylene" refers to a group in which any hydrogen atom on the arylene group has been replaced with a substituent.
The beneficial effects that this application can produce include:
1) The invention combines dynamic covalent bond into diarylethene structure to obtain a series of molecules with solid-phase fluorescence, wherein 1-naphthalene compound also has aggregation-induced luminescence phenomenon, and the luminescence molecule itself contains dynamic covalent bond, thereby realizing the purpose of controlling luminescence by means of Dynamic Covalent Chemistry (DCC).
2) The present application provides cyclic chain isomerism fluorescent molecules of diarylethenes and their preparation; the ring chain isomerism fluorescent molecule can regulate the luminescence of the fluorescent molecule through acid and alkali (pH); the luminescence of the fluorescent molecules can be regulated and controlled by nucleophilic reagents (amine); the fluorescence is regulated and controlled through oxidation-reduction reaction, and the fluorescent lamp is used as an oxidation-reduction switch; the fluorescent molecules can be regulated and controlled by light stimulation, and the fluorescent molecule can be used as an optical switch.
Drawings
FIG. 1 (a) is a nuclear magnetic resonance hydrogen spectrum of compound 2 in deuterated acetonitrile;
FIG. 1 (b) is a nuclear magnetic resonance hydrogen spectrum of compound 12 in deuterated acetonitrile;
FIG. 1 (c) is a nuclear magnetic resonance hydrogen spectrum of compound 2a in deuterated acetonitrile;
FIG. 1 (d) is a nuclear magnetic resonance hydrogen spectrum of compound 2c in deuterated acetonitrile;
FIG. 1 (e) nuclear magnetic resonance hydrogen spectrum of compound 2ca in deuterated acetonitrile;
FIG. 1 (f) is a nuclear magnetic resonance hydrogen spectrum of compound 12c in deuterated acetonitrile;
FIGS. 2 (a), 2 (b), 2 (c), 2 (d), 2 (e), 2 (f) are fluorescence spectra of Compound 1, compound 2, compound 8, compound 9, compound 10, compound 11, respectively, in different solvents, at a concentration of 10. Mu.M;
FIG. 3 (a) is a fluorescence spectrum of compound 2a in different solvents at a concentration of 10. Mu.M;
FIG. 3 (b) is a fluorescence spectrum of compound 9a in different solvents at a concentration of 10. Mu.M;
FIG. 4 (a) is the response of fluorescence of Compound 2 to base (DBU);
FIG. 4 (b) is the response of fluorescence of Compound 9 to base (DBU);
FIG. 5 (a) is the response of fluorescence of compound 2a to acid (methanesulfonic acid);
FIG. 5 (b) is the response of the fluorescence of compound 9a to acid (methanesulfonic acid);
FIG. 6 is a comparison of redox regulated fluorescence of Compound 2 and Compound 12;
FIGS. 7 (a), 7 (b), 7 (c), and 7 (d) are fluorescence in different solvents of compound 2c, compound 4c, compound 12c, and compound 13c, respectively, with the intercalating moiety being fluorescence of the corresponding non-photocyclized compound;
fig. 8 (a) is a fluorescence spectrum of fluorescence of compound 2ca in different solvents obtained by amine control after photocyclization, with the intercalating portion being fluorescence of raw material 2c, λex=331 nm;
Fig. 8 (b) shows the fluorescence spectrum corresponding to the acid-base modulation of compound 2c after photocyclization, λex=331 nm;
fig. 8 (c) shows the fluorescence spectrum corresponding to the acid-base modulation of compound 4c after photocyclization, λex=300 nm;
FIG. 8 (d) is a graph comparing redox-mediated fluorescence of compounds 2c and 5c after photocyclization.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
Possible embodiments are described below:
1. a preparation route and a preparation method of diaryl vinyl lactone and lactam.
The preparation routes are shown in (1) and (2):
the fluorescent molecules of the diaryl vinyl lactone and the lactam can be prepared integrally through Suzuki coupling, condensation, reduction and other reactions. The specific preparation process can be seen in example 1.
3. Luminescence (exemplified by n-butylamine and t-butylamine) is modulated by amine (dynamic covalent chemistry DCC)
The diaryl vinyl lactone molecule is in a switch ring balance state, and the ring-opened aldehyde can react with amine to obtain a corresponding amine product, and the fluorescence is changed. Taking compounds 2 and 9 as examples, the compounds 2 and 9 react with n-butylamine to obtain corresponding amine products 2a and 9a, which show obvious fluorescence reduction phenomenon, so that the light emission of diarylethene molecules is regulated by amine (dynamic covalent chemistry (DCC)), and the spectrum is shown in figure 3.
4. Luminescence (exemplified by 1, 8-diazabicyclo undec-7-ene (DBU) and methylsulfonic acid (MsA)) is modulated by acid base (pH)
The reaction of the fluorescent switch by pH is shown in formula-4:
as the diaryl vinyl lactone molecule is in a switching ring balance state, the ring opening of the five-membered ring lactone can be promoted under the alkaline condition to obtain a ring opening structure, and the ring closing is facilitated under the acidic condition to obtain a ring closing structure. The switching ring of the lactone moiety can greatly affect the luminescence of the molecule. The molecule shows strong fluorescence in a closed-loop form under an acidic condition, and the fluorescence is quenched in an open-loop form under an alkaline condition, so that the regulation and control of acid-base on the fluorescence are realized.
In addition, the reaction products of the molecules and the amine can be regulated and controlled through acid and alkali.
5. Regulation of luminescence by redox
The diarylethylenelactone and lactam molecules are in the form of hemiacetals and can be oxidized to anhydrides and imides where the molecules emit light in the hemiacetal form and the anhydride or imide form.
6. Light-mediated diarylethenes
The schematic diagram is shown in a formula-6, the diaryl ethylene part contained in the diaryl ethylene lactone and lactam molecule is a photochromic group, the diaryl ethylene part is subjected to a photocyclization reaction under ultraviolet light, the photocyclization compound is unstable and easy to lose hydrogen to obtain an aromatized large pi system compound, and the molecule after photocyclization has stronger and shorter wavelength fluorescence due to the increase of molecular planarization and rigidity, so that the purpose of regulating the luminescence of the molecule by light is achieved.
7. Related modulation of diarylethenes after photocyclization
The light-cyclized diarylethylene lactone and amide molecules can also be controlled to emit light by acid-base (pH), amine (DCC) and redox controls, as shown in formula-7.
The diaryl vinyl lactone and amide after photocyclization show similar properties to the molecule before photocyclization, with the fluorescence gradually decreasing to no fluorescence with increasing pH, and can be replaced by MnO 2 Oxidation to give anhydrides and imides is accompanied by a red shift in fluorescence wavelength, which can react with amines resulting in a dramatic decrease in fluorescence. Taking 2c,4c and 5c as examples, haveThe embodiment is the same as the above process, and the fluorescence change is shown in fig. 8.
Example 1
Synthesis of Compound 1:
the specific preparation process of the diaryl vinyl lactone comprises the following steps: 1 equivalent of mucor-bromoacid, 3 equivalents of arylboronic acid (specifically p-dimethylaminophenylboronic acid), 0.05 equivalent of bis (triphenylphosphine) palladium dichloride and 0.05 equivalent of triethylbenzyl ammonium chloride are weighed into a double-neck round-bottom flask, a reflux device and a nitrogen protection device are installed, the vacuum nitrogen is pumped for three times, 20 ml of toluene and an aqueous solution containing 4 equivalents of CsF (V) are added through a rubber stopper by a syringe H2O :V toluene =1:5), heated to 90 ℃ for 4 hours. The reaction was cooled to room temperature and extracted three times with DCM, the combined organic phases were dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporator followed by column chromatography (SiO 2 ) Separating, wherein the eluent is petroleum ether: ethyl acetate=15:1. Diaryl target compounds can be obtained.
Synthesis of Compound 2
Similar to the preparation of compound 1, the difference is that: the boric acid used is p-methoxyphenylboric acid.
Synthesis of Compound 3
Similar to the preparation of compound 1, the difference is that: the boric acid used was 3-methoxyphenylboric acid.
Synthesis of Compound 4
Similar to the preparation of compound 1, the difference is that: the boric acid used was 3, 5-dimethoxyphenylboric acid.
Synthesis of Compound 6
Similar to the preparation of compound 1, the difference is that: the boric acid used is p-bromophenylboric acid.
Synthesis of Compound 7
Similar to the preparation of compound 1, the difference is that: the boric acid used is para-trifluoromethyl phenylboronic acid.
Synthesis of Compound 8
Similar to the preparation of compound 1, the difference is that: the boric acid used was 1-naphthalene boric acid.
Synthesis of Compound 10
Similar to the preparation of compound 1, the difference is that: the boric acid used was 2-thiopheneboronic acid.
Synthesis of Compound 11
Similar to the preparation of compound 1, the difference is that: the boric acid used is polyethylene glycol phenylboronic acid.
Synthesis of Compound 12
Synthesis of diarylethene lactam
The route is as follows:
1 equivalent of maleic anhydride is weighed into a double-neck round-bottom flask, a condenser tube and a tail gas absorbing device are arranged, the temperature is increased to 60 ℃, at this time, the maleic anhydride is dissolved, 0.02 equivalent of anhydrous aluminum trichloride is added, and the temperature is increased to 130 ℃. 2 equivalents of bromine were added dropwise to the flask via a constant pressure dropping funnel. After the bromine is added dropwise, the temperature is kept at 130 ℃ for one hour, and the reaction system is solidified. The yellow solid obtained is dibromomaleic anhydride and is used directly in the next step without purification.
1 equivalent of dibromomaleic anhydride was weighed into a single neck round bottom flask, 20 ml of acetic acid was added for dissolution, a reflux apparatus was installed, heated to 120℃and then 1.1 equivalent of amine (specifically methylamine) was added, and heating was continued for one hour at 120 ℃. The reaction mixture was cooled to room temperature, poured into ice water, extracted three times with DCM, and the solvent was removed by rotary evaporation of the dried organic phase over anhydrous sodium sulfate followed by column chromatography (SiO 2 ) Separating, wherein the eluent is petroleum ether: ethyl acetate=150:1. Dibromomaleimide solids can be obtained.
1 equivalent of dibromomaleimide, 3 equivalents of arylboronic acid (specifically p-methoxyphenylboronic acid) and 0.05 equivalent of PdCl are weighed out 2 (dppf) (dppf represents bis (diphenylphosphino) ferrocene as a ligand) and 4 equivalents of sodium carbonate were placed in a double-necked round bottom flask, a reflux apparatus and a nitrogen protection apparatus were installed, and vacuum nitrogen was evacuated and replaced three times with a syringe via rubberThe plug was charged with 20ml of 1, 4-dioxane and an aqueous solution containing 4 equivalents of sodium carbonate (V H2O :V dioxane =1:5), heated to 90 ℃ for 4 hours. The reaction was cooled to room temperature and extracted three times with DCM, the combined organic phases were dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporator followed by column chromatography (SiO 2 ) Separating, wherein the eluent is petroleum ether: ethyl acetate=150:1. Diaryl maleimide can be obtained.
Dissolving 1 diaryl maleimide in 20ml methanol, cooling to 0deg.C in ice bath, adding 1 equivalent sodium borohydride three times, stirring at room temperature for half an hour, adding diluted hydrochloric acid (2N) for quenching, extracting with ethyl acetate three times, mixing organic phases, drying with anhydrous sodium sulfate, and removing solvent column chromatography (SiO) by rotary evaporator 2 ) Separating, wherein the eluent is petroleum ether: ethyl acetate=10:1.
Synthesis of Compound 13
Similar to the preparation of compound 12, the difference is that: the boric acid used was 3, 5-dimethoxyphenylboric acid.
Structural characterization of the Compounds of example 2
The nuclear magnetic resonance hydrogen spectrum test is carried out on the compounds 1 to 13 respectively, and the test result shows that the obtained compounds have the structural formula shown in the formula I.
In the case of compounds 2 and 12 as an example,
example compound 2 nuclear magnetic resonance hydrogen spectrum, 1 H NMR(400MHz，CD 3 CN) delta 7.39-7.42 (m, 2H), 7.31-7.35 (m, 2H), 6.96-7.00 (m, 2H), 6.89-6.93 (m, 2H), 6.45-6.47 (d, j=8.8 hz, 1H), 5.40-5.42 (d, j=8.8 hz, 1H), 3.83 (s, 3H), 3.82 (s, 3H).
Nuclear magnetic resonance hydrogen spectrum of example compound 12: 1 H NMR(400MHz,CD 3 CN) delta 7.38-7.26 (m, 4H), 6.95-6.86 (m, 4H), 5.68 (d, j=9.6 hz, 1H), 4.08 (d, j=9.6 hz, 1H), 3.82 (s, 3H), 3.81 (s, 3H), 3.00 (s, 3H).
Nuclear magnetic resonance hydrogen spectrum of example compound 2 a: 1 H NMR(400MHz,CD 3 CN)δ7.39,7.37,7.31,7.29,6.96,6.94,6.88,6.86,6.14,6.12,3.82,3.80,2.78,2.76,2.74,2.52,2.51,2.49,2.46,1.42,1.40,1.38,1.36,1.32,1.30,1.27,0.88,0.86,0.85 the specific spectrogram is shown in figure 1 (c).
Nuclear magnetic resonance hydrogen spectrum of example compound 2 c: 1 H NMR(400MHz,CD 3 CN): δ8.89 (d, j=8.8 hz, 1H), 8.18-8.12 (m, 3H), 7.43 (d, j=8.8 hz, 2H), 6.86 (s, 1H), 5.71 (s, 1H), 4.09 (s, 3H), 4.06 (s, 3H). Specific spectra are shown in fig. 1 (d).
Nuclear magnetic resonance hydrogen spectrum of example compound 2 ca: 1 h NMR (400 MHz, CD3 CN) delta 8.96,8.94,8.39,8.37,8.10,8.10,8.09,8.09,7.41,7.41,7.39,7.37,7.37,6.49,6.47,4.07,4.05,2.91,2.89,2.88,2.87,2.85,2.84,2.82,2.81,2.78,2.76,2.75,2.73,2.72,1.52,1.50,1.48,1.47,1.41,1.39,1.37,1.35,0.92,0.90,0.88. The specific spectrum is shown in FIG. 1 (e).
Nuclear magnetic resonance hydrogen spectrum of example compound 12 c: 1H NMR (400 MHz, CD3 CN) delta 9.18,9.16,8.29,8.27,8.17,8.17,8.15,8.14,7.43,7.42,7.41,7.41,7.40,7.40,7.38,7.38,6.04,6.01,5.43,5.41,4.08,4.06,3.13. The specific spectrum is shown in FIG. 1 (f).
The diaryl vinyl lactone and the lactam compound can be obtained by the method, and the compounds are characterized by means of nuclear magnetic resonance, mass spectrum and the like.
Example 3
The fluorescence was measured by preparing 1mM tetrahydrofuran standard solutions of compound 1, compound 2, compound 8, compound 9, compound 10 and compound 11, respectively, and diluting the standard solutions with 10. Mu.M diluted solutions of n-hexane, toluene, tetrahydrofuran, chloroform, acetonitrile, methanol and water, respectively.
The luminous intensity and wavelength of the diarylethene compound can be greatly changed along with the difference of solvents, the fluorescence intensity in nonpolar solvents is larger, the wavelength is shorter, and the fluorescence intensity gradually weakens the wavelength red shift along with the increase of the polarity of the solvents. As an example of the compound 1,2,8,9,10,11, fluorescence spectra in different solvents are shown in fig. 2 (a), 2 (b), 2 (c), 2 (d), 2 (e), and 2 (f).
Example 4
Amine modulation
To a deuterated acetonitrile solution of the compound of 10mM, 1.2 equivalents of n-butylamine was added, respectively, until the starting material was completely converted into its amine product, after which a tetrahydrofuran standard solution of 1mM was prepared, and the standard solution was diluted with hexane, toluene, tetrahydrofuran, chloroform, acetonitrile, methanol, water to 10. Mu.M diluted solutions, respectively, and fluorescence was measured, respectively.
Taking compounds 2 and 9 as examples, the compounds 2 and 9 react with n-butylamine to obtain corresponding amine products 2a and 9a, which show obvious fluorescence reduction phenomenon, so that the amine (dynamic covalent chemistry (DCC)) can regulate and control the luminescence of diarylethene molecules, and the spectra of the compounds are shown in the accompanying figures 3 (a) and 3 (b).
Example 5
Alkali regulation: to a 10. Mu.M acetonitrile solution of the test compound, various equivalent amounts of DBU (0 to 10 equivalent amounts) were added to measure fluorescence spectra thereof, respectively.
Acid regulation: to a 10. Mu.M acetonitrile solution of the test compound, methanesulfonic acid having different equivalent weights was added to measure fluorescence spectra thereof, respectively.
Taking compounds 2 and 9 as examples, these two compounds were titrated with base (DBU) in acetonitrile solution, and the fluorescence changes are shown in fig. 4 (a) and 4 (b).
Taking 2 and 9 as examples, the reaction products 2a and 9a of 2 and 9 and N-butylamine are protonated under acidic conditions, which is detrimental to the ring opening process that reduces fluorescence and thus has a significant fluorescence response to acid, as shown by the gradual increase in fluorescence with the addition of acid, the spectra being shown in fig. 5 (a) and 5 (b).
Example 6
Redox regulation of fluorescence:
oxidation regulation: 10 equivalents of MnO are added to a 10mM solution of the compound in acetonitrile 2 Filtering to remove MnO 2 A1 mM acetonitrile solution was prepared and compared to the fluorescence of the unoxidized compound.
Reduction regulation: to a 10mM methanolic solution of the compound was added 0.5 equivalent of sodium borohydride in methanol, which was then formulated into a 1mM solution of acetonitrile, which was compared to the fluorescence of the unoxidized compound.
In the case of compound 2, compound 12, mnO 2 Is an oxidant, naBH 4 The switching of different oxidation states and luminescence states of the molecules can be realized for the reducing agent. Diaryl vinyl lactones in reduced form andthe amide is blue fluorescence with shorter wavelength, and the diaryl vinyl lactone and amide in oxidation state are yellow fluorescence with longer wavelength. The fluorescence is shown in fig. 6.
Example 7
Light regulation:
the photocyclized compound was obtained by exposing a 10mM solution of the compound in deuterated acetonitrile to a 313nm UV lamp for 2 hours and following the reaction using nuclear magnetism.
The photocyclized compound was prepared as a 1mM tetrahydrofuran standard solution, and the standard solution was diluted with n-hexane, toluene, tetrahydrofuran, chloroform, acetonitrile, methanol, and water to 10. Mu.M diluted solution, and fluorescence was measured.
Taking compound 2,4,12,13 as an example, the series of compounds undergo photocyclization reaction under 313nm ultraviolet irradiation to obtain compounds 2c, 4c, 12c and 13c, the fluorescence of which is greatly enhanced, as shown in figures 7 (a), 7 (b), 7 (c) and 7 (d).
Example 8
Amine modulation of post-photocyclized diarylethenes
The specific regulation and control mode is as follows: to a solution of 10mM of the photocyclized compound in deuterated acetonitrile, 1.2 equivalents of n-butylamine was added until the starting material was completely converted into its amine product, after which a 1mM standard solution of tetrahydrofuran was prepared, and the standard solution was diluted to 10. Mu.M with n-hexane, toluene, tetrahydrofuran, chloroform, acetonitrile, methanol and water, respectively, and fluorescence was measured, respectively.
Taking compound 2c as an example, the compound 2ca is obtained after amine regulation, and the fluorescence spectrum is shown in fig. 8 (a), and the graph shows that the fluorescence intensity of the compound 2ca in different solvents is obviously reduced compared with that of the compound 2 c.
Acid-base modulation of photocyclized diarylethenes
The specific regulation and control mode is as follows: the fluorescence of the diarylethylene lactone compound after photocyclization was measured by dissolving it in a buffer solution (PBS buffer) having a different pH (pH 2-12) to prepare a 10. Mu.M solution.
Taking compounds 2c and 4c as an example, the fluorescence spectra are shown in FIGS. 8 (b) and 8 (c), from which it can be seen that the fluorescence of both 2c and 4c gradually decreases with increasing pH and is completely quenched at pH 10.
Redox modulation of diarylethenes after photocyclization
The specific regulation and control mode is as follows: oxidation is controlled by adding MnO to the acetonitrile solution of the photo-cyclized diaryl ethylene compound 2 The method comprises the steps of carrying out a first treatment on the surface of the The reduction is regulated by adding NaBH into acetonitrile solution of oxidized diaryl ethylene compound 4 。
By taking compounds 2c and 5c as examples, the fluorescence pair is shown in FIG. 8 (d), from which MnO can be seen 2 The fluorescence of oxidized 2c changes from dark blue to green, and conversely, the fluorescence changes from green to dark blue after reduction and regulation. Similar changes occur for 5c as well.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (25)
1. A preparation method of a cyclic chain isomerism stilbene fluorescent molecule I, which is characterized by comprising the following steps:
s100, obtaining diaryl maleimide;
s200, reacting a solution containing the diaryl maleimide in the presence of a reducing agent to obtain the ring chain isomerism stilbene fluorescent molecule I;
Wherein the diaryl maleimide is selected from any one of compounds with structural formulas shown in a formula II;
II type
In formula II, ar is selected from C 8 ~C 12 Aryl group,C 6 ~C 10 Substituted aryl I, C 4 ~C 9 Any one of heteroaryl I;
R 1 selected from C 1 ~C 8 Alkyl, C 6 ~C 12 Aryl, C 6 ~C 10 Substituted aryl II, C 4 ~C 9 Any one of heteroaryl II;
the C is 4 ~C 9 Heteroaryl I, C 4 ~C 9 The heteroatoms in heteroaryl ii are independently selected from at least one of S, N;
the C is 6 ~C 10 Substituted aryl I, C 6 ~C 10 The substituent in the substituted aryl II is independently selected from any one of halogen, alkoxy, halogenated alkyl, tertiary amino, nitro, hydroxyl and a group shown in a formula a;
a, a
In the formula a, n 1 The value range of (2) is not less than n 1 ≤6；
The alkoxy is selected from any one of groups with a structural formula shown in a formula b;
b
In formula b, R 2 Selected from C 1 ~C 5 Any one of alkyl groups;
the haloalkyl is C 1 ~C 5 A group formed by substitution of at least one H atom in the alkyl group with halogen;
the tertiary amine group is selected from any one of groups with a structural formula shown in a formula d;
d, d
In formula d, R 4 、R 5 Independently selected from C 1 ~C 5 Any one of alkyl groups.
2. The method of claim 1, wherein Ar is selected from the group consisting of、、/>、/>、/>、、/>、/>、/>Any one of them;
R 1 selected from the group consisting of
Any one of them.
3. The method of claim 1, wherein the reducing agent comprises sodium borohydride.
4. The preparation method according to claim 1, wherein in step S200, the reaction is stopped by quenching, the quenching comprising quenching with a quencher comprising an inorganic acid compound.
5. The method according to claim 1, wherein the reaction condition is a reaction temperature of 0 to 10 ℃.
6. The method of claim 4, further comprising a post-treatment step after quenching;
the post-treatment step comprises the following steps:
extracting the quenched solution to obtain an extract;
and then removing the solvent in the extract liquid, and performing chromatography to obtain the ring chain isomerism stilbene fluorescent molecule I.
7. Use of a fluorescent molecule of the cyclic-chain-isomerised stilbene i obtained by the process according to any of claims 1 to 6 as a fluorescent switch.
8. A method of modulating a fluorescent switch, the method comprising: regulating and controlling the loop chain fluorescent molecules in a preset regulation mode to isomerize the loop chain fluorescent molecules, so that conversion between fluorescence and fluorescence quenching or weakening is realized;
Wherein the preset regulation mode comprises any one of amine regulation, acid-base regulation, redox regulation and light regulation;
the cyclic chain fluorescent molecule is selected from any one of the cyclic chain isomerism stilbene fluorescent molecules I obtained by the preparation method according to any one of claims 1 to 6.
9. The method of claim 8, wherein when the predetermined modulation scheme is amine modulation, the method comprises:
adding alkylamine into the solution containing the ring chain isomerism stilbene fluorescent molecule I to react with the alkylamine, so as to realize conversion between fluorescence luminescence and fluorescence quenching;
the alkylamine has any one of substances shown in a structural formula a:
a, a
Wherein R is 6 Is C 1~ C 5 An alkyl group.
10. The method according to claim 8, wherein when the preset regulation mode is acid-base regulation, the method comprises:
adding an acid regulator or an alkali regulator into a solution containing the ring chain isomerism stilbene fluorescent molecule I to react II, thereby realizing the conversion between fluorescence and fluorescence quenching;
wherein the alkali regulator comprises any one of 1, 8-diazabicyclo undec-7-ene and sodium hydroxide;
The acid regulator comprises any one of methanesulfonic acid, trifluoroacetic acid and hydrochloric acid.
11. The method of claim 8, wherein when the predetermined modulation scheme is redox modulation, the method comprises:
adding an oxidizing reagent or a reducing reagent into a solution containing the ring chain isomerism stilbene fluorescent molecule I to react III, thereby realizing conversion between fluorescence luminescence and fluorescence quenching;
wherein the oxidizing agent comprises MnO 2 、H 2 O 2 Any one of them;
the reducing agent comprises NaBH 4 。
12. The method of claim 8, wherein when the preset modulation scheme is light modulation, the method comprises:
and (3) reacting IV to a solution containing the ring chain isomerism stilbene fluorescent molecule I under ultraviolet irradiation, so as to realize conversion between fluorescence and fluorescence quenching.
13. The method of claim 12, wherein the ultraviolet light has a wavelength of 300-350 nm.
14. The method according to any one of claims 9 to 12, wherein the solvent in the solution containing the cyclochain isomerised stilbene fluorescent molecule i comprises a deuterating agent;
the deuterated reagent comprises any one of deuterated acetonitrile, deuterated chloroform and deuterated dichloromethane.
15. The method of claim 14, wherein the solvent in the solution containing the cyclochain isomerised stilbene fluorescent molecule i further comprises reagent a;
the reagent A is selected from any one of normal hexane, toluene, tetrahydrofuran, chloroform, acetonitrile, methanol and water.
16. The fluorescent molecule II is characterized in that the fluorescent molecule II is selected from any one of compounds with a structural formula shown in a formula III;
III
In formula III, A' is selected from C 8 ~C 12 Arylene group, C 6 ~C 10 Substituted arylene I, C 4 ~C 9 Any one of heteroarylene I;
x is selected from；
R 1 Selected from C 1 ~C 8 Alkyl, C 6 ~C 12 Aryl, C 6 ~C 10 Substituted aryl II, C 4 ~C 9 Any one of heteroaryl II;
the C is 4 ~C 9 Heteroarylenes I, C 4 ~C 9 The heteroatoms in heteroaryl ii are independently selected from at least one of S, N;
the C is 6 ~C 10 Substituted aryl I, C 6 ~C 10 The substituent in the substituted aryl II is independently selected from any one of halogen, alkoxy, halogenated alkyl, tertiary amino, nitro, hydroxyl and a group shown in a formula a;
a, a
In the formula a, n 1 The value range of (2) is not less than n 1 ≤6；
The alkoxy is selected from any one of groups with a structural formula shown in a formula b;
b
In formula b, R 2 Selected from C 1 ~C 5 Any one of alkyl groups;
the haloalkyl is C 1 ~C 5 A group formed by substitution of at least one H atom in the alkyl group with halogen;
the tertiary amine group is selected from any one of groups with a structural formula shown in a formula d;
d, d
In formula d, R 4 、R 5 Independently selected from C 1 ~C 5 Any one of alkyl groups.
17. The method for preparing the cyclic-chain-isomerism stilbene fluorescent molecule II as claimed in claim 16, wherein the method comprises the following steps:
reacting iv under ultraviolet irradiation to a solution containing the cyclic-chain-isomerised stilbene fluorescent molecule i obtained by the preparation method according to any one of claims 1 to 6, thereby obtaining said cyclic-chain-isomerised stilbene fluorescent molecule ii.
18. The method for preparing the ultraviolet light according to claim 17, wherein the wavelength of the ultraviolet light is 300-350 nm.
19. A method of modulating a fluorescent switch, the method comprising: regulating and controlling the ring chain isomerism stilbene fluorescent molecule II in a preset regulation and control mode to isomerize the ring chain isomerism stilbene fluorescent molecule II, so that conversion between fluorescence luminescence and fluorescence weakening or quenching is realized;
the preset regulation mode comprises any one of amine regulation, acid-base regulation and redox regulation;
The cyclic-chain-isomerism stilbene fluorescent molecule II is selected from one of the cyclic-chain-isomerism stilbene fluorescent molecule II in claim 16 or the cyclic-chain-isomerism stilbene fluorescent molecule II prepared by the preparation method in claim 17 or 18.
20. The fluorescent molecule III is characterized in that the fluorescent molecule III is selected from any one of compounds with a structural formula shown in a formula IV;
IV
In formula IV, ar is selected from C 8 ~C 12 Aryl, C 6 ~C 10 Substituted aryl I, C 4 ~C 9 Any one of heteroaryl I;
x is selected from；
R 1 Selected from C 1 ~C 8 Alkyl, C 6 ~C 12 Aryl, C 6 ~C 10 Substituted aryl II, C 4 ~C 9 Heteroaryl groupII, any one of the following is adopted;
the C is 4 ~C 9 Heteroaryl I, C 4 ~C 9 The heteroatoms in heteroaryl ii are independently selected from at least one of S, N;
R 6 selected from C 1~ C 5 Any one of alkyl groups;
the C is 6 ~C 10 Substituted aryl I, C 6 ~C 10 The substituent in the substituted aryl II is independently selected from any one of halogen, alkoxy, halogenated alkyl, tertiary amino, nitro, hydroxyl and a group shown in a formula a;
a, a
In the formula a, n 1 The value range of (2) is not less than n 1 ≤6；
The alkoxy is selected from any one of groups with a structural formula shown in a formula b;
b
In formula b, R 2 Selected from C 1 ~C 5 Any one of alkyl groups;
the haloalkyl is C 1 ~C 5 A group formed by substitution of at least one H atom in the alkyl group with halogen;
the tertiary amine group is selected from any one of groups with a structural formula shown in a formula d;
d, d
In formula d, R 4 、R 5 Independently selected from C 1 ~C 5 Any one of alkyl groups.
21. The method for preparing the cyclic-chain-isomerism stilbene fluorescent molecule III as claimed in claim 20, characterized in that the method comprises the following steps:
adding alkylamine into the solution containing the ring-chain isomerism stilbene fluorescent molecule I, and reacting V to obtain the ring-chain isomerism stilbene fluorescent molecule III;
the cyclic-chain-isomerism-stilbene fluorescent molecule I is selected from any one of the cyclic-chain-isomerism-stilbene fluorescent molecules I obtained by the preparation method according to any one of claims 1 to 6.
22. The process according to claim 21, wherein the conditions of reaction v are: stirring at 15-30 ℃.
23. A method of modulating a fluorescent switch, the method comprising: regulating and controlling the ring chain isomerism stilbene fluorescent molecule III in an acid-base regulation mode to isomerize the ring chain isomerism stilbene fluorescent molecule III, thereby realizing the conversion between fluorescence luminescence and fluorescence quenching;
The cyclic-chain-isomerism stilbene fluorescent molecule III is at least one selected from the cyclic-chain-isomerism stilbene fluorescent molecule III in claim 20 or the cyclic-chain-isomerism stilbene fluorescent molecule III prepared by the preparation method in claim 21 or 22.
24. The ring chain isomerism stilbene fluorescent molecule IV is characterized in that the ring chain isomerism stilbene fluorescent molecule IV is selected from any one of compounds with a structural formula shown in a formula V;
v (V)
In formula V, A', X are the same as in formula III and R6 is the same as in formula IV.
25. The method for preparing the cyclic-chain-isomerism stilbene fluorescent molecule IV, which is characterized in that the cyclic-chain isomerism stilbene fluorescent molecule IV can be obtained by carrying out amine regulation and control on the cyclic-chain isomerism stilbene fluorescent molecule II.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110184903.XA CN114907249B (en) | 2021-02-10 | 2021-02-10 | Cyclic chain isomerism stilbene fluorescent molecule, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110184903.XA CN114907249B (en) | 2021-02-10 | 2021-02-10 | Cyclic chain isomerism stilbene fluorescent molecule, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114907249A CN114907249A (en) | 2022-08-16 |
| CN114907249B true CN114907249B (en) | 2023-07-21 |
Family
ID=82761034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110184903.XA Active CN114907249B (en) | 2021-02-10 | 2021-02-10 | Cyclic chain isomerism stilbene fluorescent molecule, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114907249B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497610A (en) * | 2009-03-06 | 2009-08-05 | 华东理工大学 | Dithiazole ethylene compound containing 2,1,3-diazosulfide unit |
| CN104098555A (en) * | 2014-07-15 | 2014-10-15 | 江西科技师范大学 | Method for synthesizing ultrashort-wavelength photochromic diarylethene compound by using imidazole-thiophene aromatic heterocycle and application of compound |
| CN107118757A (en) * | 2017-04-24 | 2017-09-01 | 上海电力学院 | A kind of diarylethene organic photochromic material based on furans and its preparation method and application |
| CN112300142A (en) * | 2020-11-13 | 2021-02-02 | 华中科技大学 | Dithienylethylene fluorescent molecular switch regulated and controlled by visible light, and preparation and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107033144B (en) * | 2017-04-25 | 2019-08-30 | 华中科技大学 | Dithienyl ethylene-terylene acid imide near-infrared fluorescent molecular switch and preparation method thereof |
| CN107652279B (en) * | 2017-10-31 | 2020-05-19 | 华中科技大学 | Diaryl ethylene fluorescent molecular switch, and preparation method and application thereof |
-
2021
- 2021-02-10 CN CN202110184903.XA patent/CN114907249B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497610A (en) * | 2009-03-06 | 2009-08-05 | 华东理工大学 | Dithiazole ethylene compound containing 2,1,3-diazosulfide unit |
| CN104098555A (en) * | 2014-07-15 | 2014-10-15 | 江西科技师范大学 | Method for synthesizing ultrashort-wavelength photochromic diarylethene compound by using imidazole-thiophene aromatic heterocycle and application of compound |
| CN107118757A (en) * | 2017-04-24 | 2017-09-01 | 上海电力学院 | A kind of diarylethene organic photochromic material based on furans and its preparation method and application |
| CN112300142A (en) * | 2020-11-13 | 2021-02-02 | 华中科技大学 | Dithienylethylene fluorescent molecular switch regulated and controlled by visible light, and preparation and application thereof |
Non-Patent Citations (6)
| Title |
|---|
| "Silver-catalyzed ring-opening [3+2] annulation of cyclopropenones with amides";Takanori Matsuda等;《NewJ.Chem.》;第42卷;第19178-19182页 * |
| 1265594-42-0.《STN REGISTRY》.2011,全文. * |
| 238734-38-8.《STN REGISTRY》.1999,全文. * |
| 863916-86-3.《STN REGISTRY》.2005,全文. * |
| 938069-76-2.《STN REGISTRY》.2007,全文. * |
| 新型烯桥二芳基乙烯光致变色体系;朱世琴;李文龙;朱为宏;;化学进展(第07期);第975-992页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114907249A (en) | 2022-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Patrick et al. | Synthesis of some polymerisable fluorescent dyes | |
| CN109762000A (en) | Based on the spirooxazine H-like ion fluorescent probe compounds and its synthetic method of 1,8- naphthalimide unit and application | |
| CN110407682A (en) | A kind of polypropylene luminescent material of europium complex, its ligand and europium complex doping | |
| CN107759504B (en) | Dual-phase organic fluorescent material with strong fluorescence in solid and liquid states and preparation method thereof | |
| JP5895297B2 (en) | Phosphor and use thereof | |
| CN114907249B (en) | Cyclic chain isomerism stilbene fluorescent molecule, preparation method and application | |
| CN111574578B (en) | Circular polarization luminescent material with intelligent response multicolor conversion and preparation method and application thereof | |
| Swamy et al. | Non-template synthesis of ‘N4’di-and tetra-amide macrocylic ligands with variable ring sizes | |
| Duan et al. | Slight substituent modification in coumarin molecular structures for strong solid emission and application in light-emitting devices | |
| CN114874145B (en) | Water-soluble trityl free base material, preparation method and application thereof | |
| CN114773875B (en) | Azaindole-squaraine dye, and synthetic method and application thereof | |
| JP5130521B2 (en) | Heteropolycyclic phenazine compounds | |
| CN110590794B (en) | Novel dicarboxy spiropyran derivative and preparation method thereof | |
| CN114957313A (en) | Siloxane-bridged tetraphenylethylene derivatives, process for their preparation and their use | |
| CN105175310B (en) | Asymmetric aza diisoindole methylene compound and its synthesis and use of boron fluoride compound | |
| CN110357880B (en) | Folded body-based chiral fluorescent compound with circular polarization luminescence property and preparation method and application thereof | |
| CN106749076A (en) | O-hydroxy-phenyl azole derivative as organic blue light material application | |
| WO2005087835A1 (en) | Molecular-wire type fluorescent chiral sensor | |
| CN115504938B (en) | Compound with photoinduced solid fluorescence change and preparation method thereof | |
| CN117624117A (en) | Dithiophene ethylene 1, 3-dione compound and preparation method and application thereof | |
| CN115368220B (en) | Double-ring molecule with stimulus response fluorescence property, and synthetic method and application thereof | |
| CN110054635A (en) | The imide derivatives and preparation method of a kind of asymmetric sulphur cyclisation | |
| CN109761930B (en) | Fluorescent switch and preparation method and application thereof | |
| CN105367595B (en) | A kind of electroluminescent hole mobile material and preparation method thereof | |
| CN117756706A (en) | Fluorescent molecule, host-guest complex based on fluorescent molecule, and preparation and application thereof |
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 |