RESUMEN
The lack of chemical diversity in light-driven reactions for 3D printing poses challenges in the production of structures with long-term ambient stability, recyclability, and breadth in properties (mechanical, optical, etc.). Herein we expand the scope of photochemistries compatible with 3D printing by introducing onium photocages for the rapid formation of poly(thiourethanes) (PTUs). Efficient nonsensitized visible-light photolysis releases organophosphine and -amine derivatives that catalyze thiol-isocyanate polyaddition reactions with excellent temporal control. Two resin formulations comprising commercial isocyanates and thiols were developed for digital light processing (DLP) 3D printing to showcase the fast production of high-resolution PTU objects with disparate mechanical properties. Onium photocages represent valuable tools to advance light-driven manufacturing of next-generation high-performance sustainable materials.
RESUMEN
The ability to 3D print structures with low-intensity, long-wavelength light will broaden the materials scope to facilitate inclusion of biological components and nanoparticles. Current materials limitations arise from the pervasive absorption, scattering, and/or degradation that occurs upon exposure to high-intensity, short-wavelength (ultraviolet) light, which is the present-day standard used in light-based 3D printers. State-of-the-art techniques have recently extended printability to orange/red light. However, as the wavelength of light increases, so do the inherent challenges to match the speed and resolution of traditional UV light-induced solidification processes (i.e., photocuring). Herein, a photosystem is demonstrated to enable low-intensity (<5 mW/cm2), long-wavelength (â¼850 nm) near-infrared (NIR) light-driven 3D printing, "invisible" to the human eye. The combination of a NIR absorbing cyanine dye with electron-rich and -deficient redox pairs was required for rapid photocuring in a catalytic manner. The rate of polymerization and time to solidification upon exposure to NIR light were characterized via in situ spectroscopic and rheological monitoring. Translation to NIR digital light processing (projection-based) 3D printing was accomplished through rigorous optimization of resin composition and printing parameters to balance the speed (<60 s/layer) and resolution (<300 µm features). As a proof-of-concept, composite 3D printing with nanoparticle-infused resins was accomplished. Preliminary analysis showed improved feature fidelity for structures produced with NIR relative to UV light. The present report provides key insight that will inform next-generation light-based photocuring technology, such as wavelength-selective multimaterial 3D bio- and composite-printing.
RESUMEN
With 3D printing, the desire is to be "limited only by imagination," and although remarkable advancements have been made in recent years, the scope of printable materials remains narrow compared to other forms of manufacturing. Light-driven polymerization methods for 3D printing are particularly attractive due to unparalleled speed and resolution, yet the reliance on high-energy UV/violet light in contemporary processes limits the number of compatible materials due to pervasive absorption, scattering, and degradation at these short wavelengths. Such issues can be addressed with visible-light photopolymerizations. However, these lower-energy methods often suffer from slow reaction times and sensitivity to oxygen, precluding their utility in 3D printing processes that require rapid hardening (curing) to maximize build speed and resolution. Herein, multifunctional thiols are identified as simple additives to enable rapid high-resolution visible-light 3D printing under ambient (atmospheric O2 ) conditions that rival modern UV/violet-based technology. The present process is universal, providing access to commercially relevant acrylic resins with a range of disparate mechanical responses from strong and stiff to soft and extensible. Pushing forward, the insight presented within this study will inform the development of next-generation 3D-printing materials, such as multicomponent hydrogels and composites.
RESUMEN
Light-driven 3D printing to convert liquid resins into solid objects (i.e., photocuring) has traditionally been dominated by engineering disciplines, yielding the fastest build speeds and highest resolution of any additive manufacturing process. However, the reliance on high-energy UV/violet light limits the materials scope due to degradation and attenuation (e.g., absorption and/or scattering). Chemical innovation to shift the spectrum into more mild and tunable visible wavelengths promises to improve compatibility and expand the repertoire of accessible objects, including those containing biological compounds, nanocomposites, and multimaterial structures. Photochemistry at these longer wavelengths currently suffers from slow reaction times precluding its utility. Herein, novel panchromatic photopolymer resins were developed and applied for the first time to realize rapid high-resolution visible light 3D printing. The combination of electron-deficient and electron-rich coinitiators was critical to overcoming the speed-limited photocuring with visible light. Furthermore, azo-dyes were identified as vital resin components to confine curing to irradiation zones, improving spatial resolution. A unique screening method was used to streamline optimization (e.g., exposure time and azo-dye loading) and correlate resin composition to resolution, cure rate, and mechanical performance. Ultimately, a versatile and general visible-light-based printing method was shown to afford (1) stiff and soft objects with feature sizes <100 µm, (2) build speeds up to 45 mm/h, and (3) mechanical isotropy, rivaling modern UV-based 3D printing technology and providing a foundation from which bio- and composite-printing can emerge.
RESUMEN
With the availability of complete genome sequence for Drosophila melanogaster, one of the next strategic goals for fly researchers is a complete gene knockout collection. The P-element transposon, the workhorse of D. melanogaster molecular genetics, has a pronounced nonrandom insertion spectrum. It has been estimated that 87% saturation of the approximately 13,500-gene complement of D. melanogaster might require generating and analyzing up to 150,000 insertions. We describe specific improvements to the lepidopteran transposon piggyBac and the P element that enabled us to tag and disrupt genes in D. melanogaster more efficiently. We generated over 29,000 inserts resulting in 53% gene saturation and a more diverse collection of phenotypically stronger insertional alleles. We found that piggyBac has distinct global and local gene-tagging behavior from that of P elements. Notably, piggyBac excisions from the germ line are nearly always precise, piggyBac does not share chromosomal hotspots associated with P and piggyBac is more effective at gene disruption because it lacks the P bias for insertion in 5' regulatory sequences.
