Macroscopic Assembly of Sericin toward Self-Healable Silk.

Silk contains an adhesive glycoprotein, silk sericin, in which silk fibroins can be enfolded and chemically stabilized. Silk sericin is gaining importance as the material for the creation of functional bioscaffolds. However, the assembly of silk sericin is generally limited to the blend of polymers or proteins due to its inherent poor mechanical strength. Here, we report a simple macroscopic controlled assembly of silk sericin fibers based on their secondary structure via wet-spinning. In addition, plasticization of silk sericin using glycerol immobilized with glutaraldehyde was found to induce dimensional stability, affording stable linear fibers with self-adhesion. Furthermore, cyclo-phenylalanine nanowires were incorporated into the silk sericin dope for a practical demonstration of their potential in artificial silk production with superstructure formation. The physicochemical characteristics of the spun fibers have also been elucidated using Fourier-transform infrared spectroscopy, electron microscopy, tensile test, differential scanning calorimetry, and 2D X-ray diffraction.

Catalyst Halogenation Enables Rapid and Efficient Polymerizations with Visible to Far-Red Light.

The driving of rapid polymerizations with visible to near-infrared light will enable nascent technologies in the emerging fields of bio- and composite-printing. However, current photopolymerization strategies are limited by long reaction times, high light intensities, and/or large catalyst loadings. The improvement of efficiency remains elusive without a comprehensive, mechanistic evaluation of photocatalysis to better understand how composition relates to polymerization metrics. With this objective in mind, a series of methine- and aza-bridged boron dipyrromethene (BODIPY) derivatives were synthesized and systematically characterized to elucidate key structure-property relationships that facilitate efficient photopolymerization driven by visible to far-red light. For both BODIPY scaffolds, halogenation was shown as a general method to increase polymerization rate, quantitatively characterized using a custom real-time infrared spectroscopy setup. Furthermore, a combination of steady-state emission quenching experiments, electronic structure calculations, and ultrafast transient absorption revealed that efficient intersystem crossing to the lowest excited triplet state upon halogenation was a key mechanistic step to achieving rapid photopolymerization reactions. Unprecedented polymerization rates were achieved with extremely low light intensities (<1 mW/cm2) and catalyst loadings (<50 µM), exemplified by reaction completion within 60 s of irradiation using green, red, and far-red light-emitting diodes. Halogenated BODIPY photoredox catalysts were additionally employed to produce complex 3D structures using high-resolution visible light 3D printing, demonstrating the broad utility of these catalysts in additive manufacturing.

Biomass-Derived Optically Clear Adhesives for Foldable Displays.

Novel acrylate monomers, derived from terpenes are synthesized for use in optically clear adhesives (OCAs) suitable for foldable displays. These OCAs are prepared using visible-light-driven polymerization, an eco-friendly method. Through physical, rheological, and mechanical characterization, the prepared OCAs possess low modulus and exhibit outstanding creep and recovery properties, making them suitable for foldable devices.

Visible-Light-Driven Rapid 3D Printing of Photoresponsive Resins for Optically Clear Multifunctional 3D Objects.

Light-driven 3D printing is gaining significant attention for its unparalleled build speed and high-resolution in additive manufacturing. However, extending vat photopolymerization to multifunctional, photoresponsive materials poses challenges, such as light attenuation and interference between the photocatalysts (PCs) and photoactive moieties. This study introduces novel visible-light-driven acrylic resins that enable rapid, high-resolution photoactive 3D printing. The synergistic combination of a cyanine-based PC, borate, and iodonium coinitiators (HNu 254) achieves an excellent printing rate and feature resolution under low-intensity, red light exposure. The incorporation of novel hexaarylbiimidazole (HABI) crosslinkers allows for spatially-resolved photoactivation upon exposure to violet/blue light. Furthermore, a photobleaching mechanism inhibited by HNu 254 during the photopolymerization process results in the production of optically-clear 3D printed objects. Real-time Fourier transform infrared spectroscopy validates the rapid photopolymerization of the HABI-containing acrylic resin, whereas mechanistic evaluations reveal the underlying dynamics that are responsible for the rapid photopolymerization rate, wavelength-orthogonal photoactivation, and observed photobleaching phenomenon. Ultimately, this visible-light-based printing method demonstrates: (i) rapid printing rate of 22.5 mm h-1, (ii) excellent feature resolution (≈20 µm), and (iii) production of optically clear object with self-healing capability and spatially controlled cleavage. This study serves as a roadmap for developing next-generation "smart" 3D printing technologies.

Iterative SuFEx approach for sequence-regulated oligosulfates and its extension to periodic copolymers.

The synthesis of sequence-regulated oligosulfates has not yet been established due to the difficulties in precise reactivity control. In this work, we report an example of a multi-directional divergent iterative method to furnish oligosulfates based on a chain homologation approach, in which the fluorosulfate unit is regenerated. The oligosulfate sequences are determined by high resolution mass spectrometry of the hydrolyzed fragments, and polysulfate periodic copolymers are synthesized by using oligomeric bisfluorosulfates in a bi-directional fashion. The synthetic utility of this iterative ligation is demonstrated by preparing crosslinked network polymers as synthetic adhesive materials.

Realizing Cross-linking-free Acrylic Pressure-Sensitive Adhesives with Intensive Chain Entanglement through Visible-Light-Mediated Photoiniferter-Reversible Addition-Fragmentation Chain-Transfer Polymerization.

A versatile and simplified synthesis scheme for intensively entangled acrylic pressure-sensitive adhesives (PSAs) was developed in this study by leveraging visible-light-driven controlled radical polymerization (photoiniferter/reversible addition-fragmentation chain-transfer polymerization) of acrylic copolymers under a controlled manner; the approach was differentiated by a single factor; molecular weight (Mw up to 2.8 MDa) with identical compositions. By manipulating Mw up to ultra-high ranges, PSAs with diversified viscoelastic properties were prepared and then assessed with a focus on realizing PSAs with a maximized degree of entanglement per chain through domination of high Mw contents, to help achieve excellent cohesiveness without a reinforcing cross-linking network. Moreover, fully linear solvent-soluble poly(acrylate)s were synthesized to facilitate reprocessing and reuse, highlighting the sustainability of the devised method and, consequently, its potential to be applied for effectively reducing industrial or daily waste.

Visible-Light-Curable Acrylic Resins toward UV-Light-Blocking Adhesives for Foldable Displays.

Current technological advances in the organic light-emitting diode panel design of foldable smartphones demand advanced adhesives with UV-blocking abilities, beyond their conventional roles of bonding objects and relieving deformation stress. However, optically clear adhesives (OCAs) with UV-blocking ability cannot be prepared using conventional UV-curing methods relying on a photoinitiator. Herein, a new acrylic resin that can be efficiently cured using visible light without oxygen removal is presented, which may be used to develop UV-blocking OCAs for use in current flexible displays. A novel photocatalyst and a specific combination of additives facilitate sufficiently rapid curing under visible light in the presence of UV-absorbers. Only a very small amount of the highly active photocatalyst is required to prepare UV-blocking OCA films with very high transparency in the visible region. Using this system, a UV-blocking OCA that nearly meets the specifications of an OCA used in commercialized foldable smartphones is realized. This technology can also be utilized in other applications that require highly efficient visible light curing, such as optically clear resins, dental resins, and 3D/4D-printable materials.

Photo-configurable embossed liquid crystal alignment layer with high azimuthal anchoring strength.

Herein we describe a photo-alignment layer of improved azimuthal anchoring energy comparable to conventional rubbing method. In order to address the inherent low anchoring stability of photo-alignment layer, we applied embossing technique to conventional photosensitive polymer film, based on the cinnamoyl photoreactive groups, to introduce physical micro-groove effect for additional anchoring energy. From this, 2.5 × 10⁻4 J/m² of azimuthal anchoring energy was achieved, which is considered as synergistic effect from both photoinduced chemical interaction and physical microgroove alignment. In this study, we conducted systematic study on change in anchoring energy as a function of both aspect ratio of embossed pattern and UV exposure dose. We also demonstrated fabrication of sophisticated multi-domain structure of LC cells and discussed theoretical interpretation through LC simulation.

Additives for Ambient 3D Printing with Visible Light.

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.

Blue laser-sensitized photopolymer for a holographic high density data storage system.

We present a new blue-sensitized photopolymer to achieve a higher storage density compared to green/red-recordable media. Photopolymers are prepared based on a two-chemistry system and their holographic recording properties are investigated. A matrix of long and flexible ether units of an epoxy precursor and a multi-crosslinkable amine hardener enhances energetic sensitivity and suppresses volume shrinkage effectively. Page-wise recording of 961 bits/page of digital data is demonstrated and long term recording stability is also verified for a period of roughly 2 months.

UV-driven in-plane rotation of a liquid crystal director in poly(vinyl cinnamate) films having microscale grooves.

The micropatterned poly(vinyl cinnamate) (PVCi) alignment layers are fabricated by a solvent-assisted micromolding method. Without UV irradiation, the alignment layer can induce the unidirectional liquid crystal (LC) orientation, which is influenced by topography-based anchoring energies. With photodimerization of PVCi by UV irradiation, we could modulate the anchoring energies caused by chemical interactions of the alignment layer. It is observed that these two different contributions compete against each other in determining LC rotation on the surface of the alignment layer. The rotation angle of LC directors could be controlled from 45° to 70° by simply changing the UV exposure dose.

Rapid High-Resolution Visible Light 3D Printing.

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.

Control of liquid crystal pretilt angles by using organic/inorganic hybrid interpenetrating networks.

A new photoalignment method of controlling the pretilt angle of liquid crystals (LCs) by using organic/inorganic hybrid interpenetrating polymer networks (IPNs) is proposed and demonstrated. In the hybrid IPN alignment layer system, the competition between poly(vinyl cinnamate) (PVCi) favoring planar alignment and poly(dimethyl siloxane) (PDMS) favoring vertical alignment made it possible to achieve pretilt angle in a wide range from 0 degrees to 90 degrees, and adjust pretilt angle as a function of PDMS content. In addition, we achieved the high azimuthal anchoring energy at the intermediate pretilt angle by using PDMS as the vertical-aligning component.

Hexaarylbiimidazoles as visible light thiol-ene photoinitiators.

OBJECTIVES: The aim of this study is to determine if hexaarylbiimidazoles (HABIs) are efficient, visible light-active photoinitiators for thiol-ene systems. We hypothesize that, owing to the reactivity of lophyl radicals with thiols and the necessarily high concentration of thiol in thiol-ene formulations, HABIs will effectively initiate thiol-ene polymerization upon visible light irradiation. METHODS: UV-vis absorption spectra of photoinitiator solutions were obtained using UV-vis spectroscopy, while EPR spectroscopy was used to confirm radical species generation upon HABI photolysis. Functional group conversions during photopolymerization were monitored using FTIR spectroscopy, and thermomechanical properties were determined using dynamic mechanical analysis. RESULTS: The HABI derivatives investigated exhibit less absorptivity than camphorquinone at 469nm; however, they afford increased sensitivity at this wavelength when compared with bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide. Photolysis of the investigated HABIs affords lophyl radicals. Affixing hydroxyhexyl functional groups to the HABI core significantly improved solubility. Thiol-ene resins formulated with HABI photoinitiators polymerized rapidly upon irradiation with 469nm. The glass transition temperatures of the thiol-ene resin formulated with a bis(hydroxyhexyl)-functionalized HABI and photopolymerized at room and body temperature were 49.5±0.5°C and 52.2±0.1°C, respectively. SIGNIFICANCE: Although thiol-enes show promise as continuous phases for composite dental restorative materials, they show poor reactivity with the conventional camphorquinone/tertiary amine photoinitiation system. Conversely, despite their relatively low visible light absorptivity, HABI photoinitiators afford rapid thiol-ene photopolymerization rates. Moreover, minor structural modifications suggest pathways for improved HABI solubility and visible light absorption.