CN108299574B - Water-soluble two-photon initiator and preparation and application thereof - Google Patents
Water-soluble two-photon initiator and preparation and application thereof Download PDFInfo
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- 239000003999 initiator Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 carbazole vinylpyridine derivative Chemical class 0.000 claims abstract description 17
- MSBXTPRURXJCPF-DQWIULQBSA-N cucurbit[6]uril Chemical compound N1([C@@H]2[C@@H]3N(C1=O)CN1[C@@H]4[C@@H]5N(C1=O)CN1[C@@H]6[C@@H]7N(C1=O)CN1[C@@H]8[C@@H]9N(C1=O)CN([C@H]1N(C%10=O)CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@@H]6[C@H]4N2C(=O)N6CN%10[C@H]1N3C5 MSBXTPRURXJCPF-DQWIULQBSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000008346 aqueous phase Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- ZDOBFUIMGBWEAB-XGFHMVPTSA-N cucurbit[7]uril Chemical compound N1([C@H]2[C@H]3N(C1=O)CN1[C@H]4[C@H]5N(C1=O)CN1[C@H]6[C@H]7N(C1=O)CN1[C@H]8[C@H]9N(C1=O)CN1[C@H]%10[C@H]%11N(C1=O)CN([C@@H]1N(C%12=O)CN%11C(=O)N%10CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@H]6[C@@H]4N2C(=O)N6CN%12[C@@H]1N3C5 ZDOBFUIMGBWEAB-XGFHMVPTSA-N 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001338 self-assembly Methods 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- VKSVEHYLRGITRK-QVQDFVARSA-N cucurbit[5]uril Chemical compound N1([C@H]2[C@H]3N(C1=O)CN1[C@H]4[C@H]5N(C1=O)CN1[C@H]6[C@H]7N(C1=O)CN([C@@H]1N(C8=O)CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@H]6[C@@H]4N2C(=O)N6CN8[C@@H]1N3C5 VKSVEHYLRGITRK-QVQDFVARSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 24
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000671 polyethylene glycol diacrylate Polymers 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Abstract
The invention discloses a water-soluble two-photon initiator, and preparation and application thereof, and belongs to the technical field of laser micro-nano processing. The water-soluble two-photon initiator is formed by self-assembling a host molecule cucurbituril and a guest molecule carbazole vinylpyridine derivative. The water-soluble two-photon initiator has a larger two-photon absorption cross section, overcomes the problems of complex initiator system, residual organic solvent and the like in the prior art, is used as a single-component initiator in a water phase to directly initiate two-photon polymerization, and prepares a three-dimensional structure with low polymerization threshold and high resolution.
Description
Technical Field
The invention relates to the technical field of laser micro-nano processing. More particularly, relates to a water-soluble two-photon initiator, and preparation and application thereof.
Background
Two-photon absorption means that under the excitation of strong laser, a molecule or an atom can simultaneously absorb two photons with the same frequency or different frequencies, and the two photons are transited from a ground state to an excited state through a virtual state. Photopolymerization refers to a process that the molecular weight of a polymer is increased due to light absorption, and two-photon polymerization processing, different from the traditional ultraviolet single-photon polymerization, is to initiate polymerization reaction by using a photoinitiator with a large two-photon absorption section, and generally adopts near-infrared laser to perform high-precision polymerization processing of a three-dimensional structure. The technology is widely applied to the fields of biological tissue engineering construction, high-density optical information storage, functional micro-device preparation and the like.
In recent years, two-photon polymerization processing is one of the simplest and most effective methods for realizing high-resolution three-dimensional structure processing, so that the application of the two-photon polymerization processing in tissue engineering is widely concerned, and the three-dimensional microstructure prepared by utilizing the photopolymerization of a biocompatible polymerization monomer in a water phase is used as a tissue engineering scaffold, so that the two-photon polymerization processing has important significance in the field of biomedicine. Two-photon initiators are important components of two-photon polymerization systems, and are related to the polymerization speed and the precision of three-dimensional structures. Therefore, the lack of water-solubility of highly efficient two-photon initiators is an important factor limiting the application of this technology in tissue engineering. On one hand, the existing two-photon initiator has poor water solubility, the processing of the tissue engineering scaffold is often carried out in an organic solution, and the use safety of a three-dimensional structure is greatly influenced by residual organic solvent after polymerization; on the other hand, the initiator applied to the aqueous two-photon polymerization is usually small in two-photon absorption cross section and low in initiation efficiency, and the polymerization can be effectively initiated by adding a photosensitizer, so that the components of a two-photon initiator system become very complex, the initiation threshold is large during polymerization, the resolution of a processed three-dimensional structure is low, and potential safety hazards can be introduced. (Journal of Biomedical Optics,2012,17(10): 105008-. Therefore, it is a key to solve this problem to develop a water-soluble initiator that has a large two-photon absorption cross section in an aqueous phase and can directly and efficiently initiate two-photon polymerization.
Existing studies have shown that some carbazole vinylpyridine derivatives can be used as two-photon initiators, but due to their water solubility limitations, can only be used for three-dimensional structural processing by adding photosensitizers in organic solvents. (New Journal of chemistry,2007,31(1):63-68.)
Disclosure of Invention
In order to overcome the defects of poor water solubility, complex initiator system components, low initiation efficiency and residual organic solvent of the traditional initiator for two-photon polymerization processing in the water phase, the invention provides a water-soluble two-photon initiator with a large two-photon absorption cross section, and provides preparation and application of the water-soluble two-photon initiator.
In order to achieve the purpose, the invention adopts the following technical scheme:
a water-soluble two-photon initiator is formed by self-assembling a host molecule cucurbituril and a guest molecule carbazole vinylpyridine derivative; the cucurbituril is cucurbit [7] uril or cucurbit [5] uril, and the carbazole vinylpyridine derivative has the following structural general formula:
wherein R is1Is H, ethyl, propyl, butyl, pentyl, phenyl or hydroxy;
R2is methyl, ethyl or isopropyl;
Preferably, the carbazole vinylpyridine derivative has the following general structural formula:
wherein R is1Is H, ethyl, propyl, butyl, pentyl, phenyl or hydroxy;
R2is methyl, ethyl or isopropyl;
The invention also provides a preparation method of the water-soluble two-photon initiator, which comprises the following steps:
s1, mixing the carbazole vinyl pyridine derivative with water;
s2, adding cucurbituril molecules, stirring and carrying out self-assembly;
and S3, drying the self-assembled aqueous solution to obtain the water-soluble two-photon initiator.
Preferably, the final concentration of the carbazole vinylpyridine derivative after mixing with water is 1-5 mmol/L.
Preferably, the molar ratio of the cucurbituril to the carbazole vinylpyridine derivative is 1-10: 1.
Preferably, the stirring temperature is room temperature, and the stirring time is 5-15 minutes.
Preferably, the drying is freeze drying.
The invention also provides application of the water-soluble two-photon initiator in laser micro-nano processing in a water phase.
The invention has the following beneficial effects:
the water-soluble two-photon initiator provided by the invention is formed by self-assembling cucurbituril and carbazole vinylpyridine derivatives, the cucurbituril molecule has good water solubility, an inclusion compound is formed by interaction of a pyridine cationic group of the initiator and a hydrophobic cavity of the cucurbituril, the two-photon absorption cross section of the initiator is obviously improved (1500 GM), the water solubility of the initiator is increased, the initiator serving as a single-component initiator can efficiently initiate two-photon photopolymerization in a water phase, the initiation threshold value is low (6.15 mW) during processing, and the problems of complex initiator system, organic solvent residue and the like in the prior art are solved.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows the UV-visible absorption and single photon fluorescence spectra of molecule a and water-soluble two-photon initiator A in example 1 of the present invention.
FIG. 2 is a two-photon absorption cross section of the molecule a and the water-soluble two-photon initiator A in the aqueous phase in example 1 of the present invention.
Figure 3 is a three-dimensional structure diagram prepared in the aqueous phase using a water soluble dual photoinitiator a.
Fig. 4 is a three-dimensional structure diagram prepared in the aqueous phase using a water-soluble dual photoinitiator B.
Fig. 5 is a three-dimensional structure diagram prepared in the aqueous phase using a water-soluble dual photoinitiator D.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The preparation of carbazole vinylpyridine derivatives is described in the cited documents [1] and [2 ].
[1]Gu J,Yulan W,Chen W-Q,et al.Carbazole-based 1D and 2Dhemicyanines:synthesis,two-photon absorption properties and application fortwo-photon photopolymerization 3D lithography[J].New Journal of Chemistry,2007,31(1):63-68.
[2]Zheng Y-C,Zheng M-L,Chen S,et al.Biscarbazolylmethane-basedcyanine:a two-photon excited fluorescent probe for DNA and selective cellimaging[J].Journal of Materials Chemistry B 2014,2(16),2301-2310.
Example 1
Preparation of Water-soluble two-photon initiator A
The self-assembly method of the water-soluble two-photon initiator uses a molecule a as a guest molecule, the molecular structure is shown as a, cucurbit [7] urea is used as a host molecule, and the self-assembly method comprises the following steps:
s1, 0.36mg of the molecule a is weighed and mixed with 200. mu.L of ultrapure water.
S2, adding 2.3mg cucurbit [7] uril molecules into the system, mixing, stirring for 15 minutes in a vortex mode, wherein the final concentration of the dissolved molecules a is 2.0mmol/L, and the final molar ratio of the molecules a to the cucurbit [7] uril is 1: 5.
S3, freezing and drying the aqueous solution to obtain the water-soluble two-photon initiator A.
The ultraviolet visible absorption spectrum and single-photon fluorescence spectrum of the molecule a before and after the interaction with cucurbit [7] uril in the aqueous solution are shown in figure 1. Due to the formation of the inclusion complex, the ultraviolet-visible absorption spectrum of the molecule a undergoes a significant red shift after the reaction. The interaction of the cucurbituril cavity and the pyridine cation group increases the rigidity of the molecule a, and the fluorescence intensity of the molecule a is increased after the inclusion complex is formed.
The two-photon absorption cross-section of molecule a before and after interaction with cucurbit [7] uril in aqueous solution is shown in FIG. 2. The two-photon absorption cross sections of molecule a before and after the formation of the inclusion complex were significantly increased, 522GM and 2499GM, respectively.
Example 2
The processing of the three-dimensional microstructure was carried out using the water-soluble two-photon initiator a of example 1 to initiate two-photon polymerization in the aqueous phase:
1.5mg of water-soluble two-photon initiator A is weighed and dissolved in 200 mu L of ultrapure water, then 0.5g of polyethylene glycol diacrylate (PEGda) monomer is added and stirred uniformly, and the mixture is wrapped by aluminum foil paper and stored in a dark place. The processing threshold of the initiator is 6.18mW obtained by processing the two-dimensional polymer nanowires under different powers, and the three-dimensional structure is processed by using laser power higher than the threshold. The prepared photoresist is dripped in the center of a clean glass plate, a titanium sapphire femtosecond laser is used as a light source, the center wavelength is 780nm, the pulse width is 80fs, the pulse repetition frequency is 80MHz, the output power is 9.2mW, a laser beam is focused into the photoresist through a microscope objective with the amplification factor of 100 times and the numerical aperture NA of 1.45, the glass sheet with the photoresist is placed on a three-dimensional moving platform controlled by a computer to process a three-dimensional structure through two-photon polymerization, after the processing is finished, the unpolymerized photoresist is removed by using ethanol to obtain a fine processing structure, and the processed three-dimensional structure chart is shown in figure 3.
Example 3
Preparation of Water-soluble two-photon initiator B
The self-assembly method of the water-soluble two-photon initiator uses a molecule b as a guest molecule, the molecular structure is shown as b, cucurbit [5] urea is used as a host molecule, and the self-assembly method comprises the following steps:
s1, 0.2mg of the molecule b is weighed and mixed with 200. mu.L of ultrapure water.
S2, adding 2.0mg cucurbit [5] uril molecules into the system, mixing, stirring for 8 minutes in a vortex mode, wherein the final concentration of the dissolved molecules b is 1.5mmol/L, and the final molar ratio of the dissolved molecules b to the cucurbit [5] uril is 1: 8.
S3, freezing and drying the aqueous solution to obtain the water-soluble two-photon initiator B.
Example 4
The processing of the three-dimensional microstructure was carried out using the water-soluble two-photon initiator B of example 3 to initiate two-photon polymerization in the aqueous phase:
2.0mg of water-soluble two-photon initiator B is weighed and dissolved in 200 mu L of ultrapure water, then 0.5g of polyethylene glycol diacrylate (PEGda) monomer is added and stirred uniformly, and the mixture is wrapped by aluminum foil paper and stored in a dark place. The processing threshold of the initiator is 6.85mW by processing the two-dimensional polymer nanowires under different powers, and the three-dimensional structure is processed by using the laser power higher than the threshold. The prepared photoresist is dripped in the center of a clean glass plate, a titanium sapphire femtosecond laser is used as a light source, the center wavelength is 780nm, the pulse width is 80fs, the pulse repetition frequency is 80MHz, the output power is 13mW, a laser beam is focused into the photoresist through a microscope objective with the amplification factor of 60 times and the numerical aperture NA of 1.42, the glass sheet with the photoresist is placed on a three-dimensional moving platform controlled by a computer to process a three-dimensional structure through two-photon polymerization, after the processing is finished, the unpolymerized photoresist is removed by using ethanol to obtain a fine processing structure, and the processed three-dimensional structure chart is shown in figure 4.
Example 5
Preparation of Water-soluble two-photon initiator D
The self-assembly method of the water-soluble two-photon initiator uses a molecule d as a guest molecule, the molecular structure is shown as d, cucurbit [7] urea is used as a host molecule, and comprises the following steps:
s1, 0.5mg of the molecule d is weighed and mixed with 200. mu.L of ultrapure water.
S2, adding 2.0mg cucurbit [7] uril molecules into the system, mixing, stirring for 5 minutes in a vortex mode, wherein the final concentration of the dissolved molecules d is 3.45mmol/L, and the final molar ratio of the dissolved molecules d to the cucurbit [7] uril is 1: 3.
S3, freezing and drying the aqueous solution to obtain the water-soluble two-photon initiator D.
Example 6
The processing of the three-dimensional microstructure was carried out using the water-soluble two-photon initiator D of example 5 to initiate two-photon polymerization in the aqueous phase:
1.8mg of water-soluble two-photon initiator D is weighed and dissolved in 200 mu L of ultrapure water, then 0.5g of polyethylene glycol diacrylate (PEGda) monomer is added and stirred uniformly, and the mixture is wrapped by aluminum foil paper and stored in a dark place. The processing threshold of the initiator is 6.50mW obtained by processing the two-dimensional polymer nanowires under different powers, and the three-dimensional structure is processed by using the laser power higher than the threshold. The prepared photoresist is dripped in the center of a clean glass plate, a titanium sapphire femtosecond laser is used as a light source, the center wavelength is 780nm, the pulse width is 80fs, the pulse repetition frequency is 80MHz, the output power is 11.5mW, a laser beam is focused into the photoresist through a microscope objective with the amplification factor of 60 times and the numerical aperture NA of 1.42, the glass sheet with the photoresist is placed on a three-dimensional moving platform controlled by a computer to process a three-dimensional structure through two-photon polymerization, after the processing is finished, the unpolymerized photoresist is removed by using ethanol to obtain a fine processing structure, and the processed three-dimensional structure chart is shown in figure 5.
Compared with the molecule d, the flexible connection of the carbazolyl molecules in the molecule a can effectively avoid the steric hindrance effect of the action of the pyridine cation group and the cucurbituril, the molecule is more likely to react with the cucurbituril to generate an inclusion compound, the space electron transfer action of the molecule also enables the two-photon absorption cross section to be obviously increased, and the initiator A obtains a lower processing threshold value.
In the case of cucurbit 5 urea as the host molecule, the cucurbit 5 urea has a smaller hydrophobic cavity, and compared with the molecule d, the molecule B has a smaller molecular weight, so that the molecule B can better interact with cucurbit 5 urea, and the usage amount and the processing threshold of the initiator B are lower.
Therefore, when the skeleton of the guest molecule carbazole vinyl pyridine derivative in the invention is the molecular skeleton of the molecules a and b, the obtained water-soluble two-photon initiator has more excellent performance, and the usage amount and the processing threshold value are lower.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (8)
1. A water-soluble two-photon initiator is characterized in that the initiator is formed by self-assembling a host molecule cucurbituril and a guest molecule carbazole vinylpyridine derivative;
the cucurbituril is cucurbit [7] uril or cucurbit [5] uril; the carbazole vinyl pyridine derivative has a structural general formula as follows:
wherein R is1Is H, ethyl, propyl, butyl, pentyl, phenyl or hydroxy;
R2is methyl, ethyl or isopropyl;
2. The water-soluble two-photon initiator of claim 1, wherein the carbazole vinyl pyridine derivative has the following general structural formula:
wherein R is1Is H, ethyl, propyl, butyl, pentyl, phenyl or hydroxy;
R2is methyl, ethyl or isopropyl;
3. A method of preparing a water-soluble two-photon initiator according to claim 1 or 2, comprising the steps of:
s1, mixing the carbazole vinyl pyridine derivative with water;
s2, adding cucurbituril molecules, stirring and carrying out self-assembly;
and S3, drying the self-assembled aqueous solution to obtain the water-soluble two-photon initiator.
4. The preparation method according to claim 3, wherein the final concentration of the carbazole vinylpyridine derivative after mixing with water is 1 to 5 mmol/L.
5. The preparation method according to claim 3, wherein the molar ratio of cucurbituril to carbazole vinyl pyridine derivative is 1-10: 1.
6. The preparation method according to claim 3, wherein the stirring temperature is room temperature and the stirring time is 5 to 15 minutes.
7. The method of claim 3, wherein the drying is freeze-drying.
8. Use of the water-soluble two-photon initiator according to claim 1 or 2 for laser micro-nano processing in an aqueous phase.
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| CN1887883A (en) * | 2005-06-27 | 2007-01-03 | 中国科学院理化技术研究所 | V-shaped conjugated light-absorbing organic salt compound and its use |
| CN103864964B (en) * | 2014-02-26 | 2016-01-13 | 天津大学 | A kind of water-soluble two-photon polymerization initiator and assemble method and purposes |
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