CN114539208A - Trianiline-based optical trigger molecule and application thereof - Google Patents
Trianiline-based optical trigger molecule and application thereof Download PDFInfo
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- CN114539208A CN114539208A CN202210101546.0A CN202210101546A CN114539208A CN 114539208 A CN114539208 A CN 114539208A CN 202210101546 A CN202210101546 A CN 202210101546A CN 114539208 A CN114539208 A CN 114539208A
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- -1 amino, sulfydryl Chemical group 0.000 claims abstract description 19
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- 125000001424 substituent group Chemical group 0.000 claims abstract description 13
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
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- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- 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
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Abstract
A light trigger molecule based on triphenylamine has a structural formula shown as below, wherein R1，R2，R3The substituents are the same or different and are respectively and independently selected from hydrogen, substituted or unsubstituted alkyl, alkoxy, hydroxyl, nitro, cyano, ester group, carboxyl, amino, sulfydryl, halogen atom, aryl, aromatic heterocyclic group or the combination of the hydrogen, the substituted or unsubstituted alkyl, the alkoxy, the hydroxyl, the nitro, the cyano, the ester group, the carboxyl, the amino, the sulfydryl, the halogen atom, the aryl and the aromatic heterocyclic group; the invention designs and synthesizes a new type of optical trigger molecules, and the excitation wavelength and the emission wavelength of the optical trigger molecules are adjusted by adjusting a ligand; and the photolysis speed is high, the photolysis efficiency is high, and the method can be applied to the field needing rapid photo-activation.
Description
Technical Field
The invention relates to an optical trigger molecule and application thereof. Specifically, the invention relates to a triphenylamine-based optical trigger molecule and application thereof.
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-nitroanilines, aromatic benzyls, coumarins, and the like. However, the existing plate-light machine system has the problems of slow photolysis speed, low photolysis efficiency, low fluorescence intensity increase multiple after light activation compared with the fluorescence intensity increase multiple before activation and the like, so the research and development of improving the performance of the light trigger are still very important.
Disclosure of Invention
The invention provides a triphenylamine-based optical trigger molecule which has the advantages of high photolysis speed, high photolysis efficiency and the like.
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:
the structural formula of the optical trigger molecule is shown 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:
wherein, Ar can be any one of the following aromatic structures:
wherein R is1，R2，R3The substituents are the same or different and are respectively and independently selected from hydrogen, substituted or unsubstituted alkyl, alkoxy, hydroxyl, nitro, cyano, ester group, carboxyl, amino, sulfydryl, halogen atom, aryl, aromatic heterocyclic group or combination thereof.
Said R1，R2，R3Any one group of the substituent groups can be respectively positioned at the ortho-position, meta-position or para-position of the benzene ring;
the unsubstituted alkyl group has 1 to 20 carbon atoms. Preferably, the unsubstituted alkyl group is selected from one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, or n-octyl;
the substituted alkyl group has 1 to 20 carbon atoms, and preferably, the substituted alkyl group is selected from one of hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, aminomethyl, aminoethyl, aminopropyl and aminobutyl;
the substituted alkoxy group is a group represented by-OR, wherein the group represented by R is an unsubstituted alkyl group having 1 to 20 carbon atoms, preferably, the unsubstituted alkyl group is one selected from a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group OR an n-octyl group;
the substituted amino is represented by-NRxRyA group of the formula (I), wherein RxAnd RyThe group represented is hydrogen or a group having 1 to 20 carbon atoms, and preferably, the group having 1 to 20 carbon atoms is one selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and phenyl;
the substituted aryl is a group with 6 to 50 ring carbon atoms, and is preferably one of phenyl, naphthyl, o-tolyl, m-tolyl, p-tolyl and p-tert-butylphenyl;
the substituted aromatic heterocyclic group is a group with 4 to 50 ring carbon atoms, and is preferably one of furyl, thienyl, pyrrolyl, pyridyl, pyranyl, carbazolyl, indolyl and quinolyl;
according to one embodiment of the invention, the optical trigger molecule is selected from any one of the following structures:
according to one embodiment of the invention, the light activation time of the light trigger molecule is 1-10 min, preferably 5-30 s, more preferably 10-20 s, and is regulated and controlled by adjusting the structure of the light trigger molecule, and different activation times can be applied to different fields, such as anti-counterfeiting or research on the movement and diffusion dynamics of materials, and the result has important significance in revealing metabolism and transport pathways in organisms.
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 the emission wavelength can be adjusted by adjusting the substituent on the triphenylamine mother nucleus, for example, if the excitation wavelength needs to be lengthened, a strongly conjugated group can be added on the triphenylamine mother nucleus.
According to one embodiment of the present invention, a method for synthesizing a photo trigger molecule comprises:
s1 preparation of benzoin intermediate
Adding benzaldehyde containing a substituent group and triphenylamine aldehyde containing a substituent group into a reaction bottle, adding a catalyst, alkali and ethanol, and carrying out heating reflux reaction for more than 12 hours under the protection of nitrogen to obtain a solid substance, namely a benzoin intermediate;
s2, will contain substituent R1，R2，R3With addition of benzoin and ethylene glycolAdding a catalyst into an organic solvent, heating for reaction for a period of time, and performing post-treatment to obtain light trigger molecules;
an embodiment of the present invention provides a nano luminescent probe comprising the photo trigger molecule of any one of claims 1 to 13 and a carrier microsphere, the photo trigger molecule being 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.
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 an embodiment of the present invention, for example, the mass percentage of the photo trigger molecules 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 the photo-trigger molecule TPA-2 in example 2 of the present invention;
FIG. 2 is a single crystal X-ray diffraction pattern of the optical trigger molecule TPA-2 of example 2 of the present invention;
FIG. 3 shows the nuclear magnetic spectrum of the photo-trigger molecule TPA-3 in example 3 of the present invention;
FIG. 4 shows the nuclear magnetic spectrum of the photo-trigger molecule TPA-8 in example 4 of the present invention;
FIG. 5 is a single crystal X-ray diffraction pattern of the optical trigger molecule TPA-8 of example 4 of the present invention;
FIG. 6 shows the nuclear magnetic spectrum of the photo-trigger molecule TPA-9 in example 5 of the present invention;
FIG. 7 is a single crystal X-ray diffraction pattern of the optical trigger molecule TPA-9 of example 5 of the present invention;
FIG. 8 shows the nuclear magnetic spectrum of the photo-trigger molecule TPA-10 of example 6 of the present invention;
FIG. 9 is a single crystal X-ray diffraction pattern of the optical trigger molecule TPA-10 of example 6 of this invention;
FIG. 10 is a graph showing the change in fluorescence intensity before and after activation of the photo-trigger molecular solution in example 7 of the present invention (photographed by a mobile phone);
FIG. 11 is a graph showing the fluorescence intensity decay of the light trigger molecules TPA-2, TPA-8, TPA-9, TPA-10 of the present invention;
FIG. 12 shows the fluorescence intensity decay curves of the light trigger molecules TPA-2, TPA-8, TPA-9, TPA-10 of the present invention;
FIG. 13 shows the afterglow emission spectra of light trigger molecules TPA-2, TPA-8, TPA-9, TPA-10 of the present invention after activation;
FIG. 14 is a graph showing fluorescence spectra of the photo-trigger molecules TPA-2, TPA-8, TPA-9, TPA-10 before and after activation in example 8 of the present invention;
FIG. 15 shows the NMR spectra of TPE-8 molecules of example 9 of the present invention;
FIG. 16 shows the nuclear magnetic spectrum of TPE-9 in example 10 of this invention;
FIG. 17 is a schematic diagram showing afterglow luminescence of an optical trigger film according to embodiment 11 of the present invention;
FIG. 18 is a diagram showing an application of forgery prevention in example 12 of the present invention;
fig. 19 is a diagram showing an application of forgery prevention in embodiment 13 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 photo-trigger molecule TPA-1
1-1) synthesis of intermediate Benzoin-1.
Benzaldehyde (0.53g,5mmol), 4- (N, N-diphenylamino) benzaldehyde (2.73g,10mmol), triethylamine (505mg,5mmol) and 20mL of ethanol were added to a reaction flask and stirred at 60 ℃ for 24 hours. After completion of the reaction, the reaction mixture was quenched with 30mL of water and extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate and the organic solvent was evaporated to dryness. The crude product was purified by silica gel column chromatography to give intermediate Benzoin-1 as an orange solid.1H NMR(400MHz,CD2Cl2):δ7.63(m,2H),7.42(m,4H),7.31(m,8H),7.13(m,2H),6.94(m,2H),5.89(s,1H).
1-2) Synthesis of Phototrigger molecule TPA-1
The benzoin intermediate of the above formula (381mg,1mmol) was dissolved in 15mL of toluene, to which was added chlorotrimethylsilane (0.5mL) and ethylene glycol (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 by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product.1H NMR(400MHz,CD2Cl2):δ7.22(m,6H),7.11(m,8H),6.96(m,4H),4.32(s,4H).
Example 2
Synthesis of photo-trigger molecule TPA-2
2-1) synthesis of intermediate Benzoin-2.
4-fluorobenzaldehyde (0.62g,5mmol), 4- (N, N-diphenylamino) benzaldehyde (2.73g,10mmol), triethylamine (505mg,5mmol) and 20mL of ethanol were added to a reaction flask and stirred at 60 ℃ for 24 hours. After completion of the reaction, the reaction mixture was quenched with 30mL of water and extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate and the organic solvent was evaporated to dryness. The crude product was purified by silica gel column chromatography to give intermediate Benzoin-2 as an orange solid.1H NMR(400MHz,CD2Cl2):δ7.83(m,2H),7.40(m,4H),7.31(m,8H),7.10(m,2H),6.93(m,2H),5.88(s,1H).
2-2) Synthesis of Phototrigger molecule TPA-2
The benzoin intermediate of the above formula (381mg,1mmol) was dissolved in 15mL of toluene, to which was added chlorotrimethylsilane (0.5mL) and ethylene glycol (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 by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product. The nuclear magnetic spectrum is shown in FIG. 1.1H NMR(400MHz,CD2Cl2) δ 7.32(m,6H),7.13(m,8H),6.97(m,4H),4.34(s,4H). Single-crystal X-ray diffraction structure of light panel machine molecule TPA-2 is shown in FIG. 2.
Example 3
Synthesis of photo-trigger molecule TPA-3
3-1) synthesis of intermediate Benzoin-3.
4-bromobenzaldehyde (0.93g, 5mmol)) 4- (N, N-diphenylamino) benzaldehyde (2.73g,10mmol), triethylamine (505mg,5mmol) and 20mL of ethanol were added to a reaction flask and stirred at 60 ℃ for 24 hours. After completion of the reaction, the reaction mixture was quenched with 30mL of water and extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate and the organic solvent was evaporated to dryness. The crude product was purified by silica gel column chromatography to give intermediate Benzoin-2 as an orange solid.1H NMR(400MHz,CD2Cl2):δ7.83(m,2H),7.41(m,4H),7.29(m,8H),7.10(m,2H),6.93(m,2H),5.86(s,1H).
3-2) Synthesis of Phototrigger molecule TPA-3
The benzoin intermediate of the above formula (381mg,1mmol) was dissolved in 15mL of toluene, to which was added chlorotrimethylsilane (0.5mL) and ethylene glycol (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 by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product. The nuclear magnetic spectrum is shown in FIG. 3.1H NMR(400MHz,CD2Cl2):δ7.37(m,6H),7.20(d,J＝8.0Hz,2H),7.14(m,8H),6.92(d,J＝8.0Hz,2H),4.33(s,4H).
Example 4
Synthesis of photo-trigger molecule TPA-8
4-1) synthesis of intermediate Benzoin-8.
4-dimethylaminobenzaldehyde (0.75g,5mmol), 4- (N, N-diphenylamino) benzaldehyde (2.73g,10mmol), triethylamine (505mg,5mmol) and 20mL of ethanol were added to a reaction flask and stirred at 60 ℃ for 24 hours. After completion of the reaction, the reaction mixture was quenched with 30mL of water and extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate and the organic solvent was evaporated to dryness. The crude product was purified by silica gel column chromatography to give intermediate Benzoin-2 as an orange solid.1H NMR(400MHz,CD2Cl2):δ7.63(m,2H),7.45(m,4H),7.20(m,8H),7.05(m,2H),6.90(m,2H),5.82(s,1H).
4-2) Synthesis of Phototrigger molecule TPA-8
The benzoin intermediate of the above formula (381mg,1mmol) was dissolved in 15mL of toluene, to which was added chlorotrimethylsilane (0.5mL) and ethylene glycol (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 by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product. The nuclear magnetic spectrum is shown in FIG. 4.1H NMR(400MHz,CD2Cl2) δ 7.30(m,4H),7.16(m,8H),7.06(m,2H),6.90(d, J ═ 8.0Hz,2H),6.61(d, J ═ 8.0Hz,2H),4.31(s,4H),2.96(s,6H), the single crystal X-ray diffraction structure of light panel molecule TPA-8 is shown in fig. 5.
Example 5
Synthesis of photo-trigger molecule TPA-9
5-1) synthesis of intermediate Benzoin-9.
4-N-methylbenzaldehyde (1.02g,5mmol), 4- (N, N-diphenylamino) benzaldehyde (2.73g,10mmol), triethylamine (505mg,5mmol) and 20mL of ethanol were added to a reaction flask and stirred at 60 ℃ for 24 hours. After completion of the reaction, the reaction mixture was quenched with 30mL of water and extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate and the organic solvent was evaporated to dryness. The crude product was purified by silica gel column chromatography to give intermediate Benzoin-9 as an orange solid.
5-2) Synthesis of Phototrigger molecule TPA-9
The benzoin intermediate of the above formula (381mg,1mmol) was dissolved in 15mL of toluene, to which was added chlorotrimethylsilane (0.5mL) and ethylene glycol (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 by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product. The nuclear magnetic spectrum is shown in FIG. 6.1H NMR(400MHz,CD2Cl2):δ7.34(m,6H),7.19(m,4H),7.11(m,6H),7.07(m,3H),6.92(d,J＝8.Fig. 7 shows a single-crystal X-ray diffraction structure of optical plate molecule TPA-9 at 0Hz,2H),6.86(d, J ═ 8.0Hz,2H),4.32(s,4H),3.33(s,3H).
Example 6
Synthesis of photo-trigger molecule TPA-10
6-1) synthesis of intermediate Benzoin-10.
4- (N, N-diphenylamino) benzaldehyde (2.73g,10mmol), triethylamine (505mg,5mmol) and 20mL of ethanol were added to a reaction flask and stirred at 60 ℃ for 24 hours. After completion of the reaction, the reaction mixture was quenched with 30mL of water and extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate and the organic solvent was evaporated to dryness. The crude product was purified by silica gel column chromatography to give intermediate Benzoin-15 as an orange solid.
6-2) Synthesis of Phototrigger molecule TPA-10
The benzoin intermediate of the above formula (381mg,1mmol) was dissolved in 15mL of toluene, to which was added chlorotrimethylsilane (0.5mL) and ethylene glycol (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 by using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product. The nuclear magnetic spectrum is shown in FIG. 8.1H NMR(400MHz,CD2Cl2) δ 7.30(m,8H),7.19(d, J ═ 8.0Hz,4H),7.11(m,12H),6.93(d, J ═ 8.0Hz,2H),4.32(s,4H), and the single crystal X-ray diffraction structure of photoelastic molecule TPA-10 is shown in fig. 9.
Example 7
7-1) two portions of the optical trigger molecule TPA-2 of example 2 in dichloromethane were prepared at a concentration of 50. mu.M and placed in bottles numbered 1a and 1b, respectively;
two portions of the optical trigger molecule TPA-8 solution of example 4 in methylene chloride at a concentration of 50 μ M were prepared and placed in bottles numbered 2a and 2b, respectively;
two portions of the optical trigger molecule TPA-9 of example 5 in dichloromethane were prepared at a concentration of 50. mu.M and placed in bottles numbered 3a and 3b, respectively;
two portions of the optical trigger molecule TPA-10 of example 6 in methylene chloride at a concentration of 50 μ M were prepared and placed in bottles numbered 4a and 4b, respectively;
7-2) as shown in FIG. 10:
1a, 2a, 3a and 4a are irradiated by a 365nm portable ultraviolet lamp, and no fluorescence is generated. (ii) a
Irradiating the 1b bottle for 10s by adopting a 365nm LED lamp, and finding that the 1b bottle is bright and luminous, and the fluorescence color is blue; irradiating the 2b bottle for 10s by adopting a 365nm LED lamp, and then irradiating by using a 365nm portable ultraviolet lamp to find that the 2b bottle is bright and luminous, and the fluorescence color is blue; irradiating the 3b bottle for 10s by adopting a 365nm LED lamp, and then irradiating by using a 365nm portable ultraviolet lamp to find that the 3b bottle is bright and luminous, and the fluorescence color is blue; irradiating the 4b bottle for 10s by using a 365nm LED lamp, and then irradiating by using a 365nm portable ultraviolet lamp to find that the 4b bottle is bright and luminous, and the fluorescence color is blue; the 365nm LED lamp is irradiated to enable the light trigger molecules to complete the process of light activation, and the light trigger molecules can regulate and control the light emitting properties of the light trigger molecules, such as excitation wavelength, emission wavelength, light emitting intensity, photolysis speed or photolysis efficiency, by replacing substituents.
The above-described optical trigger molecules TPA-2, TPA-8, TPA-9, and TPA-10 were also tested for their decay in fluorescence intensity, as shown in fig. 11 and 12, and all had afterglow emission properties after removal of the excitation light source. The life of TPA-2 was 50.9min, that of TPA-8 was 28.6s, that of TPA-9 was 5.5min, and that of TPA-10 was 24.1 min. As shown in FIG. 13 (the four curves in the figure almost coincide), the afterglow emission peaks of the light trigger molecules TPA-2, TPA-8, TPA-9 and TPA-10 after removing the excitation light are about 456 nm. These properties can be applied in the fields of information storage, anti-counterfeiting, biological tracing, biological imaging and the like.
Example 8
8-1) a dichloromethane solution of the optical trigger molecule TPA-2 of example 2 was prepared, the concentration was 50 μ M, the excitation was performed with a 365nm LED lamp, and the change in fluorescence intensity before and after the excitation was tested with a 365nm xenon lamp on a fluorescence spectrometer, as shown in fig. 14a, the fluorescence intensity before and after the excitation was enhanced by 162 times;
8-2) the methylene chloride solution of the optical trigger molecule TPA-8 of example 4 was prepared at a concentration of 50 μ M, activated with a 365nm LED lamp, and the change in fluorescence intensity before and after activation was tested on a fluorescence spectrometer using a 365nm xenon lamp, as shown in fig. 14b, the fluorescence intensity before and after activation was enhanced by 98 times;
8-3) a dichloromethane solution of the photo-trigger molecule TPA-9 of example 5 was prepared at a concentration of 50 μ M, activated with a 365nm LED lamp, and the change in fluorescence intensity before and after activation was tested on a fluorescence spectrometer using a 365nm xenon lamp, as shown in fig. 14c, the fluorescence intensity before and after activation was increased by 92 times;
8-4) A methylene chloride solution of the photo trigger molecule TPA-10 of example 6 was prepared at a concentration of 50 μ M, activated with a 365nm LED lamp, and the change in fluorescence intensity before and after activation was measured on a fluorescence spectrometer using a 365nm xenon lamp, as shown in FIG. 14d, with the fluorescence intensity before and after activation being enhanced by a factor of 99.
The experiment proves that the fluorescence intensity of the optical trigger molecule provided by the embodiment of the invention is obviously enhanced after the optical trigger molecule is activated by light.
Example 9
TPA-8(50mg) was dissolved in methylene chloride (400mL), and irradiated with a 365nm laser without leaving any afterglow. The reaction solution was quenched by adding 200mL of water, and the organic layer was quenched with anhydrous Na2SO4Drying, spin-drying the solvent using a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product (eluent: dichloromethane/petroleum ether ═ 20:1), yield: 88.7%, NMR spectrum as shown in FIG. 15.1H NMR(400MHz,CD2Cl2):δ7.93(m,4H),7.38(m,4H),7.19(m,6H),7.01(d,J＝8.0Hz,2H),6.71(d,J＝8.0Hz,2H),4.60(m,4H),3.06(s,6H).
Example 10
TPA-9(50mg) was dissolved in methylene chloride (400mL), stirred and irradiated with a 450nm laser until no afterglow occurred. The reaction solution was quenched by adding 200mL of water, and the organic layer was quenched with anhydrous Na2SO4Drying, spin-drying the solvent with a rotary evaporator, and separating by silica gel column chromatography to obtain a pure product (eluent volume ratio dichloromethane/petroleum ether is 20:1), yield: 85.6%, nuclear magnetic spectrum as shown in FIG. 16.1H NMR(400MHz,CD2Cl2):δ7.91(m,4H),7.47(m,2H),7.38(m,4H),7.27(m,3H),7.19(m,6H),7.01(d,J＝8.0Hz,2H),6.81(d,J＝8.0Hz,2H),4.60(s,4H),3.39(s,3H).
The molecules TPA-8 and TPA-9 of the optical trigger molecule are subjected to photolysis to obtain the molecules TPE-8 and TPE-9, photons are released to generate fluorescence, the photolysis yield is close to 90%, and side reactions are basically avoided, so that the series of optical trigger molecules are high in photolysis yield.
Example 11
11-1) respectively dissolving optical trigger molecules TPA-8 and TPA-9 in dichloromethane to prepare 100 mu M solution;
11-2) 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;
11-3) adding the solutions of the light trigger molecules TPA-8 and TPA-9 into the AB glue solution respectively, heating at 60 ℃ for 2 hours, curing to generate a light trigger film, irradiating the film for 5 seconds by using a 365nm LED light source, and then closing an excitation light source, wherein long afterglow luminescence of the light trigger molecules can be seen as shown in figure 17.
Example 12
12-1) dissolving non-optical trigger molecule TPA in dichloromethane to prepare 1mM TPA solution; dissolving optical trigger molecule TPA-8 in dichloromethane to prepare 1mM TPA-8 solution;
12-2) mixing the glue A (the glue) and the glue B (the hardened glue) according to the mass ratio of 1:1 to prepare an AB glue solution;
12-3) sucking 100 microliter of TPA solution, adding 100 microliter of AB glue solution, laying the mixture at the position of an English logo in the pattern of the double denier university logo shown in figure 12, sucking 100 microliter of TPA-8 solution, adding 100 microliter of AB glue solution, and filling the mixture at the position of a Chinese logo in the pattern of the double denier university logo;
12-4) as shown in fig. 18 (picture is taken by mobile phone), the fluorescence pattern at the English position can be observed by using 365nm portable ultraviolet lamp for irradiation, and the fluorescence pattern of the whole 'Compound denier university logo' can be observed after using 365nm LED lamp for irradiation for 10 s.
The molecule activation characteristic of the optical trigger can be used for anti-counterfeiting technology. In short, common fluorescent dyes, such as TPA, have fluorescence under the irradiation of ultraviolet light, while the photo-trigger molecules provided by the embodiments of the present invention have excellent photo-activation characteristics, and the photo-trigger molecules with different structures need different wavelengths of excitation light for activation. For example, TPA-8 molecule has weak fluorescence and emits light after being activated by 365nm light, so that a novel anti-counterfeiting mode can be provided based on the properties of the light trigger molecule provided by the embodiment of the invention, and the mode is based on two change modes of fluorescence and afterglow before and after light activation, which is different from the current non-activated mode. And the anti-counterfeiting mode is not limited to paving mixed glue, and can also be anti-counterfeiting in other forms, such as anti-counterfeiting coating, anti-counterfeiting printing and the like.
Example 13
13-1) dissolving a light trigger molecule TPA-8 in dichloromethane, adding the solution into screen printing ink to prepare a TPA-8 solution, and screen printing a first layer of patterns (bird 1); dissolving a light trigger molecule TPA-10 in dichloromethane, adding the solution into screen printing ink to prepare a TPA-10 solution, and screen printing a second layer pattern (bird 2); non-photo trigger molecules TPA were dissolved in methylene chloride, added to screen printing ink to formulate TPA solution, and the third layer pattern (bird 1, bird 2, and peach tree) was screen printed.
13-2) as shown in fig. 19, the fluorescence patterns of birds 1, 2 and peach trees can be observed by irradiation with a 365nm portable ultraviolet lamp, the patterns of birds 1 and 2 can be observed by turning off the ultraviolet lamp for 2 seconds after irradiation with a 365nm LED lamp for 30 seconds, and the patterns of birds 2 can be observed only by turning off the ultraviolet lamp for 5 minutes.
The light trigger molecule can activate afterglow characteristic and combine fluorescence luminescence mode, and can be applied to multiple anti-counterfeiting technology. In short, a common fluorescent dye, such as TPA, only fluoresces without afterglow under the irradiation of an ultraviolet lamp, while the light trigger molecules provided by the embodiment of the invention have light-activated afterglow characteristics, and the light trigger molecules with different structures have different afterglow lives. Thus, based on the properties of the optical trigger molecules provided by embodiments of the present invention, a higher level of security is provided based on the two variations of the decay lifetime of fluorescence and afterglow, which are different from the current non-activated mode. And the anti-counterfeiting mode is not limited to screen printing ink, and can also be anti-counterfeiting of other forms, such as anti-counterfeiting paint, anti-counterfeiting printing and the like.
Example 14
Nanoprobe preparation
14-1) preparation of Water-soluble Nano luminescent Probe
The method comprises the following steps:
14-1-1) the photo trigger molecule TPA-8 from example 1 was formulated as a stock solution at a molarity of 2 mM;
14-1-2) dissolving amphiphilic polyethylene glycol (F-127) of the connecting material in an organic solvent to prepare a connecting material solution with the mass concentration of 5 mg/mL;
14-1-3) 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;
14-1-4) adding the mixed solution into pure water, stirring the mixed solution and the pure water at the volume ratio of 1:10 at room temperature for 5 minutes, removing the organic solvent, filtering the mixture through a water phase filter with the pore diameter of 0.13 mu m to obtain a TPA-8 nano probe, and storing the TPA-8 nano probe at the temperature of 4 ℃ for later use.
Repeating the steps to obtain the TPA-8 nano probe.
The above examples illustrate the applicability of the optical trigger TPA-8 nanoprobe to bioimaging.
In addition, the light trigger molecules of the present invention can achieve specific functional applications. For example, when the light trigger molecule is used, the luminescence property of the triphenylamine molecule is in a suppressed state, and only the light with specific wavelength is used for activation, the light trigger molecule can emit light signals, 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 the metabolism and transport channels 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.
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 (10)
1. A triphenylamine-based optical trigger molecule, wherein the optical trigger molecule has 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:
wherein, Ar can be any one of the following aromatic structures:
wherein R is1，R2，R3The substituent groups are the same or different and are respectively and independently selected from hydrogen, unsubstituted alkyl, unsubstituted alkoxy, unsubstituted hydroxyl, unsubstituted nitro, unsubstituted cyano, unsubstituted ester group, unsubstituted carboxyl, unsubstituted amino, unsubstituted sulfydryl, halogen atom, unsubstituted aryl, unsubstituted aromatic heterocyclic group, substituted alkyl, substituted alkoxy, substituted hydroxyl, substituted nitro, substituted cyano, substituted ester group, substituted carboxyl, substituted amino, substituted sulfydryl, substituted aryl, substituted aromatic heterocyclic group or the combination of the hydrogen, the unsubstituted alkyl, the unsubstituted alkoxy, the unsubstituted aryl, the unsubstituted aromatic heterocyclic group and the substituted hydroxyl.
2. An optical trigger molecule according to claim 1, wherein R is1，R2，R3Any one of the substituents is located at the ortho, meta or para position of the phenyl ring.
3. A light trigger molecule according to claim 1 wherein the unsubstituted alkyl group has 1 to 20 carbon atoms, preferably the unsubstituted alkyl group is selected from one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl;
preferably, the substituted alkoxy group is a group represented by-OR, wherein the group represented by R is an unsubstituted alkyl group having 1 to 20 carbon atoms, preferably, the unsubstituted alkyl group is one selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, OR n-octyl;
preferably, the substituted amino group is a group represented by-NRxRy, wherein the groups represented by Rx and Ry are hydrogen or a group having 1 to 20 carbon atoms, and preferably, the group having 1 to 20 carbon atoms is one selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and phenyl.
4. An optical trigger molecule according to claim 1, wherein the substituted aryl group has 6 to 50 ring carbon atoms, preferably one of phenyl, naphthyl, o-tolyl, m-tolyl, p-tert-butylphenyl.
5. An optical trigger molecule according to claim 1, wherein the substituted aromatic heterocyclic group has 4 to 50 ring carbon atoms, preferably one of furyl, thienyl, pyrrolyl, pyridyl, pyranyl, carbazolyl, indolyl, quinolinyl.
6. A light trigger molecule according to claim 1, wherein the light trigger molecule is selected from any one of the following structures:
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 to 1min, preferably 5 to 30s, more preferably 10 to 20 s.
8. The method of synthesizing a light trigger molecule according to any one of claims 1 to 7, wherein the method of synthesizing comprises:
s1 preparation of benzoin intermediate
Adding benzaldehyde containing a substituent group and triphenylamine aldehyde containing a substituent group into a reaction bottle, adding a catalyst, alkali and ethanol, and carrying out heating reflux reaction for more than 12 hours under the protection of nitrogen to obtain a solid substance, namely a benzoin intermediate;
s2 preparation of Phototrigger molecule
Will contain a substituent R1，R2，R3Adding benzoin and ethylene glycol into an organic solvent, adding a catalyst, heating for reaction for a period of time, and performing post-treatment to obtain the light trigger molecule.
9. A nanoprobe comprising an optical trigger molecule according to any of claims 1 to 7 and a linker material; the optical trigger molecule is coated in the connecting material, and the connecting material is selected from any one or more of hydrogel microspheres, styrene polymer microspheres, microspheres formed by protein, silicon nano-microspheres, polymethyl methacrylate microspheres, bovine serum albumin, amphiphilic polyethylene glycol or lecithin;
the mass ratio of the optical trigger molecules to the connecting material is 1: 10000-1: 100.
10. A method of preparing the nanoprobe of claim 9, the method comprising:
1) formulating the optical trigger molecule of any one of claims 1-7 into a stock solution having a mass concentration of 1mM-5mM (preferably 2 mM);
2) dissolving a connecting material (the connecting material is preferably amphiphilic polyethylene glycol (F-127)) in an organic solvent to prepare a connecting material solution with the mass concentration of 1mg/mL-10mg/mL (preferably 5 mg/mL);
3) adding the stock solution obtained in the step 1) into the connecting material solution obtained in the step 2), wherein the volume ratio of the stock solution to the connecting material solution is 1:100-1:500 (preferably 1:200), and fully mixing to obtain a mixed solution;
4) and (3) transferring the mixed solution obtained in the step 3) into pure water, wherein the volume ratio of the mixed solution to the pure water is 1:5-1:20 (preferably 1:10), stirring at room temperature, removing the organic solvent, and filtering through an aqueous phase filter (preferably with the pore diameter of 0.13 mu m) to obtain the nano probe.
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| CN115947711A (en) * | 2022-11-01 | 2023-04-11 | 上海泰辉生物科技有限公司 | Photochemical buffering agent and synthesis method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115947711A (en) * | 2022-11-01 | 2023-04-11 | 上海泰辉生物科技有限公司 | Photochemical buffering agent and synthesis method thereof |
| CN115947714A (en) * | 2022-11-01 | 2023-04-11 | 上海泰辉生物科技有限公司 | Method for synthesizing photochemical buffering agent |
| CN115947714B (en) * | 2022-11-01 | 2024-05-14 | 上海泰辉生物科技有限公司 | Synthesis method of photochemical caching agent |
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