CN110456614A - A kind of femtosecond laser inside photopolymerization direct write processing method of methacrylic acid gelatin hydrogel - Google Patents
A kind of femtosecond laser inside photopolymerization direct write processing method of methacrylic acid gelatin hydrogel Download PDFInfo
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- CN110456614A CN110456614A CN201910648156.3A CN201910648156A CN110456614A CN 110456614 A CN110456614 A CN 110456614A CN 201910648156 A CN201910648156 A CN 201910648156A CN 110456614 A CN110456614 A CN 110456614A
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- femtosecond laser
- photopolymerization
- light sensitivity
- direct write
- hydrogel
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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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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Materials For Medical Uses (AREA)
- Medicinal Preparation (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A kind of femtosecond laser inside photopolymerization direct write processing technology of methacrylic acid gelatin hydrogel, belongs to biomaterial processing and application field.The described method includes: choosing commercialized 405nm absorption bands water-soluble light trigger；Choose the efficiency of initiation that Bengal rose red improves photoinitiator as photosensitizer；Configuration can be used for metering system acid gelatin (GelMA) hydrogel light sensitivity solution of photopolymerization direct write processing inside the femtosecond laser of 780nm central wavelength；The processing characteristics that femtosecond laser direct write processes the determining experimental material used matched are carried out using metering system acid gelatin (GelMA) hydrogel light sensitivity solution of configuration.
Description
Technical field
The present invention relates to biomaterial processing and application field, in particular to a kind of metering system acid gelatin (GelMA) water
Photopolymerization direct write processing technology inside the femtosecond laser of gel.
Background technique
Tissue engineering technique is to cover multiple such as cell biology, engineering science, material science and medical surgery
Section realizes the reparation or regenerated technology of injury tissue.Its basic principle is with method: isolating from the health tissues of body
Cell, i.e. seed cell；The three-dimensional structure of specific shape is processed using the material with excellent biocompatibility, i.e. group weaver
Engineering support；Seed cell is attached to growth on tissue engineering bracket and forms cell tissue-biomaterial composites, then will be answered
Close the lesion of object implantation tissue, organ.With the continuous proliferation of cell tissue, differentiation, the life of tissue engineering bracket
Object material is gradually degraded by body, and form, function and respective organization, the consistent new tissue of organ are ultimately formed.Organizational project branch
Frame makes tissue or neomorph become possibility.
Photopolymerization direct write processing preparation natural class aquagel tissue engineering is carried out using the femtosecond laser of 780nm central wavelength
Bracket is of today one big research hotspot.In existing research achievement, researcher has symmetrical chemistry by synthesis D- π-A- π-D etc.
The photoinitiator of structure causes photopolymerization reaction using the femtosecond laser of near infrared band.
But novel photoinitiator is not commercialized, and it is larger to synthesize difficulty.And the absorption bands of commercial photoinitiator are big
Mostly in 355-405nm, and in 800nm wave band almost without absorption peak.Therefore photosensitizer is introduced in light sensitivity solution improve light
The efficiency of initiation of initiator provides a kind of new resolving ideas for the femtosecond laser photopolymerization direct write processing of natural class hydrogel.
And PBS buffer solution is used mostly in the configuration process of natural photoinitiator, so process is water phase processing, because
This needs that water-soluble and excellent bio-compatibility light initiation system is selected to configure light sensitivity solution.
Summary of the invention
Of the existing technology in order to solve the problems, such as, the invention proposes a kind of metering system acid gelatin (GelMA) water-settings
Photopolymerization direct write processing technology inside the femtosecond laser of glue.The technical solution is as follows:
Firstly, exploring a kind of metering system acid gelatin that can be used for the processing of 780nm femtosecond laser photopolymerization direct write
(GelMA) material mixture ratio of hydrogel light sensitivity solution, raw material include: GelMA hydrogel particle, the VA- being freeze-dried
086 photoinitiator, Bengal rose red (rose bengal sodium) photosensitizer, 1 × PBS buffer solution.It is characterized by:
The GelMA hydrogel particle of freeze-drying, proportion is 0.1g/mL in light sensitivity solution；
VA-086 photoinitiator, proportion is 0.01g/mL in light sensitivity solution；
Bengal rose red (rose bengal sodium) photosensitizer, proportion is 0.01g/ in light sensitivity solution
mL；
1 × PBS buffer solution, for raw material needed for dissolving configuration light sensitivity solution.
A kind of preparation methacrylic acid gelatin hydrogel that can be used for photopolymerization direct write processing inside femtosecond laser
The method of light sensitivity solution, which is characterized in that successively add GelMA, VA-086 photoinitiator and Bengal rose red photosensitizer
Enter into centrifuge tube, reuses liquid-transfering gun and 1 × PBS buffer solution is taken to be added in same centrifuge tube；Using thermostat water bath to centrifugation
37 DEG C of tepidariums of pipe are heated 10 minutes；The supersonic oscillations: using ultrasonic washing instrument to centrifuge tube supersonic oscillations 10
Minute；Configured methacrylic acid gelatin hydrogel light sensitivity solution is filtered.
Finally, having studied photopolymerization direct write processing characteristics inside the femtosecond laser of configured experimental material, it is characterised in that:
Light is carried out in metering system acid gelatin (GelMA) hydrogel light sensitivity solution using 780nm wavelength femtosecond laser
It polymerize direct write processing, is scanned using the polymer line that different laser powers and laser scanning speed are embedded in substrate of glass in advance, it can be steady
Surely the laser power range processed is 5mW to 16.5mW, and laser scanning speed range is 5 μm/s to 200 μm/s.In laser power
5mW, 10 μm/s of laser scanning speed machined parameters under the minimum process resolution ratio for obtaining 253nm.
Material processor reason of the invention is:
Function dough is carried out to gelatin, should during methacrylic anhydride ether bond rupture, the amino dehydrogenation in gelatin, hair
The GelMA hydrogel monomer that can be crosslinked is prepared in GCMS computer reaction.
Induce two-photon absorption effect in the material using ultrafast laser, the absorbing wavelength of VA-086 photoinitiator is
405nm, the femtosecond laser light source of a length of 780nm of centering cardiac wave is without absorption.Introduce Bengal rose red (rose bengal
Sodium) after photosensitizer, photosensitizer first absorbs two photons and is activated, and then transfers energy to VA-086 photoinitiator, light
Initiator absorbs energy and is cracked into free radical, and free radical has cut off the double bond in monomer or oligomer, is combined with each other into one small
Chain base.Monomeric oligomeric object constantly closes to form longer long-chain with the chainlet base junction formed before.Until two chains are connected with each other most
End form is at big long-chain or cross-linked network object reaction terminating.It is photosensitive molten when energy of light source is sufficiently strong when photoinitiator concentration is sufficiently large
Most functional groups in liquid on GelMA monomer are be combined with each other by methyl occurs fully crosslinked reaction, is eventually converged to net
Shape cross-linking agent.When photoinitiator concentration is smaller, fully crosslinked reaction, monomer can not occur for GelMA monomer when energy of light source is smaller
Upper only some functional group is be combined with each other by methyl to be crosslinked, and other functional groups do not crosslink, are eventually converged to
Organic matter long-chain, and not formed cross-linked network object.
The invention has the beneficial effects that:
Photopolymerization direct write inside a kind of femtosecond laser of metering system acid gelatin (GelMA) hydrogel proposed by the invention
Processing technology selects commercialized 405nm absorption bands VA-086 as photoinitiator, introduces commercialized Bengal rose red
The absorption efficiency that (rose bengal sodium) improves photoinitiator as photosensitizer makes to be commercialized light initiation system success
Direct write applied to 780nm central wavelength femtosecond laser is processed.Greatly reduce the configuration difficulty of light sensitivity solution.
Detailed description of the invention
Fig. 1 be 10 μm laser power 5mW, laser scanning speed/s machined parameters under gained be embedded in the poly- of substrate of glass in advance
Close the SEM photograph of the minimum feature of object line；
Fig. 2 is the procedure chart that light initiation system causes chain polymerization reaction, and wherein I is light initiation system, and R is free radical, M
For monomeric oligomeric object, R-M is chainlet base, MnFor polymer, R-MnFor chain base.
Fig. 3 is the photopolymerization mechanism of metering system acid gelatin (GelMA) hydrogel monomer, wherein figure (a) is fully crosslinked
Reaction, figure (b) are incomplete cross-linking reaction.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail.
1, it can be used for metering system acid gelatin (GelMA) hydrogel light sensitivity of photopolymerization direct write processing inside femtosecond laser
The configuration process of solution:
(1), GelMA, VA-086 photoinitiator and Bengal rose red (rose bengal sodium) photosensitizer are added
Enter into centrifuge tube, reuses liquid-transfering gun and 1mL PBS buffer solution is taken to be added in same centrifuge tube；
(2), it heats, 37 DEG C of tepidariums of centrifuge tube is heated 10 minutes using thermostat water bath；
(3), supersonic oscillations, using ultrasonic washing instrument to centrifuge tube supersonic oscillations 10 minutes；
(4), it filters, using 0.22 μm of syringe-driven filter to configured metering system acid gelatin (GelMA) water-setting
Glue light sensitivity solution is filtered.
2, photopolymerization direct write process inside a kind of femtosecond laser of metering system acid gelatin (GelMA) hydrogel:
(1), substrate of the sheet glass of 32 × 24mm, thickness 0.15mm as sample is selected in this experiment, is existed in advance before processing
Cross mark is done in order to observe the position of the three-dimensional structure of processing in sheet glass center, then successively uses detergent, deionization
Water and alcohol be cleaned by ultrasonic to sheet glass respectively to be saved backup after ten minutes.
(2), it takes the sheet glass pre-processed to be fixed on three-D displacement platform, places " returning " font with a thickness of 100 μm
Gasket takes the photosensitive solution of 30-50 μ L hydrogel to be added dropwise at gasket center, then covers solution using the coverslip of 20 × 20mm.
(3), femtosecond laser beam realizes the change of optical path direction by reflecting mirror after expanding and introduces oil immersion focusing objective len,
Focus on femtosecond laser in light sensitivity solution.It is opposite in light sensitivity solution by laser spot
Selectivity solidification is realized in displacement.
Claims (3)
1. a kind of methacrylic acid gelatin hydrogel light sensitivity solution that can be used for photopolymerization direct write processing inside femtosecond laser,
It is characterized in that, raw material include: the GelMA hydrogel particle, VA-086 photoinitiator, bengal rose feux rouges being freeze-dried
Quick dose, 1 × PBS buffer solution；The GelMA hydrogel particle, proportion is 0.1g/mL in light sensitivity solution；It is described
VA-086 photoinitiator, in light sensitivity solution proportion be 0.01g/mL；The Bengal rose red photosensitizer, In
Proportion is 0.01g/mL in light sensitivity solution.
2. a kind of preparation methacrylic acid that can be used for photopolymerization direct write processing inside femtosecond laser as described in claim 1 is bright
The method of hydrogel light sensitivity solution, which is characterized in that GelMA, VA-086 photoinitiator and Bengal rose red is photosensitive
Agent is added in centrifuge tube, reuses liquid-transfering gun and 1 × PBS buffer solution is taken to be added in same centrifuge tube；Use thermostat water bath pair
37 DEG C of tepidariums of centrifuge tube are heated 10 minutes；The supersonic oscillations: it is shaken using ultrasonic washing instrument to centrifuge tube ultrasonic wave
It swings 10 minutes；Configured methacrylic acid gelatin hydrogel light sensitivity solution is filtered.
3. photopolymerization direct write processing technology inside a kind of femtosecond laser of methacrylic acid gelatin hydrogel, it is characterised in that: make
Femtosecond laser photopolymerization direct write is carried out in methacrylic acid gelatin hydrogel light sensitivity solution with 780nm wavelength femtosecond laser to add
Work, laser power range are 5mW to 16.5mW, and laser scanning speed range is 5 μm/s to 200 μm/s.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112835268A (en) * | 2020-12-30 | 2021-05-25 | 烟台魔技纳米科技有限公司 | Bio-based water-soluble negative photoresist and application thereof in femtosecond laser direct writing processing method |
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| 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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| JPS52135341A (en) * | 1976-05-08 | 1977-11-12 | Kansai Paint Co Ltd | Method for forming colored and cured coatings by irradiation with light |
| 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 |
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| CN112835268A (en) * | 2020-12-30 | 2021-05-25 | 烟台魔技纳米科技有限公司 | Bio-based water-soluble negative photoresist and application thereof in femtosecond laser direct writing processing method |
| CN112835268B (en) * | 2020-12-30 | 2022-12-30 | 烟台魔技纳米科技有限公司 | Bio-based water-soluble negative photoresist and application thereof in femtosecond laser direct writing processing method |
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