CN110456614B - Femtosecond laser internal photopolymerization direct writing processing method of methacrylic acid gelatin hydrogel - Google Patents
Femtosecond laser internal photopolymerization direct writing processing method of methacrylic acid gelatin hydrogel Download PDFInfo
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- CN110456614B CN110456614B CN201910648156.3A CN201910648156A CN110456614B CN 110456614 B CN110456614 B CN 110456614B CN 201910648156 A CN201910648156 A CN 201910648156A CN 110456614 B CN110456614 B CN 110456614B
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- femtosecond laser
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- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
- G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser
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- 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
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/70383—Direct write, i.e. pattern is written directly without the use of a mask by one or multiple beams
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Abstract
A femtosecond laser internal photopolymerization direct writing processing technology of methacrylic acid gelatin hydrogel belongs to the field of biological material processing and application. The method comprises the following steps: selecting a commercial 405nm absorption waveband water-soluble photoinitiator; rose bengal is selected as a photosensitizer to improve the initiation efficiency of a photoinitiator; preparing a methacrylic acid gelatin (GelMA) hydrogel photosensitive solution which can be used for femtosecond laser internal photopolymerization direct writing processing with a center wavelength of 780 nm; the processing characteristics of the experimental materials in the used proportions were determined by femtosecond laser direct writing processing using the prepared methacrylic gelatin (GelMA) hydrogel photosensitive solution.
Description
Technical Field
The invention relates to the field of biomaterial processing and application, in particular to a femtosecond laser internal photopolymerization direct writing processing technology of methacrylic acid gelatin (GelMA) hydrogel.
Background
Tissue engineering technology covers many disciplines such as cell biology, engineering science, material science, medical surgery and the like, and realizes the repair or regeneration of damaged tissues. The basic principle and the method are as follows: separating cells, namely seed cells, from healthy tissues of a body; processing a three-dimensional structure with a specific shape, namely a tissue engineering scaffold, by using a material with excellent biocompatibility; the seed cells are attached to the tissue engineering scaffold to grow to form a cell tissue-biomaterial compound, and then the compound is implanted into the lesion parts of human tissues and organs. With the continuous proliferation and differentiation of cell tissues, the biological materials of the tissue engineering scaffold are gradually degraded by organisms, and finally new tissues with the shapes and functions consistent with those of corresponding tissues and organs are formed. Tissue engineering scaffolds allow tissue or organ regeneration.
The preparation of natural hydrogel tissue engineering scaffold by using femtosecond laser with 780nm central wavelength for photopolymerization direct writing processing is a great research hotspot nowadays. In the existing research results, researchers use femtosecond laser with near infrared wave band to initiate photopolymerization reaction by synthesizing photoinitiators with symmetric chemical structures such as D-pi-A-pi-D.
However, the novel photoinitiators are not commercialized and are difficult to synthesize. While the absorption band of commercial photoinitiators is mostly 355-405nm, almost no absorption peak is found in the 800nm band. Therefore, the photosensitizer is introduced into the photosensitive solution to improve the initiation efficiency of the photoinitiator, and a new solution is provided for the femtosecond laser photopolymerization direct writing processing of the natural hydrogel. In addition, PBS buffer solution is mostly used in the preparation process of the natural photoinitiator, so the processing process is aqueous phase processing, and a photoinitiation system with water solubility and excellent biocompatibility needs to be selected to prepare the photosensitive solution.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a femtosecond laser internal photopolymerization direct writing processing technology of methacrylic acid gelatin (GelMA) hydrogel. The technical scheme is as follows:
firstly, the material proportion of methacrylic acid gelatin (GelMA) hydrogel photosensitive solution which can be used for 780nm femtosecond laser photopolymerization direct writing processing is explored, and the raw materials comprise: GelMA hydrogel particles that have been freeze-dried, VA-086 photoinitiator, rose bengal (rose bengal sodium) photosensitizer, 1 XPBS buffer. The method is characterized in that:
the proportion of the freeze-dried GelMA hydrogel particles in the photosensitive solution is 0.1 g/mL;
VA-086 photoinitiator accounts for 0.01g/mL in the photosensitive solution;
rose bengal (rose bengal sodium) photosensitizer, the proportion of which in the photosensitive solution is 0.01 g/mL;
1 XPBS buffer, used to dissolve the light sensitive solution required raw materials.
The method for preparing the methacrylic acid gelatin hydrogel photosensitive solution for femtosecond laser internal photopolymerization direct writing processing is characterized in that GelMA, VA-086 photoinitiators and rose bengal photosensitizer are sequentially added into a centrifuge tube, and then a pipette is used for taking 1 XPBS buffer solution and adding the buffer solution into the same centrifuge tube; heating the centrifuge tube in 37 deg.C water bath for 10 min; the ultrasonic oscillation: ultrasonically oscillating the centrifugal tube for 10 minutes by using an ultrasonic cleaner; and filtering the prepared methacrylic acid gelatin hydrogel photosensitive solution.
Finally, the femtosecond laser internal photopolymerization direct writing processing characteristic of the configured experimental material is researched, and the characteristics are as follows:
the method comprises the steps of carrying out photopolymerization direct writing processing in methacrylic acid gelatin (GelMA) hydrogel photosensitive solution by using 780nm wavelength femtosecond laser, scanning polymer lines pre-embedded in a glass substrate by using different laser power and laser scanning speed, wherein the laser power range capable of being stably processed is 5-16.5 mW, and the laser scanning speed range is 5-200 mu m/s. The minimum processing resolution of 253nm is obtained under the processing parameters of 5mW of laser power and 10 mu m/s of laser scanning speed.
The material processing mechanism of the invention is as follows:
and (3) functionalizing the gelatin, wherein ether bonds of methacrylic anhydride are broken in the process, amino groups in the gelatin are dehydrogenated, and a synthetic reaction is carried out to obtain the GelMA hydrogel monomer capable of being crosslinked.
The two-photon absorption effect is induced in the material by using ultrafast laser, the absorption wavelength of the VA-086 photoinitiator is 405nm, and the absorption wavelength of the VA-086 photoinitiator is not absorbed by a femtosecond laser source with the center wavelength of 780 nm. After a rose bengal (rose bengal sodium) photosensitizer is introduced, the photosensitizer absorbs two photons to be activated, then energy is transferred to a VA-086 photoinitiator, the photoinitiator absorbs the energy and is cracked into free radicals, and the free radicals cut off double bonds in monomers or oligomers to combine into a small chain radical. The monomeric oligomers are continuously combined with previously formed small chain groups to form longer long chains. Until the two chains are linked to each other and eventually form large long chains or network crosslinks. When the concentration of the photoinitiator is large enough and the energy of the light source is strong enough, most of functional groups on the GelMA monomer in the photosensitive solution are combined with each other through methyl groups to generate complete crosslinking reaction, and finally, the functional groups are polymerized into a network crosslinking product. When the concentration of the photoinitiator is small and the energy of a light source is small, the GelMA monomer cannot generate complete crosslinking reaction, only a part of functional groups on the monomer are mutually combined through methyl to generate crosslinking, and other functional groups are not crosslinked, and finally polymerized into an organic matter long chain without forming a network crosslinking matter.
The invention has the following beneficial effects:
the femtosecond laser internal photopolymerization direct writing processing technology of methacrylic acid gelatin (GelMA) hydrogel provided by the invention selects a commercialized 405nm absorption wave band VA-086 as a photoinitiator, introduces a commercialized rose bengal (rose bengal sodium) as a photosensitizer, improves the absorption efficiency of the photoinitiator, and enables a commercialized photoinitiation system to be successfully applied to direct writing processing of 780nm center wavelength femtosecond laser. Greatly reducing the preparation difficulty of the photosensitive solution.
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FIG. 1 is an SEM photograph of the minimum line width of a polymer line pre-buried in a glass substrate, which is obtained under the processing parameters of 5mW of laser power and 10 μm/s of laser scanning speed;
FIG. 2 is a diagram showing the process of initiating a chain polymerization reaction by a photoinitiating system, wherein I is the photoinitiating system, R is a radical, M is a monomer oligomer, R-M is a small chain group, MnIs a polymer, R-MnIs a chain group.
Fig. 3 shows a mechanism of photopolymerization of a methacrylic gelatin (GelMA) hydrogel monomer, in which (a) shows a complete crosslinking reaction and (b) shows an incomplete crosslinking reaction.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
1. The preparation process of the methacrylic acid gelatin (GelMA) hydrogel photosensitive solution which can be used for femtosecond laser internal photopolymerization direct writing processing comprises the following steps:
(1) adding GelMA, VA-086 photoinitiator and rose bengal (rose bengal sodium) photosensitizer into a centrifuge tube, and adding 1mL of PBS buffer solution into the same centrifuge tube by using a pipette;
(2) heating, namely heating the centrifuge tube in 37 ℃ warm water bath for 10 minutes by using a constant-temperature water bath kettle;
(3) performing ultrasonic oscillation, namely performing ultrasonic oscillation on the centrifuge tube for 10 minutes by using an ultrasonic cleaning instrument;
(4) the prepared methacrylic gelatin (GelMA) hydrogel photosensitive solution was filtered using a 0.22 μm syringe filter.
2. A femtosecond laser internal photopolymerization direct writing processing process of methacrylic acid gelatin (GelMA) hydrogel:
(1) in the experiment, a glass sheet with the thickness of 32 multiplied by 24mm and the thickness of 0.15mm is selected as a substrate of a sample, a cross mark is made in the center of the glass sheet in advance before processing so as to observe the position of a processed three-dimensional structure, and then the glass sheet is subjected to ultrasonic cleaning by sequentially using a cleaning agent, deionized water and alcohol for 10 minutes respectively and then stored for later use.
(2) Fixing the pretreated glass sheet on a three-dimensional displacement platform, placing a reversed-square gasket with the thickness of 100 mu m, dropwise adding 30-50 mu L of hydrogel photosensitive solution into the center of the gasket, and then covering the gasket with a cover glass with the thickness of 20 multiplied by 20 mm.
(3) After the femtosecond laser beam passes through the beam expansion, the change of the light path direction is realized by the reflector, the oil immersion focusing objective lens is introduced, and the femtosecond laser beam is focused in the photosensitive solution in a lower exposure mode. Selective curing is achieved by relative displacement of the laser focus in a photosensitive solution.
Claims (2)
1. A methacrylic gelatin hydrogel photosensitive solution for femtosecond laser internal photopolymerization direct writing processing, which is characterized in that the raw materials comprise: GelMA hydrogel particles which are frozen and dried, a VA-086 photoinitiator, a rose bengal photosensitizer and a 1 XPBS buffer solution; the GelMA hydrogel particles account for 0.1g/mL in the photosensitive solution; the VA-086 photoinitiator accounts for 0.01g/mL in the photosensitive solution; the proportion of the rose bengal photosensitizer in the photosensitive solution is 0.01 g/mL.
2. The method for preparing the methacrylic gelatin hydrogel photosensitive solution for femtosecond laser internal photopolymerization direct writing processing according to claim 1, wherein GelMA, VA-086 photoinitiator and rose bengal photosensitizer are added into a centrifugal tube, and a 1 XPBS buffer solution is taken by using a pipette and added into the same centrifugal tube; heating the centrifuge tube in 37 deg.C water bath for 10 min; ultrasonically oscillating the centrifugal tube for 10 minutes by using an ultrasonic cleaner; and filtering the prepared methacrylic acid gelatin hydrogel photosensitive solution.
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| CN101006373A (en) * | 2003-12-05 | 2007-07-25 | 3M创新有限公司 | Process for producing photonic crystals |
| CN104174999A (en) * | 2014-08-13 | 2014-12-03 | 清华大学 | Method for preparing surface micro-nano figure through two steps |
| CN109870879A (en) * | 2019-03-15 | 2019-06-11 | 烟台市魔技纳米科技有限责任公司 | Two-photon polymerized photoresist, preparation method and its curing method |
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| CN101006373A (en) * | 2003-12-05 | 2007-07-25 | 3M创新有限公司 | Process for producing photonic crystals |
| CN104174999A (en) * | 2014-08-13 | 2014-12-03 | 清华大学 | Method for preparing surface micro-nano figure through two steps |
| CN109870879A (en) * | 2019-03-15 | 2019-06-11 | 烟台市魔技纳米科技有限责任公司 | Two-photon polymerized photoresist, preparation method and its curing method |
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