CN112457336A - Optical trigger molecule based on BODIPY and application - Google Patents

Abstract

A light trigger molecule based on BODIPY has a structure shown as formula PPG, wherein LK is a connecting functional group or a chemical bond connecting the upper part structure of the light trigger molecule LK and the lower part structure of LK; r₁、R₂And R₃Are respectively independentIs selected from hydrogen, halogen, cyano, alkyl, alkenyl, alkynyl, alkoxy, alkylamino, alkylcyano, aryl, aralkyl, thiophene, cycloalkyl or a combination thereof, or two adjacent substituents form a ring. The BODIPY-based light panel machine molecule is simple to synthesize, and the excitation wavelength and the emission wavelength of the light panel machine molecule can be adjusted by adjusting the substituent on the BODIPY mother nucleus. And the photolysis speed is high, the photolysis efficiency is high, and the method can be applied to the field needing rapid light activation.

Description

Optical trigger molecule based on BODIPY and application

Technical Field

The invention relates to a BODIPY-based optical trigger molecule and application thereof. Specifically, the invention relates to a BODIPY mother nucleus-based optical trigger molecule and application thereof in the field of photochemistry.

Background

The light triggers (PPGs) refer to a class of molecules with light response functions, and are mainly embodied in that light activation, light shearing and light release are realized to realize light regulation and control on a target system. The light activation is a mode of connecting a light trigger at an active site through a chemical bond, so that the function of the active small molecules or the biomacromolecules is shielded, and the activation of the functional molecules is realized through illumination when needed. PPGs have important applications in a plurality of fields such as biology, biomedicine, volatile substance release, polymer chemistry, fluorescence activation and the like.

In recent years, various optical trigger systems have been developed around the improvement of optical trigger performance, such as arylketones, o-nitrobenzyls, o-nitroanilides, arylbenzenes, coumarins, but BODIPY (borondipyrrole) is currently few, and there are problems of slow photolysis speed, low photolysis efficiency, and low increase multiple of fluorescence intensity before and after photo activation, so that the development of optical trigger molecules based on a BODIPY mother nucleus is still important.

Disclosure of Invention

The invention provides a BODIPY-based optical trigger molecule, which has high photolysis speed and high photolysis efficiency, and the photochemical property of the optical trigger molecule can be adjusted by adjusting a substituent on a BODIPY mother nucleus.

The present invention will be described in further detail below.

In a first aspect, the present invention provides an optical trigger molecule having a structural formula as follows:

wherein LK is a linking functional group or a chemical bond linking an upper portion structure of the optical trigger molecule LK and a lower portion structure of LK;

the connecting functional group is selected from any one of the following:

R₁、R₂and R₃Each independently selected from hydrogen, halogen, cyano, alkyl, alkenyl, alkynyl, alkoxy, alkylamino, alkylcyano, aryl, aralkyl, thiophene, cycloalkyl or a combination thereof, or two adjacent substituents form a ring; r₄And R₅Each independently selected from hydrogen, alkyl groups having 1 to 50 carbon atoms, alkoxy groups having 1 to 50 carbon atoms, and alkylamino groups having 1 to 50 carbon atoms.

According to one embodiment of the invention, for example, R₁、R₂And R₃Each independently selected from alkyl, alkoxy, alkylamino, alkylcyano, aryl or a combination thereof having 1 to 50, preferably 1 to 20, more preferably 1 to 16 carbon atoms, or two adjacent substituents form a ring;

wherein said aryl is unsubstituted or substituted by one or more groups L;

l is selected from alkoxy, hydroxyl, carboxyl, amino, ester group, nitro, sulfonic group, halogen or amide group;

preferably, R₄And R₅Each independently selected from hydrogen,An alkyl group having 1 to 18 carbon atoms;

preferably, the adjacent two substituents form a ring meaning R₁And R₂Form a ring, e.g. R₁And R₂Form a five-membered ring or a six-membered ring therebetween, and further preferably, R₁And R₂Form benzene ring;

preferably, the adjacent two substituents form a ring meaning R₂And R₃Form a ring, e.g. R₂And R₃Form a five-membered ring or a six-membered ring therebetween, and further preferably, R₂And R₃Form benzene ring in between.

According to one embodiment of the invention, for example, R₁And R₃The radicals are identical and are each selected from linear or branched alkyl radicals of 1 to 8 carbon atoms or phenyl radicals;

R₂selected from hydrogen, halogen, cyano, straight or branched alkyl of 1 to 6 carbon atoms, straight or branched substituted alkenyl of 2 to 8 carbon atoms or straight or branched substituted alkynyl of 2 to 8 carbon atoms;

R₄and R₅Each independently an alkyl group of 1 to 10 carbon atoms; more preferably, R₄And R₅Each independently an alkyl group of 1 to 6 carbon atoms; more preferably, R₄And R₅Is methyl.

According to one embodiment of the invention, for example, R₁、R₂And R₃Are not identical;

preferably, R₁、R₂And R₃Are different from each other;

preferably, R₁、R₂And R₃Are independently selected from hydrogen, halogen, cyano, phenyl, straight or branched alkyl of 1 to 8 carbon atoms, straight or branched substituted alkenyl of 2 to 8 carbon atoms, or straight or branched substituted alkynyl of 2 to 8 carbon atoms.

According to one embodiment of the invention, for example, R₁、R₂Or R₃Selected from the group consisting of terminal Y₁、Y₂、Y₃Alkyl, alkenyl or alkynyl of (a);

Y₁、Y₂、Y₃each independently selected from aryl, halogen, cyano, thiophene, thiazole, furan, pyridine or pyrrole.

According to one embodiment of the invention, for example, the optical trigger molecule is any one of the following compounds:

according to one embodiment of the present invention, for example, the photo-activation time of the photo-trigger molecule is 0.1 to 15s, preferably 0.1 to 10s, and more preferably 1 to 5 s.

According to one embodiment of the present invention, for example, the excitation wavelength of the optical trigger molecule is 300 to 800nm, and the emission wavelength is 400 to 1000 nm. The excitation wavelength and emission wavelength can be adjusted by adjusting the substituents on the BODIPY parent nucleus. For example, it is necessary to increase the excitation wavelength, and a strongly conjugated group may be added to the 1-and 7-positions of the BODIPY nucleus.

The embodiment of the present invention further provides a method for synthesizing the above optical trigger molecule, where the method for synthesizing includes:

s1, will contain substituent R₁，R₂，R₃Dissolving pyrrole in organic solvent, adding R containing substituent₄Adding a catalyst into benzaldehyde, reacting for a period of time, adding 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, and carrying out oxidation reaction for a period of time to obtain an intermediate MA;

s2, will contain substituent R₅Adding the benzoin and mercaptoethanol into an organic solvent, adding a catalyst, heating for reaction for a period of time, and performing post-treatment to obtain an intermediate MB;

s3, preparing a light trigger molecule by the intermediate MA and the intermediate MB through condensation reaction, coupling reaction, substitution reaction or Click reaction;

according to an embodiment of the present invention, in the above synthesis method, for example, the condensation reaction in the step S3 includes:

adding the intermediate MA and the intermediate MB into an organic solvent, adding a condensing agent, reacting for 12-24 hours to obtain a target solution, and carrying out post-treatment to obtain a photoinitiation molecule PPG, wherein the molar ratio of the intermediate MA to the intermediate MB to the condensing agent is 1:1: 1;

the coupling reaction in step S3 (the coupling reaction includes Suzuki coupling, Heck coupling, Sonogoshira coupling) step includes:

adding the intermediate MA and the intermediate MB into an organic solvent, adding a coupling reaction catalyst and alkali, wherein the molar ratio of the intermediate MA to the intermediate MB to the catalyst to the alkali is 1:1:0.01: 3-1: 1:0.1:8, preferably 1:1:0.05:5, reacting for 8-24 hours to obtain a target solution, and performing post-treatment to obtain a photo-trigger molecule PPG;

preferably, the substitution reaction in step S3 includes:

adding the intermediate MA and the intermediate MB into an organic solvent, adding alkali, reacting for 12-24 hours to obtain a target solution, and performing post-treatment to obtain a photo-trigger molecule PPG, wherein the molar ratio of the intermediate MA to the intermediate MB to the alkali is 1:1: 3-1: 1:10, preferably 1:1: 5;

preferably, the Click reaction in step S3 includes:

adding the intermediate MA and the intermediate MB into an organic solvent, adding a Click reaction catalyst, reacting for 12-24 hours to obtain a target solution, and carrying out post-treatment to obtain the photo-trigger molecule, wherein the molar ratio of the intermediate MA to the intermediate MB to the Click reaction catalyst is 1:1: 0.01-1: 1:0.09, preferably 1:1: 0.05.

According to an embodiment of the present invention, in the above synthesis method, for example, the intermediate MA is selected from any one of the following compounds:

the intermediate MB is selected from any one of the following compounds:

the embodiment of the invention provides a nano luminescent probe, which comprises the above optical trigger molecule and a carrier microsphere, wherein the optical trigger molecule is coated in the carrier microsphere;

the carrier microsphere is at least one selected from hydrogel microspheres, styrene polymer microspheres, microspheres formed by protein, silicon nano microspheres and polymethyl methacrylate microspheres;

preferably, the carrier microspheres are styrene polymer microspheres;

more preferably, the carrier microsphere is a styrene polymer microsphere with amino, carboxyl, amido and/or aldehyde groups on the surface.

The embodiment of the invention provides a water-soluble nano luminescent probe, which comprises the light trigger molecule and a water-phase-transfer wrapping material, wherein the water-phase-transfer wrapping material is any one or more of bovine serum albumin, amphiphilic polyethylene glycol or lecithin.

An embodiment of the present invention provides a trademark anti-counterfeiting composition, comprising: the optical trigger molecules, gum and hardened gum as previously described;

the light trigger molecule the this glue with harden and glue and can form the membrane to be applied to the trade mark and prevent falsification.

According to one embodiment of the present invention, for example, the mass percentage of the molecules of the optical trigger in the trademark anti-counterfeiting composition is 0.01 to 0.1%, preferably 0.06 to 0.1%;

the mass ratio of the natural rubber to the hardening rubber is 5: 1-1: 2, preferably 3: 1-1: 2, and more preferably 1: 1.

Drawings

FIG. 1 shows the nuclear magnetic spectrum of a photo-trigger molecule PPG-1 in example 1 of the present invention;

FIG. 2 shows the nuclear magnetic spectrum of the photo-trigger molecule PPG-2 in example 2 of the present invention;

FIG. 3 shows the nuclear magnetic spectrum of the photo-trigger molecule PPG-3 in example 3 of the present invention;

FIG. 4 shows photographs taken of a photo trigger molecule solution of example 17 of the present invention, both unexcited and after excitation; in the figure, 1a is shot when the PPG-1 solution is not excited, and 1b is shot after the PPG-1 solution is excited; 2a is shot when the PPG-2 solution is not excited, and 2b is shot after the PPG-2 solution is excited; 3a is shot when the PPG-3 solution is not excited, and 3b is shot after the PPG-3 solution is excited;

FIG. 5 is a graph showing a fluorescence spectrum of a photo trigger molecule PPG-1 in example 17 of the present invention;

FIG. 6 is a graph showing a fluorescence spectrum of a photo trigger molecule PPG-2 in example 17 of the present invention;

FIG. 7 is a graph showing a fluorescence spectrum of a photo trigger molecule PPG-3 in example 17 of the present invention;

FIG. 8 is a graph showing the fluorescence intensity decay of the photo trigger molecules PPG-1, PPG-2 and PPG-3 in example 17 of the present invention;

FIG. 9 is a graph showing a fluorescence spectrum in comparative example 1 of the present invention; in the figure, a is a fluorescence spectrum diagram of 0s, 1s, 2s, 3s, 4s, 5s, 6s and 7s respectively irradiated by exciting light, and b is a change diagram of fluorescence intensity at a maximum emission peak of 548nm along with irradiation time;

FIG. 10 is a graph showing the comparison between the percentage of unreleased BODIPY1-Cb molecules and the percentage of unreleased PPG-17 molecules in comparative example 1 of the present invention with the increase in the irradiation time of excitation light;

FIG. 11 shows a nuclear magnetic spectrum of a PPG-SE-1 molecule in example 19 of the present invention;

FIG. 12 shows the nuclear magnetic spectrum of PPG-SE-2 molecule in example 20 of the present invention;

FIG. 13 shows a nuclear magnetic spectrum of a PPG-SE-3 molecule in example 21 of the present invention;

FIG. 14 is a graph showing the relationship between the Cb release rate and the irradiation time of excitation light in comparative example 2 of the present invention;

FIG. 15 is a graph showing the relationship between the fluorescence intensity of the BODIPY-BN molecule in comparative example 3 of the present invention and the light irradiation time;

FIG. 16 is a schematic diagram showing the preparation of a water-soluble nano-luminescent probe in example 22 of the present invention;

fig. 17 is an in vivo optical imaging chart of a mouse according to embodiment 22 of the present invention; the figure shows the light field, the luminous field and the superposed pictures of PPG-1, PPG-2 and PPG-3 nanometer probes injected into a mouse;

FIG. 18 is a diagram showing an application of anti-counterfeit in embodiment 23 of the present invention; in the figure, a is an image before 532nm LED irradiation, and b is an image after 532nm LED irradiation for 5 seconds;

FIG. 19 is a schematic diagram showing afterglow luminescence of an optical trigger film according to embodiment 24 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Synthesis of Phototrigger molecule PPG-1

1-1) synthesis of intermediate MA-1-1.

P-bromobenzaldehyde (300mg, 1.22mmol) and 2, 4-bisMethylpyrrole (255mg, 2.46mmol) was dissolved in dry CH₂Cl₂(100mL), and 5. mu.L of trifluoroacetic acid was added thereto, followed by reaction at room temperature overnight. To the solution was added 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ) (290mg, 1.26mmol) slowly and stirred for two hours, triethylamine (1.5mL) was added dropwise and stirred for 30 minutes, then boron trifluoride ether (1.5mL) was added dropwise slowly and stirred for 6 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

¹H NMR(400MHz,CDCl₃):δ7.68(d,J＝12.0Hz,2H),7.21(d,J＝8.0Hz,2H),6.01(s,2H),2.57(s,6H),1.44(s,6H)；HRMS for[M+H]⁺Calculated 403.0787, found 403.0783.

1-2) Synthesis of intermediate MB-2-1.

Benzoin containing borate ester (381mg,1mmol) was dissolved in 15mL toluene, trimethylchlorosilane (0.5mL) and mercaptoethanol (0.5mL) were added to the solution, and refluxed for 24 hours under argon. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

¹H NMR(400MHz,CD₂Cl₂):δ7.55(d,J＝8.0Hz,2H),7.22(d,J＝8.0Hz,2H),7.10(d,J＝8.0Hz,2H),6.61(d,J＝8.0Hz,2H),4.52(t,J＝4.0Hz,2H),3.27(t,J＝4.0Hz,2H),2.95(s,6H),1.34(s,12H)；HRMS for[M+H]⁺:424.2120。

1-3) Synthesis of Phototrigger molecule PPG-1

Intermediate MA-1-1(346mg, 0.86mmol), intermediate MB-2-1(364mg, 0.86mmol), Pd (PPh)₃)₄(50mg, 5% mol) and sodium carbonate (432mg, 4.08mmol) were put into a 50mL three-necked flask, 10mL of ethanol/water (4:1) was added, and the reaction was refluxed under nitrogen for 2 hours. The reaction was quenched by adding 20mL of water to the reaction solution, the reaction solution was extracted with dichloromethane, and the organic layer was washed with anhydrous Na₂SO₄Drying, rotary evaporating to remove solvent, separating with silica gel column chromatographyThe product was obtained (eluent: dichloromethane/petroleum ether ═ 2:1) and the nuclear magnetic spectrum was as shown in fig. 1.

¹H NMR(400MHz,CD₂Cl₂):δ7.77(d,J＝8.0Hz,2H),7.53(d,J＝12.0Hz,2H),7.38(d,J＝8.0Hz,2H),7.33(d,J＝8.0Hz,2H),7.16(d,J＝8.0Hz,2H),6.63(s,2H),6.06(s,2H),4.55(t,J＝4.0Hz,2H),3.30(t,J＝4.0Hz,2H),2.96(s,6H),2.55(s,6H),1.48(s,6H)；HRMS for[M+H]⁺:620.2728。

Example 2

Synthesis of Phototrigger molecule PPG-2

2-1) Synthesis of intermediate MA-1-2

Para-bromobenzaldehyde (300mg, 1.22mmol) and 2, 4-dimethyl-3-ethylpyrrole (302mg, 2.46mmol) were dissolved in dry CH₂Cl₂(100mL), and 5. mu.L of trifluoroacetic acid was added thereto, followed by reaction at room temperature overnight. DDQ (290mg, 1.26mmol) was slowly added to the solution and stirred for two hours, triethylamine (1.5mL) was added dropwise and stirred for 30 minutes, and then boron trifluoride ether (1.5mL) was added dropwise and stirred for 6 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

¹H NMR(400MHz,CDCl₃):δ7.67(d,J＝8.0Hz,2H),7.21(d,J＝8.0Hz,2H),2.55(s,6H),2.34(q,J＝8.0Hz,4H),1.34(s,6H),1.01(t,J＝8.0Hz,6H)；HRMS for[M+H]⁺:459.1411。

2-2) Synthesis of Phototrigger molecule PPG-2

Intermediate MA-1-2(394mg, 0.86mmol), intermediate MB-2-1(364mg, 0.86mmol), Pd (PPh)₃)₄(50mg, 5% mol) and sodium carbonate (432mg, 4.08mmol) were put into a 50mL three-necked flask, 10mL of ethanol/water (4:1) was added, and the reaction was refluxed under nitrogen for 2 hours. The reaction mixture was quenched by adding 20mL of water, extracted with dichloromethane, and taken outAnhydrous Na for organic layer₂SO₄Drying, rotary evaporation to remove solvent, and silica gel column chromatography to obtain product (eluent: dichloromethane/petroleum ether 2:1), with nuclear magnetic spectrum as shown in FIG. 2.

¹H NMR(400MHz,CD₂Cl₂):δ7.77(d,J＝8.0Hz,2H),7.54(d,J＝8.0Hz,2H),7.38(d,J＝8.0Hz,2H),7.34(d,J＝12.0Hz,2H),7.16(d,J＝8.0Hz,2H),6.64(s,2H),4.56(t,J＝4.0Hz,2H),3.30(t,J＝4.0Hz,2H),2.96(s,6H),2.53(s,6H),2.39(q,J＝8.0Hz,4H),1.39(s,6H),1.04(t,J＝8.0Hz,6H)；HRMS for[M+H]⁺:676.3355。

Example 3

Synthesis of Phototrigger molecule PPG-3

3-1) Synthesis of intermediate MA-1-3

Para-bromobenzaldehyde (300mg, 1.22mmol) and 2-thiophenepyrrole (367mg, 2.46mmol) were dissolved in dry CH₂Cl₂(100mL), and 5. mu.L of trifluoroacetic acid was added thereto, followed by reaction at room temperature overnight. DDQ (290mg, 1.26mmol) was slowly added to the solution and stirred for two hours, triethylamine (1.5mL) was added dropwise and stirred for 30 minutes, and boron trifluoride ether (1.5mL) was added dropwise and stirred for another 6 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

¹H NMR(400MHz,CDCl₃):δ8.24(d,J＝4.0Hz,2H),7.69(d,J＝8.0Hz,2H),7.54(d,J＝8.0Hz,2H),7.44(d,J＝8.0Hz,2H),7.24(d,J＝4.0Hz,2H),6.85(d,J＝4.0Hz,2H),6.79(d,J＝4.0Hz,2H)；HRMS for[M+H]⁺:510.9925。

3-2) Synthesis of Phototrigger molecule PPG-3

Intermediate MA-1-3(439mg, 0.86mmol), intermediate MB-2-1(364mg, 0.86mmol), Pd (PPh)₃)₄(50mg, 5% mol) and sodium carbonate (432mg, 4.08mmol) were put in a 50mL three-necked flask,10mL of ethanol/water (4:1) was added and the reaction was heated under reflux for 2 hours under nitrogen. The reaction was quenched by adding 20mL of water to the reaction solution, the reaction solution was extracted with dichloromethane, and the organic layer was washed with anhydrous Na₂SO₄Drying, rotary evaporation to remove solvent, and silica gel column chromatography to obtain product (eluent: dichloromethane/petroleum ether 2:1), with nuclear magnetic spectrum as shown in FIG. 3.

¹H NMR(400MHz,CD₂Cl₂):δ8.21(d,J＝4.0Hz,2H),7.78(d,J＝8.0Hz,2H),7.66(d,J＝8.0Hz,2H),7.60(d,J＝4.0Hz,2H),7.54(d,J＝8.0Hz,2H),7.35(d,J＝8.0Hz,2H),7.27(d,J＝8.0Hz,2H),7.20(s,2H),6.95(d,J＝4.0Hz,2H),6.91(d,J＝4.0Hz,2H),6.69(s,2H),4.56(s,2H),3.31(s,2H),2.99(s,6H)；HRMS for[M+H]⁺:728.1859。

Example 4

Synthesis of Phototrigger molecule PPG-4

4-1) Synthesis of intermediate MA-1-4

P-bromobenzaldehyde (300mg, 1.22mmol) and 2, 4-dimethyl-3-phenylethynylpyrrole (480mg, 2.46mmol) were dissolved in dry CH₂Cl₂(100mL), and 5. mu.L of trifluoroacetic acid was added thereto, followed by reaction at room temperature overnight. DDQ (290mg, 1.26mmol) was slowly added to the solution and stirred for two hours, triethylamine (1.5mL) was added dropwise and stirred for 30 minutes, and boron trifluoride ether (1.5mL) was added dropwise and stirred for another 6 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

4-2) Synthesis of Phototrigger molecule PPG-4

Mixing MA-1-4(518mg, 0.86mmol), MB-2-1(364mg, 0.86mmol), Pd (PPh)₃)₄(50mg, 5% mol) and sodium carbonate (432mg, 4.08mmol) were put into a 50mL three-necked flask, 10mL of ethanol/water (4:1) was added, and the reaction was refluxed under nitrogen for 2 hours. 20mL of water was added to the reaction mixtureQuenching the reaction, extracting the reaction solution with dichloromethane, and extracting the organic layer with anhydrous Na₂SO₄Drying, rotary evaporation to remove solvent, silica gel column chromatography to obtain the product (eluent: dichloromethane/petroleum ether 2: 1).

Example 5

Synthesis of Phototrigger molecule PPG-5

5-1) Synthesis of intermediate MA-7-1

P-iodobenzaldehyde (283mg, 1.22mmol) and 2, 4-dimethyl-3-chloropyrrole (320mg, 2.46mmol) were dissolved in dry CH₂Cl₂(100mL), and 5. mu.L of trifluoroacetic acid was added thereto, followed by reaction at room temperature overnight. DDQ (290mg, 1.26mmol) was slowly added to the solution and stirred for two hours, triethylamine (1.5mL) was added dropwise and stirred for 30 minutes, and then boron trifluoride ether (1.5mL) was slowly added dropwise and stirred for 6 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

5-2) Synthesis of intermediate MB-1-1

Benzoin containing alkynyl groups (279mg,1mmol) was dissolved in 15mL toluene, trimethylchlorosilane (0.5mL) and mercaptoethanol (0.5mL) were added to the solution, and the mixture was refluxed under argon for 24 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

5-3) Synthesis of Phototrigger molecule PPG-5

Intermediate MA-7-1(446mg, 0.86mmol), intermediate MB-1-1(276mg, 0.86mmol) and Pd (PPh)₃)₄(50mg, 5% mol) and sodium carbonate (432mg, 4.08mmol) were put into a 50mL three-necked flask, 10mL of ethanol/water (4:1) was added, and the reaction was refluxed under nitrogen for 2 hours. The reaction solution was quenched by adding 20mL of water, extracted with dichloromethane,anhydrous Na for organic layer₂SO₄Drying, rotary evaporation to remove solvent, silica gel column chromatography to obtain the product (eluent: dichloromethane/petroleum ether 2: 1).

Example 6

Synthesis of Phototrigger molecule PPG-6

6-1) Synthesis of intermediate MA-7-2

P-iodobenzaldehyde (283mg, 1.22mmol) and 2, 4-dimethyl-3-bromopyrrole (426mg, 2.46mmol) were dissolved in dry CH₂Cl₂(100mL), and 5. mu.L of trifluoroacetic acid was added thereto, followed by reaction at room temperature overnight. DDQ (290mg, 1.26mmol) was slowly added to the solution and stirred for two hours, triethylamine (1.5mL) was added dropwise and stirred for 30 minutes, and then boron trifluoride ether (1.5mL) was slowly added dropwise and stirred for 6 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

6-2) Synthesis of Phototrigger molecule PPG-6

Intermediate MA-7-2(521mg, 0.86mmol), intermediate MB-1-1(276mg, 0.86mmol) and Pd (PPh)₃)₄(50mg, 5% mol) and sodium carbonate (432mg, 4.08mmol) were put into a 50mL three-necked flask, 10mL of ethanol/water (4:1) was added, and the reaction was refluxed under nitrogen for 2 hours. The reaction was quenched by adding 20mL of water to the reaction solution, the reaction solution was extracted with dichloromethane, and the organic layer was washed with anhydrous Na₂SO₄Drying, rotary evaporation to remove solvent, silica gel column chromatography to obtain the product (eluent: dichloromethane/petroleum ether 2: 1).

Example 7

Synthesis of Phototrigger molecule PPG-7

7-1) Synthesis of intermediate MA-7-3

P-iodobenzaldehyde (283mg, 1.22mmol) and 2, 4-dimethyl-3-iodopyrrole (544mg, 2.46mmol) were dissolved in dry CH₂Cl₂(100mL), and 5. mu.L of trifluoroacetic acid was added thereto, followed by reaction at room temperature overnight. DDQ (290mg, 1.26mmol) was slowly added to the solution and stirred for two hours, triethylamine (1.5mL) was added dropwise and stirred for 30 minutes, and then boron trifluoride ether (1.5mL) was slowly added dropwise and stirred for 6 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

7-2) Synthesis of Phototrigger molecule PPG-7

Intermediate MA-7-3(604mg, 0.86mmol), intermediate MB-1-1(276mg, 0.86mmol), Pd (PPh)₃)₄(50mg, 5% mol) and sodium carbonate (432mg, 4.08mmol) were put into a 50mL three-necked flask, 10mL of ethanol/water (4:1) was added, and the reaction was refluxed under nitrogen for 2 hours. The reaction was quenched by adding 20mL of water to the reaction solution, the reaction solution was extracted with dichloromethane, and the organic layer was washed with anhydrous Na₂SO₄Drying, rotary evaporation to remove solvent, silica gel column chromatography to obtain the product (eluent: dichloromethane/petroleum ether 2: 1).

Example 8

Synthesis of Phototrigger molecule PPG-8

8-1) Synthesis of intermediate MA-7-4

P-iodobenzaldehyde (283mg, 1.22mmol) and 2, 4-dimethyl-3-cyanopyrrole (295mg, 2.46mmol) were dissolved in dry CH₂Cl₂(100mL), and 5. mu.L of trifluoroacetic acid was added thereto, followed by reaction at room temperature overnight. DDQ (290mg, 1.26mmol) was slowly added to the solution and stirred for two hours, triethylamine (1.5mL) was added dropwise and stirred for 30 minutes, and then boron trifluoride ether (1.5mL) was slowly added dropwise and stirred for 6 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

8-2) Synthesis of Phototrigger molecule PPG-8

Intermediate MA-7-4(446mg, 0.86mmol), intermediate MB-1-1(276mg, 0.86mmol) and Pd (PPh)₃)₄(50mg, 5% mol) and sodium carbonate (432mg, 4.08mmol) were put into a 50mL three-necked flask, 10mL of ethanol/water (4:1) was added, and the reaction was refluxed under nitrogen for 2 hours. The reaction was quenched by adding 20mL of water to the reaction solution, the reaction solution was extracted with dichloromethane, and the organic layer was washed with anhydrous Na₂SO₄Drying, rotary evaporation to remove solvent, silica gel column chromatography to obtain the product (eluent: dichloromethane/petroleum ether 2: 1).

Example 9

Synthesis of Phototrigger molecule PPG-9

9-1) Synthesis of intermediate MA-2-1

P-hydroxybenzaldehyde (149mg, 1.22mmol) and 2-phenylpyrrole (295mg, 2.46mmol) were dissolved in dry CH₂Cl₂(100mL), and 5. mu.L of trifluoroacetic acid was added thereto, followed by reaction at room temperature overnight. DDQ (290mg, 1.26mmol) was slowly added to the solution and stirred for two hours, triethylamine (1.5mL) was added dropwise and stirred for 30 minutes, and then boron trifluoride ether (1.5mL) was slowly added dropwise and stirred for 6 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

9-2) Synthesis of intermediate MB-5-1

Benzoinum containing a carboxyl group (299mg,1mmol) was dissolved in 15mL of toluene, to the solution was added chlorotrimethylsilane (0.5mL) and mercaptoethanol (0.5mL), and the mixture was refluxed under argon for 24 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent with a rotary evaporatorAnd then, carrying out silica gel column chromatography separation to obtain a pure product.

9-3) Synthesis of Phototrigger molecule PPG-9

Intermediate MA-2-1(375mg, 0.86mmol), intermediate MB-5-1(293mg, 0.86mmol), dicyclohexylcarbodiimide (177mg, 0.86mmol) and 4-dimethylaminopyridine (525mg, 4.3mmol) were added to 15mL of dichloromethane and stirred at room temperature for 24 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

Example 10

Synthesis of Phototrigger molecule PPG-10

10-1) Synthesis of intermediate MA-2-2

P-hydroxybenzaldehyde (149mg, 1.22mmol) and 2, 4-Diphenylpyrrole (539mg, 2.46mmol) were dissolved in dry CH₂Cl₂(100mL), and 5. mu.L of trifluoroacetic acid was added thereto, followed by reaction at room temperature overnight. DDQ (290mg, 1.26mmol) was slowly added to the solution and stirred for two hours, triethylamine (1.5mL) was added dropwise and stirred for 30 minutes, and then boron trifluoride ether (1.5mL) was slowly added dropwise and stirred for 6 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

10-2) Synthesis of Phototrigger molecule PPG-10

Intermediate MA-2-2(375mg, 0.86mmol), intermediate MB-5-1(293mg, 0.86mmol), dicyclohexylcarbodiimide (177mg, 0.86mmol) and 4-dimethylaminopyridine (525mg, 4.3mmol) were added to 15mL of dichloromethane and stirred at room temperature for 24 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

Example 11

Synthesis of Phototrigger molecule PPG-11

11-1) Synthesis of intermediate MA-3-1

P-aminobenzaldehyde (149mg, 1.22mmol) and 2-benzopyrrole (539mg, 2.46mmol) were dissolved in dry CH₂Cl₂(100mL), and 5. mu.L of trifluoroacetic acid was added thereto, followed by reaction at room temperature overnight. DDQ (290mg, 1.26mmol) was slowly added to the solution and stirred for two hours, triethylamine (1.5mL) was added dropwise and stirred for 30 minutes, and then boron trifluoride ether (1.5mL) was slowly added dropwise and stirred for 6 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

11-2) Synthesis of Phototrigger molecule PPG-11

Intermediate MA-3-1(329mg, 0.86mmol), intermediate MB-5-1(293mg, 0.86mmol), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (165mg, 0.86mmol), N-hydroxysuccinimide (494mg, 4.3mmol) were added to 15mL of dichloromethane and stirred at room temperature for 24 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

Example 12

Synthesis of Phototrigger molecule PPG-12

12-1) Synthesis of intermediate MA-3-2

P-aminobenzaldehyde (149mg, 1.22mmol) and 2-phenylbenzopyrrole (475mg, 2.46mmol) were dissolved in dry CH₂Cl₂(100mL), and 5. mu.L of trifluoroacetic acid was added thereto, followed by reaction at room temperature overnight. To the solution, DDQ (2) was slowly added90mg, 1.26mmol) was stirred for two hours, triethylamine (1.5mL) was added dropwise and stirred for 30 minutes, and then boron trifluoride ethyl ether (1.5mL) was added dropwise slowly and stirred for 6 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

12-2) Synthesis of Phototrigger molecule PPG-12

Intermediate MA-3-2(329mg, 0.86mmol), intermediate MB-5-1(293mg, 0.86mmol), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (165mg, 0.86mmol), and N-hydroxysuccinimide (494mg, 4.3mmol) were added to 15mL of dichloromethane and stirred at room temperature for 24 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

Example 13

Synthesis of Phototrigger molecule PPG-13

13-1) Synthesis of intermediate MA-9-1

Bromobenzaldehyde (259mg, 1.22mmol) and 2-methyl-4-styrylpyrrole (450mg, 2.46mmol) were dissolved in dry CH₂Cl₂(100mL), and 5. mu.L of trifluoroacetic acid was added thereto, followed by reaction at room temperature overnight. DDQ (290mg, 1.26mmol) was slowly added to the solution and stirred for two hours, triethylamine (1.5mL) was added dropwise and stirred for 30 minutes, and then boron trifluoride ether (1.5mL) was slowly added dropwise and stirred for 6 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

13-2) Synthesis of intermediate MB-6-1

Benzoinum containing hydroxyl groups (299mg,1mmol) was dissolved in 15mL of toluene, and trimethylchlorosilane (0.5mL) and mercaptoethanol were added to the solution(0.5mL) was refluxed for 24 hours under argon. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

13-3) Synthesis of Phototrigger molecule PPG-13

Intermediate MA-9-1(329mg, 0.86mmol), intermediate MB-6-1(293mg, 0.86mmol) and potassium carbonate (593mg, 4.3mmol) were added to 15mL of dichloromethane and stirred at room temperature for 24 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

Example 14

Synthesis of Phototrigger molecule PPG-14

14-1) Synthesis of intermediate MA-9-2

Bromobenzaldehyde (259mg, 1.22mmol) and 2-methyl-4-styrylpyrrole (524mg, 2.46mmol) were dissolved in dry CH₂Cl₂(100mL), and 5. mu.L of trifluoroacetic acid was added thereto, followed by reaction at room temperature overnight. DDQ (290mg, 1.26mmol) was slowly added to the solution and stirred for two hours, triethylamine (1.5mL) was added dropwise and stirred for 30 minutes, and then boron trifluoride ether (1.5mL) was slowly added dropwise and stirred for 6 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

14-2) Synthesis of intermediate MB-7-1

The amino-containing benzoin (270mg,1mmol) was dissolved in 15mL of toluene, to which was added chlorotrimethylsilane (0.5mL) and mercaptoethanol (0.5mL), and refluxed under argon for 24 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent with a rotary evaporator, and dryingSeparating with silica gel column chromatography to obtain pure product.

14-3) Synthesis of Phototrigger molecule PPG-14

Intermediate MA-9-2MA-9-2(573mg, 0.86mmol), intermediate MB-7-1(268mg, 0.86mmol), and potassium carbonate (593mg, 4.3mmol) were added to 15mL of dichloromethane, and stirred at room temperature for 24 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

Example 15

Synthesis of Phototrigger molecule PPG-15

15-1) Synthesis of intermediate MA-5-1

4-alkynylbenzaldehyde (159mg, 1.22mmol) and 2-methyl-4-styrylpyrrole (556mg, 2.46mmol) were dissolved in dry CH₂Cl₂(100mL), and 5. mu.L of trifluoroacetic acid was added thereto, followed by reaction at room temperature overnight. DDQ (290mg, 1.26mmol) was slowly added to the solution and stirred for two hours, triethylamine (1.5mL) was added dropwise and stirred for 30 minutes, and then boron trifluoride ether (1.5mL) was slowly added dropwise and stirred for 6 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

15-2) Synthesis of intermediate MB-9-1

After benzoin (296mg,1mmol) containing an azide group was dissolved in 15mL of toluene, trimethylchlorosilane (0.5mL) and mercaptoethanol (0.5mL) were added to the solution, and the mixture was refluxed for 24 hours under an argon atmosphere. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

15-3) Synthesis of Phototrigger molecule PPG-15

Reacting intermediate MA-5-1(525mg, 0.86mmol),Intermediate MB-9-1(291mg, 0.86mmol) and copper sulfate (593mg, 4.3mmol) were added to 15mL of ethanol/water (4:1) and stirred at room temperature for 24 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

Example 16

Synthesis of Phototrigger molecule PPG-16

16-1) Synthesis of intermediate MA-5-2

4-alkynylbenzaldehyde (159mg, 1.22mmol) and pyrrole (492mg, 2.46mmol) were dissolved in dry CH₂Cl₂(100mL), and 5. mu.L of trifluoroacetic acid was added thereto, followed by reaction at room temperature overnight. DDQ (290mg, 1.26mmol) was slowly added to the solution and stirred for two hours, triethylamine (1.5mL) was added dropwise and stirred for 30 minutes, and then boron trifluoride ether (1.5mL) was slowly added dropwise and stirred for 6 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

16-2) Synthesis of Phototrigger molecule PPG-16

Intermediate MA-5-2(525mg, 0.86mmol), intermediate MB-9-1(291mg, 0.86mmol), and copper sulfate (593mg, 4.3mmol) were added to 15mL of ethanol/water (4:1) and stirred at room temperature for 24 hours. The reaction mixture was quenched by adding 50mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.

It should be noted that the modification or replacement of the substituent on the structure of the photo trigger molecule of the present invention is the same as the strategy of the present invention, for example, the modification of the structure on the BODIPY mother nucleus or the replacement of the substituent on the benzene ring and N in the upper half structure of LK does not affect the properties of the photo trigger molecule of the present invention.

Example 17

17-1) two portions of the photo trigger molecule PPG-1 of example 1 in dichloromethane were prepared at a concentration of 20. mu.M and placed in bottles numbered 1a and 1b, respectively;

two portions of the photo trigger molecule PPG-2 solution of example 2 in dichloromethane were prepared at 20. mu.M and placed in bottles numbered 2a and 2b, respectively;

two portions of the photo trigger molecule PPG-3 solution of example 3 in dichloromethane were prepared at 20. mu.M and placed in bottles numbered 3a and 3b, respectively;

17-2) as shown in FIG. 4:

1a, 2a and 3a were not irradiated with excitation light as a control before photoactivation;

irradiating the 1b bottle with 480nm exciting light for 2s, and finding that the 1b bottle is bright and luminous, and the color of the light is green; as shown in fig. 5, the fluorescence intensity before and after photoactivation was increased by about 36 times (i.e., the fluorescence intensity of 1b after 5s photoactivation was increased by about 36 times as compared to 1a before photoactivation, the same below);

2b, irradiating the bottle 2s with excitation light of 500nm for 2s, and finding that the bottle 2b is bright and luminous, and the color of the light is green; as shown in fig. 6, the fluorescence intensity before and after light activation was increased by about 31-fold by the test;

irradiating the 3b bottle for 2s by using 610nm exciting light, and finding that the 3b bottle is bright and luminous, and the color of the light is red; as shown in fig. 7, the fluorescence intensity before and after photoactivation was increased by about 28-fold by the test.

The BODIPY is easy to modify, and the substitution structure on the BODIPY parent nucleus can be adjusted through chemical modification to change the luminescent properties of the BODIPY parent nucleus, such as excitation wavelength, emission wavelength, luminous intensity, photolysis speed, photolysis efficiency and the like.

In addition, the fluorescence intensity attenuation of the light trigger molecules PPG-1, PPG-2 and PPG-3 is tested, and as shown in FIG. 8, the fluorescence intensity is still about 10000 at 2 s.

Example 18

18-1) a dichloromethane solution of the photo trigger molecule PPG-5 of example 5 was prepared, the concentration was 20. mu.M, 480nm excitation light was used for irradiation, and the fluorescence intensity before and after activation was enhanced by about 27 times by the test;

18-2) a dichloromethane solution of the photo trigger molecule PPG-9 of example 9 was prepared at a concentration of 20. mu.M, irradiated with 620nm excitation light, and tested to increase the fluorescence intensity by about 25 times before and after activation;

18-3) A methylene chloride solution of the photo trigger molecule PPG-13 of example 13 was prepared at a concentration of 20. mu.M, and the fluorescence intensity before and after activation was measured to be increased by about 20 times by irradiation with 620nm excitation light.

Comparative example 1

1) Synthesis of light trigger molecule BODIPY1-Cb

Synthetic methods refer to reported literature

2) Synthesis of Phototrigger molecule PPG-17

Referring to the method of example 1, a synthetic photo trigger molecule PPG-17,

3) a dichloromethane/methanol solution (volume ratio is 1:9) of the photo trigger molecule PPG-17 in example 2 is prepared, the concentration is 100 μ M, 8 parts are divided, excitation light is respectively irradiated for 0s, 1s, 2s, 3s, 4s, 5s, 6s and 7s by a 532nm LED lamp, a fluorescence change trend graph of the photo trigger molecule PPG-17 along with the increase of illumination time is shown in FIG. 9(a), and the fluorescence intensity increases along with the increase of the excitation illumination time. FIG. 9(b) is a graph showing the change of fluorescence intensity of the photo-trigger molecule at 548nm, which shows that the photo-activation process is completed substantially at 5s, and the released photon generates fluorescence.

4) A dichloromethane/methanol solution of light trigger molecule BODIPY1-Cb (volume ratio of 1:9) with concentration of 100 μ M was prepared and divided into 8 portions, and irradiated with excitation light of 625nm LED lamp for 0s, 1s, 2s, 3s, 4s, 5s, 6s, and 7s, respectively, and the Cb release rate was measured by liquid chromatography in reference literature and converted into a graph of the percentage of unreleased BODIPY1-Cb versus time, and FIG. 9(b) was converted into a graph of the percentage of unreleased PPG-17 versus time, as shown in FIG. 10.

The photo trigger molecule PPG-17 has substantially completed the photo activation process at 5s, released photons to generate fluorescence, the unreleased PPG-17 molecule is 8.1%, while BODIPY1-Cb is still in the slow release process at 0-7s, and the unreleased BODIPY1-Cb at 5s is still 79.1%.

The contrast test proves that the photopanette molecular PPG designed and synthesized by the invention has the advantage of high photolysis speed, and the high photolysis speed indicates that the activation time is short, so that the photopanette molecular PPG can be applied to the field (turn on) requiring fluorescent rapid activation or the field of rapid detection (such as rapid detection of luminous flux).

Example 19

PPG-16(1.9mg, 0.1mmol) was dissolved in dichloromethane (400mL), and 0.001mmol of palladium phthalocyanine molecule (PdPc) was added to the solution, followed by stirring and irradiation with a 730nm laser until no afterglow occurred. The reaction mixture was quenched by adding 200mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent with a rotary evaporator, and separating by silica gel column chromatography to obtain pure PPG-1-SE (eluent: dichloromethane), wherein the yield is as follows: 91% of the total nuclear magnetic spectrum, as shown in FIG. 11.

¹H NMR(400MHz,CD₂Cl₂):δ8.19(d,J＝8.0Hz,2H),7.96(d,J＝8.0Hz,2H),7.87(d,J＝12.0Hz,2H),7.83(d,J＝8.0Hz,2H),7.47(d,J＝8.0Hz,2H),6.89(d,J＝12.0Hz,2H),6.08(s,2H),4.56(t,J＝8.0Hz,2H),3.51(t,J＝8.0Hz,2H),3.10(s,6H),2.56(s,6H),1.51(s,6H)；HRMS for[M]⁺:652.2612。

The structural formula of the palladium phthalocyanine molecule (PdPc) is shown in the specification

Example 20

PPG-2(61.9mg, 0.1mmol) was dissolved in dichloromethane (400mL), and 0.001mmol of PdPc was added to the solution, followed by stirring and irradiation with a 730nm laser until no afterglow occurred. The reaction mixture was quenched by adding 200mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent with a rotary evaporator, and separating by silica gel column chromatography to obtain pure product PPG-2-SE (eluent: dichloromethane), yield: 93%, the nuclear magnetic spectrum is shown in FIG. 12.

¹H NMR(400MHz,CD₂Cl₂):δ8.20(d,J＝8.0Hz,2H),7.93(d,J＝8.0Hz,2H),7.86(t,J＝8.0Hz,4H),7.46(d,J＝8.0Hz,2H),6.75(d,J＝8.0Hz,2H),4.56(t,J＝8.0Hz,2H),3.50(t,J＝8.0Hz,2H),3.09(s,6H),2.54(s,6H),2.40(q,J＝8.0Hz,4H),1.41(s,6H),1.05(t,J＝8.0Hz,6H)；HRMS for[M]⁺:708.3239。

Example 21

PPG-3(61.9mg, 0.1mmol) was dissolved in dichloromethane (400mL), and 0.001mmol of PdPc was added to the solution, followed by stirring and irradiation with a 730nm laser until no afterglow occurred. The reaction mixture was quenched by adding 200mL of water, and the organic layer was taken out and washed with anhydrous Na₂SO₄Drying, spin-drying the solvent with a rotary evaporator, and separating by silica gel column chromatography to obtain pure PPG-2-SE (eluent: dichloromethane), wherein the yield is as follows: 90%, NMR spectrum is shown in FIG. 13.

¹H NMR(400MHz,CD₂Cl₂):δ8.22(m,4H),7.96(d,J＝12.0Hz,2H),7.87(m,4H),7.73(d,J＝8.0Hz,2H),7.62(d,J＝8.0Hz,2H),7.28(d,J＝4.0Hz,2H),6.97(m,4H),6.86(d,J＝12.0Hz,2H),4.57(d,J＝8.0Hz,2H),3.52(s,J＝8.0Hz,2H),3.10(s,6H)；HRMS for[M]⁺:760.1771。

Comparative example 2

A methylene chloride/methanol solution of the light trigger molecule BODIPY1-Cb (volume ratio of 1:9) was prepared at a concentration of 100. mu.M in N₂The saturated solution was irradiated with 625nm light, and then 0.1ep PtTPBP BODIPY1-Cb was photolyzed, as shown in FIG. 14, in which the photolysis amount of BODIPY1-Cb was about 50%, that is, the photolysis amount of BODIPY1-Cb was about 50% of the useful product.

The PPG (PPG-1, PPG-2 and PPG-3) molecules are photolyzed to obtain PPG-SE (PPG-SE-1, PPG-SE-2 and PPG-SE-3) molecules and release photons to generate fluorescence, the yield of the PPG-SE molecules reaches over 90 percent, and no side reaction exists basically, so that the photolysis yield is high and can reach over 90 percent, and is remarkably higher than the reported photolysis yield of the BODIPY 1-Cb.

Comparative example 3

Synthesis of light trigger molecule BODIPY-BN, synthesis method refers to reported literature

1) A solution of the optical trigger molecule BODIPY-BN in methylene chloride was prepared at a concentration of 20. mu.M, and the fluorescence intensity 1 was varied as shown in FIG. 15 by instantaneous and continuous irradiation with excitation light for 45s, which was 1.6 times the initial intensity at 45s irradiation.

2) In example 17, the fluorescence intensity before and after excitation was increased by about 36 times by irradiating a solution of PPG-1 in methylene chloride at a concentration of 20. mu.M for 2 s;

the concentration of a dichloromethane solution of PPG-2 is 20 MuM, the fluorescence intensity before and after excitation is enhanced by about 31 times after 2s irradiation;

a solution of PPG-3 in dichloromethane at a concentration of 20. mu.M was irradiated for 2s, and the fluorescence intensity before and after excitation was increased by about 28 times.

The experiment proves that the fluorescence intensity of the photo-trigger molecule PPG is obviously enhanced after photo-activation.

Example 22 biological imaging

22-1) preparation of Water-soluble nanometer luminescent Probe

The method comprises the following steps:

22-1-1) the photo trigger molecule PPG-1 in example 1 was formulated into a stock solution with a mass concentration of 2 mM;

22-1-2) dissolving amphiphilic polyethylene glycol (F-127, molecular weight 12600g/mol) of the connecting material in an organic solvent to prepare a connecting material solution with mass concentration of 5 mg/mL;

22-1-3) adding the optical trigger molecule stock solution obtained in the step 1) into the connecting material solution obtained in the step 2) in a volume ratio of 1:200, and mixing the two solutions through ultrasonic oscillation to obtain a mixed solution;

22-1-4) adding the mixed solution into pure water, stirring the mixed solution and the pure water at the volume ratio of 1:10 for 5 minutes at room temperature, removing the organic solvent, filtering the mixture through a water phase filter with the pore diameter of 0.13 mu m to obtain a PPG-1 nano probe, and storing the PPG-1 nano probe at the temperature of 4 ℃ for later use.

Repeating the above steps to obtain PPG-2 nanometer probe and PPG-3 nanometer probe, and the preparation process is shown in FIG. 16.

22-2) results of light imaging in mice

Three nude mice are taken, anesthetized by a gas anesthesia system, the synthesized PPG-1 nanometer probe, PPG-2 nanometer probe and PPG-3 nanometer probe are respectively injected into subcutaneous parts of the mice, the injection concentration is 10 mu mol, (in addition, the injection concentration can be 10-100 mu mol), the parts are irradiated by a laser for 2 seconds, then the laser is closed, simultaneously, a CCD camera is used for collecting luminescence signals, and the signal-to-noise ratio S/N is equal to (signal 1-signal 3)/(signal 2-signal 3). The results are shown in fig. 17, where the signal-to-noise ratio S/N of the PPG-1 nanoprobe in the mouse in the optical imaging is 220, the signal-to-noise ratio S/N of the PPG-1 nanoprobe is 252, and the signal-to-noise ratio S/N of the PPG-1 nanoprobe is 160.

In addition, the light trigger molecules of the present invention can achieve specific functional applications. For example, when a light trigger molecule is used, BODIPY luminescence performance is in a suppressed state, and only light activation with a specific wavelength can emit a light signal, so that the light trigger molecule can be used for researching the movement and diffusion dynamics of materials, and the result has important significance for disclosing metabolism and transport paths in organisms. On the other hand, the material can be used for responding to light stimulation in organisms, and activated light signals indicate state changes in organisms, such as stress response and the like.

Example 23 application in anti-counterfeiting of trademarks

23-1-1) dissolving a photophotonic device molecule PPG-1 in dichloromethane to prepare 50 mu M PPG-1-M1 solution and 1mM PPG-1-M2 solution;

23-1-2) mixing the glue A (the glue) and the glue B (the hardened glue) according to a ratio of 5:1 to prepare an AB-1 glue solution, mixing the glue A and the glue B according to a ratio of 1:1 to prepare an AB-2 glue solution, and mixing the glue A and the glue B according to a ratio of 1:5 to prepare an AB-3 glue solution;

23-1-3) sucking 100 mu L of PPG-1-M1 solution, adding 100 mu L of AB-1 glue solution (the weight percentage of PPG-1 is 0.003 percent), preparing into a film, and observing weak luminescence by naked eyes under the irradiation of a 365nm ultraviolet lamp after the film is irradiated by a 532nm LED for 1 second;

with the experimental conditions of 23-1-3),

adding 100 mu L of PPG-1-M1 solution into 100 mu L of AB-2 glue solution;

adding 100 mu L of PPG-1-M1 solution into 100 mu L of AB-3 glue solution;

adding 100 mu L of PPG-1-M2 solution into 100 mu L of AB-1 glue solution (the weight percentage of PPG-1 is 0.06%);

adding 100 mu L of PPG-1-M2 solution into 100 mu L of AB-2 glue solution;

adding 100 mu L of PPG-1-M2 solution into 100 mu L of AB-3 glue solution;

the results of the experiment are shown in table 1:

TABLE 1 trademark anti-counterfeiting application

The mass fraction is 0.003 percent	Glue A and glue B	Results
			PPG-1-M1	5:1	Hardly visible to the naked eye
PPG-1-M1	1:1	Hardly visible to the naked eye
			PPG-1-M1	1:5	Hardly visible to the naked eye
The mass fraction is 0.06 percent	Glue A and glue B	Results
			PPG-1-M2	5:1	Visibly observed obvious luminescence
PPG-1-M2	1:1	Visibly observed obvious luminescence
			PPG-1-M2	1:5	The light observed by the naked eye is not significant

As can be seen from the Table I, when the mass fraction of the PPG-1 molecule in the system is 0.003%, almost no light is seen to the naked eye after photo-activation, and therefore, it is necessary to increase the content of the PPG-1. When the mass fraction of PPG-1 molecules in a system is 0.06%, obvious luminescence can be observed by naked eyes, then the proportion of the glue A and the glue B is regulated, when the ratio of the glue A to the glue B is 5:1, the strength of a formed film is insufficient and is not suitable for the application in the anti-counterfeiting field, when the ratio of the glue A to the glue B is 1:1, the film strength is appropriate and the brightness after light activation is obviously visible by naked eyes, when the ratio of the glue A to the glue B is 1:5, the film strength is stronger, but the brightness after light activation is reduced, so that when the mass fraction of the PPG-1 molecules in the system is 0.06%, and the ratio of the glue A to the glue B is 1:1, the anti-counterfeiting field is more suitable for anti-counterfeiting.

23-2-1) dissolving non-optical trigger molecule PMA in dichloromethane to prepare 1mM PMA solution; dissolving a light trigger molecule PPG-1 in dichloromethane to prepare a 1mM PPG-1-M2 solution;

23-2-2) mixing the glue A (the glue) and the glue B (the hardened glue) according to a ratio of 1:1 to prepare an AB glue solution;

23-2-3) sucking 100 μ L of PMA solution, adding to 100 μ L of AB glue solution, filling to the letter "F" in the "FDU" pattern shown in FIG. 18, sucking 100 μ L of PPG-1-M2 solution, adding to 100 μ L of AB glue solution, filling to the letter "DU" in the "FDU" pattern;

23-2-4) as shown in fig. 18 (picture taken by cell phone), only green fluorescence pattern of "F" was observed under 365nm uv lamp. After 1 second of irradiation with a 480nm LED, a green fluorescent pattern of the entire "FDU" was observed under 365nm UV light.

Example 24

24-1) dissolving a light trigger molecule PPG-19 in dichloromethane to prepare a 100 mu M PPG-19 solution;

24-2) mixing the glue A (the glue) and the glue B (the hardened glue) according to the ratio of 1:1 to prepare an AB glue solution;

24-3) adding the PPG-19 solution into the AB glue solution, heating at 60 ℃ for 2 hours, curing to generate a light trigger film, irradiating the film with a 532nm LED light source for 5 seconds, and then turning off an excitation light source, as shown in figure 19, wherein long afterglow luminescence of light trigger molecules can be seen.

The light panel machine molecule can also be applied to anti-counterfeiting of other forms, such as anti-counterfeiting coating, anti-counterfeiting printing and the like. Common fluorescent dye, such as PMA, has fluorescence under the irradiation of ultraviolet lamp, while the light machine molecule of the invention has the excellent characteristic of light activation, and light machine molecules with different structures need excitation light with different wavelengths for activation. For example, PPG-1 molecule does not emit light under 365nm illumination, and emits light after being activated by 480nm light, so that a novel anti-counterfeiting mode can be provided based on the properties of the light panel machine molecule.

The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to the above-described embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (15)

1. An optical trigger molecule, wherein the optical trigger molecule has the following structural formula:

wherein LK is a linking functional group or a chemical bond linking an upper portion structure of the optical trigger molecule LK and a lower portion structure of LK;

the connecting functional group is selected from any one of the following:

R₁、R₂and R₃Each independently selected from hydrogen, halogen, cyano, alkyl, alkenyl, alkynyl, alkoxy, alkylamino, alkylcyano, aryl, aralkyl, thiophene, cycloalkyl or a combination thereof, or two adjacent substituents form a ring;

R₄and R₅Each independently selected from hydrogen, alkyl groups having 1 to 50 carbon atoms, alkoxy groups having 1 to 50 carbon atoms, and alkylamino groups having 1 to 50 carbon atoms.

2. An optical trigger molecule according to claim 1, wherein R is₁、R₂And R₃Each independently selected from alkyl, alkoxy, alkylamino, alkylcyano, aryl or a combination thereof having 1 to 50, preferably 1 to 20, more preferably 1 to 16 carbon atoms, or two adjacent substituents form a ring;

wherein said aryl is unsubstituted or substituted by one or more groups L;

l is selected from alkoxy, hydroxyl, carboxyl, amino, ester group, nitro, sulfonic group, halogen or amide group;

R₄and R₅Each independently selected from hydrogen, alkyl groups having 1 to 18 carbon atoms;

preferably, the adjacent two substituents form a ring meaning R₁And R₂Form a ring, e.g. R₁And R₂Form a five-membered ring or a six-membered ring therebetween, and further preferably, R₁And R₂Form benzene ring;

preferably, the adjacent two substituents form a ring meaning R₂And R₃Form a ring, e.g. R₂And R₃Form a five-membered ring or a six-membered ring therebetween, and further preferably, R₂And R₃Form benzene ring in between.

3. An optical trigger molecule according to claim 1, characterized in thatCharacterized in that R is₁And R₃The radicals are identical and are each selected from linear or branched alkyl radicals of 1 to 8 carbon atoms or phenyl radicals;

R₂selected from hydrogen, halogen, cyano, straight or branched alkyl of 1 to 6 carbon atoms, straight or branched substituted alkenyl of 2 to 8 carbon atoms or straight or branched substituted alkynyl of 2 to 8 carbon atoms;

R₄and R₅Each independently selected from alkyl groups having 1 to 18 carbon atoms;

preferably, R₄And R₅Each independently selected from alkyl groups having 1 to 10 carbon atoms.

4. An optical trigger molecule according to claim 1, wherein R is₁、R₂And R₃Are not identical;

preferably, R₁、R₂And R₃Are different from each other;

preferably, R₁、R₂And R₃Are independently selected from hydrogen, halogen, cyano, phenyl, straight or branched alkyl of 1 to 8 carbon atoms, straight or branched substituted alkenyl of 2 to 8 carbon atoms, or straight or branched substituted alkynyl of 2 to 8 carbon atoms.

5. An optical trigger molecule according to claim 3 or 4, wherein R is₁、R₂Or R₃Selected from the group consisting of terminal Y₁、Y₂、Y₃Alkyl, alkenyl or alkynyl of (a);

Y₁、Y₂、Y₃each independently selected from aryl, halogen, cyano, thiophene, thiazole, furan, pyridine or pyrrole.

6. A light trigger molecule according to claim 1, wherein the light trigger molecule is any one of the following compounds:

7. a photo trigger molecule according to any one of claims 1 to 6, wherein the photo activation time of the photo trigger molecule is 0.1 to 15s, preferably 0.1 to 10s, more preferably 1 to 5 s.

8. An optical trigger molecule according to any one of claims 1 to 6, wherein the excitation wavelength of the optical trigger molecule is 300 to 800nm and the emission wavelength is 400 to 1000 nm.

9. A method of synthesizing a photo trigger molecule according to any one of claims 1 to 8, comprising:

s1, will contain substituent R₁，R₂，R₃Dissolving pyrrole in organic solvent, adding R containing substituent₄Adding a catalyst into benzaldehyde, reacting for a period of time, adding 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, and carrying out oxidation reaction for a period of time to obtain an intermediate MA;

s2, will contain substituent R₅Adding the benzoin and mercaptoethanol into an organic solvent, adding a catalyst, heating for reaction for a period of time, and performing post-treatment to obtain an intermediate MB;

s3, preparing a light trigger molecule by the intermediate MA and the intermediate MB through condensation reaction, coupling reaction, substitution reaction or Click reaction;

10. the method of synthesis according to claim 9,

the condensation reaction in the step S3 includes:

adding the intermediate MA and the intermediate MB into an organic solvent, adding a condensing agent, reacting for 12-24 hours to obtain a target solution, and carrying out post-treatment to obtain a photoinitiation molecule PPG, wherein the molar ratio of the intermediate MA to the intermediate MB to the condensing agent is 1:1: 1;

the coupling reaction in step S3 includes:

adding the intermediate MA and the intermediate MB into an organic solvent, adding a coupling reaction catalyst and alkali, wherein the molar ratio of the intermediate MA to the intermediate MB to the catalyst to the alkali is 1:1:0.01: 3-1: 1:0.1:8, preferably 1:1:0.05:5, reacting for 8-24 hours to obtain a target solution, and performing post-treatment to obtain a photo-trigger molecule PPG;

preferably, the substitution reaction in step S3 includes:

adding the intermediate MA and the intermediate MB into an organic solvent, adding alkali, reacting for 12-24 hours to obtain a target solution, and performing post-treatment to obtain a photo-trigger molecule PPG, wherein the molar ratio of the intermediate MA to the intermediate MB to the alkali is 1:1: 3-1: 1:10, preferably 1:1: 5;

preferably, the Click reaction in step S3 includes:

adding the intermediate MA and the intermediate MB into an organic solvent, adding a Click reaction catalyst, reacting for 12-24 hours to obtain a target solution, and carrying out post-treatment to obtain the photo-trigger molecule, wherein the molar ratio of the intermediate MA to the intermediate MB to the Click reaction catalyst is 1:1: 0.01-1: 1:0.09, preferably 1:1: 0.05.

11. A method of synthesising a photo trigger molecule as claimed in claim 9 or 10 wherein the intermediate MA is selected from any one of the following compounds:

the intermediate MB is selected from any one of the following compounds:

12. a nano luminescent probe, comprising the photo trigger molecule of any one of claims 1 to 10 and a carrier microsphere, wherein the photo trigger molecule is encapsulated in the carrier microsphere;

the carrier microsphere is at least one selected from hydrogel microspheres, styrene polymer microspheres, microspheres formed by protein, silicon nano microspheres and polymethyl methacrylate microspheres;

preferably, the carrier microspheres are styrene polymer microspheres;

more preferably, the carrier microsphere is a styrene polymer microsphere with amino, carboxyl, amido and/or aldehyde groups on the surface.

13. A water-soluble nano luminescent probe, comprising the optical trigger molecule of any one of claims 1 to 8 and a water-transfer phase coating material, wherein the water-transfer phase coating material is any one or more of bovine serum albumin, amphiphilic polyethylene glycol or lecithin.

14. A trademark anti-counterfeiting composition, characterized in that the trademark anti-counterfeiting composition comprises: the optical trigger molecule of any one of claims 1-8, gum and hardened gum;

the light trigger molecule the this glue with harden and glue and can form the membrane to be applied to the trade mark and prevent falsification.

15. A trademark anti-counterfeiting composition according to claim 14, wherein the mass percentage of molecules of the optical trigger in the trademark anti-counterfeiting composition is 0.01-0.1%, preferably 0.06-0.1%;

the mass ratio of the natural rubber to the hardening rubber is 5: 1-1: 2, preferably 3: 1-1: 2, and more preferably 1: 1.

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