Micropattern Fabricated by Acropetal Migration Controlled through Sequential Photo and Thermal Polymerization.

Bottom-up patterning technology plays a significant role in both nature and synthetic materials, owing to its inherent advantages such as ease of implementation, spontaneity, and noncontact attributes, etc. However, constrained by the uncontrollability of molecular movement, energy interaction, and stress, obtained micropatterns tend to exhibit an inevitable arched outline, resulting in the limitation of applicability. Herein, inspired by auxin's action mode in apical dominance, a versatile strategy is proposed for fabricating precision self-organizing micropatterns with impressive height based on polymerization-induced acropetal migration. The copolymer containing fluorocarbon chains (low surface energy) and tertiary amine (coinitiator) is designed to self-assemble on the surface of the photo-curing system. The selective exposure under a photomask establishes a photocuring boundary and the radicals would be generated on the surface, which is pivotal in generating a vertical concentration difference of monomer. Subsequent heating treatment activates the material continuously transfers from the unexposed area to the exposed area and is accompanied by the obviously vertical upward mass transfer, resulting in the manufacture of a rectilinear profile micropattern. This strategy significantly broadens the applicability of self-organizing patterns, offering the potential to mitigate the complexity and time-consuming limitations associated with top-down methods.

RAFT Polymerisation by the Radical Decarboxylation of Carboxylic Acids.

The controlled grafting of polymers from small- and macro-molecular substrates is an essential process for many advanced polymer applications. This usually requires the pre-functionalisation of substrates with an appropriate functional group, such as a RAFT agent or ATRP initiator, which requires additional synthetic steps. In this paper, we describe the direct grafting of RAFT polymers from carboxylate containing small molecules and polymers via photochemical radical decarboxylation. This method utilises the innate functional groups present in the substrates, and achieves efficient polymer initiation in a single step with excellent control of molecular weight and dispersity.

Fast Living 3D Printing via Free Radical Promoted Cationic RAFT Polymerization.

The application of reversible deactivation radical polymerization techniques in 3D printing is emerging as a powerful method to build "living" polymer networks, which can be easily postmodified with various functionalities. However, the building speed of these systems is still limited compared to commercial systems. Herein, a digital light processing (DLP)-based 3D printing system via photoinduced free radical-promoted cationic reversible addition-fragmentation chain transfer polymerization of vinyl ethers, which can build "living" objects by a commercial DLP 3D printer at a relatively fast building speed (12.99 cm h-1 ), is reported. The polymerization behavior and printing conditions are studied in detail. The livingness of the printed objects is demonstrated by spatially controlled postmodification with a fluorescent monomer.

Immediate and Late Repair of Microhybrid Resin Composites: Effect of Silane Coupling Agent, Universal Adhesives and Photo Polymerization.

This study investigated the effect of silane coupling agent and universal adhesive application on repair bond strength of resin-based composite after bur grinding. Microhybrid resin composite (Charisma Smart) blocks (N=80; 8x8x4 mm3) were prepared, aged (37°C; 1 month), roughened, etched and randomly divided into two groups. Silane was applied to half of the groups (Porcelain Primer, Bisco), before one of the following universal primers/adhesives was applied: a) Scotchbond Universal (3M), b) All-Bond Universal (Bisco), c) G-Premio Bond (GC), and d) Clearfil SE Bond (Kuraray). In each adhesive group half of the group was photo-polymerized. The blocks were repaired with the same size resin composite and segmented into beams. Half of the beams were subjected to micro-tensile bond test (1 mm/min), while the other half was aged (37°C; 6 months) prior to testing. Failure modes were analyzed using Scanning Electron Microscopy (SEM). Data were analyzed using repeated measures of ANOVA, Tukey's post-hoc, and paired t-tests (alpha=0.05). The silane application did not affect the repair bond strength regardless of photo-polymerization of the adhesive resin. The repair bond strength decreased significantly after 6 months when adhesive resin was not photopolymerized (p⟨0.05). Photo-polymerizing universal adhesives might ensure higher repair bond strength and its maintenance after aging.

Bacteria cellulose framework-supported solid composite polymer electrolytes for ambient-temperature lithium metal batteries.

Composite polymer electrolyte (CPE) films with high room temperature ionic conductivity are urgently needed for the practical application of high-safety solid-state batteries (SSBs). Here, a flexible polymer-polymer CPE thin film reinforced by a three-dimensional (3D) bacterial cellulose (BC) framework derived from natural BC hydrogel was prepared via thein situphoto-polymerization method. The BC film was utilized as the supporting matrix to ensure high flexibility and mechanical strength. The BC-CPE attained a high room temperature ionic conductivity of 1.3 × 10-4S cm-1. The Li∣BC-CPE∣Li symmetric cell manifested stable cycles of more than 1200 h. The LCO∣BC-CPE∣Li full cell attained an initial discharge specific capacity of 128.7 mAh g-1with 82.6% discharge capacity retention after 150 cycles at 0.2 C under room temperature. The proposed polymer-polymer CPE configuration represents a promising route for manufacturing environmental SSBs, especially since cellulose biomaterials are abundant in nature.

Molecular Design of Isocyanurate Core-Based Acrylates Undergoing Volume Expansion on Radical Photo-Polymerization.

The synthesis of acrylates with an isocyanurate substituent that show significant volume expansion on radical photo-polymerization is reported. The acrylate consisting of benzyl bisurethane moieties exhibits the largest volume expansion among them and contributes to restrict volume change upon its radical photo-copolymerization with a diacrylate exhibiting volume shrinkage. Furthermore, a correlation is revealed between the volume change behavior and the polymer structure through the radical photo-polymerization of the isocyanurate core-based diacrylate with benzyl bisurethane moieties under various concentration conditions.

Adjustable Thermo-Responsive, Cell-Adhesive Tissue Engineering Scaffolds for Cell Stimulation through Periodic Changes in Culture Temperature.

A three-dimensional (3D) scaffold ideally provides hierarchical complexity and imitates the chemistry and mechanical properties of the natural cell environment. Here, we report on a stimuli-responsive photo-cross-linkable resin formulation for the fabrication of scaffolds by continuous digital light processing (cDLP), which allows for the mechano-stimulation of adherent cells. The resin comprises a network-forming trifunctional acrylate ester monomer (trimethylolpropane triacrylate, or TMPTA), N-isopropyl acrylamide (NiPAAm), cationic dimethylaminoethyl acrylate (DMAEA) for enhanced cell interaction, and 4-acryloyl morpholine (AMO) to adjust the phase transition temperature (Ttrans) of the equilibrium swollen cross-polymerized scaffold. With glycofurol as a biocompatible solvent, controlled three-dimensional structures were fabricated and the transition temperatures were adjusted by resin composition. The effects of the thermally induced mechano-stimulation were investigated with mouse fibroblasts (L929) and myoblasts (C2C12) on printed constructs. Periodic changes in the culture temperature stimulated the myoblast proliferation.

Multiphoton Laser Fabrication of Hybrid Photo-Activable Biomaterials.

The possibility to shape stimulus-responsive optical polymers, especially hydrogels, by means of laser 3D printing and ablation is fostering a new concept of "smart" micro-devices that can be used for imaging, thermal stimulation, energy transducing and sensing. The composition of these polymeric blends is an essential parameter to tune their properties as actuators and/or sensing platforms and to determine the elasto-mechanical characteristics of the printed hydrogel. In light of the increasing demand for micro-devices for nanomedicine and personalized medicine, interest is growing in the combination of composite and hybrid photo-responsive materials and digital micro-/nano-manufacturing. Existing works have exploited multiphoton laser photo-polymerization to obtain fine 3D microstructures in hydrogels in an additive manufacturing approach or exploited laser ablation of preformed hydrogels to carve 3D cavities. Less often, the two approaches have been combined and active nanomaterials have been embedded in the microstructures. The aim of this review is to give a short overview of the most recent and prominent results in the field of multiphoton laser direct writing of biocompatible hydrogels that embed active nanomaterials not interfering with the writing process and endowing the biocompatible microstructures with physically or chemically activable features such as photothermal activity, chemical swelling and chemical sensing.

Photo-Polymerization Damage Protection by Hydrogen Sulfide Donors for 3D-Cell Culture Systems Optimization.

Photo-polymerized hydrogels are ideally suited for stem-cell based tissue regeneration and three dimensional (3D) bioprinting because they can be highly biocompatible, injectable, easy to use, and their mechanical and physical properties can be controlled. However, photo-polymerization involves the use of potentially toxic photo-initiators, exposure to ultraviolet light radiation, formation of free radicals that trigger the cross-linking reaction, and other events whose effects on cells are not yet fully understood. The purpose of this study was to examine the effects of hydrogen sulfide (H2S) in mitigating cellular toxicity of photo-polymerization caused to resident cells during the process of hydrogel formation. H2S, which is the latest discovered member of the gasotransmitter family of gaseous signalling molecules, has a number of established beneficial properties, including cell protection from oxidative damage both directly (by acting as a scavenger molecule) and indirectly (by inducing the expression of anti-oxidant proteins in the cell). Cells were exposed to slow release H2S treatment using pre-conditioning with glutathione-conjugated-garlic extract in order to mitigate toxicity during the photo-polymerization process of hydrogel formation. The protective effects of the H2S treatment were evaluated in both an enzymatic model and a 3D cell culture system using cell viability as a quantitative indicator. The protective effect of H2S treatment of cells is a promising approach to enhance cell survival in tissue engineering applications requiring photo-polymerized hydrogel scaffolds.

Tailoring a Dress to Single Protein Molecules: Proteins Can Do It Themselves through Localized Photo-Polymerization and Molecular Imprinting.

Molecularly imprinted polymer nanoparticles (MIP NPs) are antibody-like recognition materials prepared by a template-assisted synthesis. MIP NPs able to target biomolecules, like proteins, are under the spotlight for their great potential in medicine, but efficiently imprinting biological templates is still very challenging. Here we propose generating a molecular imprint in single NPs, by photochemically initiating the polymerization from individual protein templates. In this way, each protein molecule tailors itself its own "polymeric dress". For this, the template protein is covalently coupled with a photoinitiator, Eosin Y. Irradiated with light at 533 nm, the Eosin moiety acts as an antenna and transfers energy to a co-initiator (an amine), which generates a radical and initiates polymerization. As a result, a polymer network is forming only around the very template molecule, producing cross-linked NPs of 50 nm, with single binding sites showing high affinity (KD 10-9 m) for their biological target, and selectivity over other proteins.

Fabrication of Multimode-Single Mode Polymer Fiber Tweezers for Single Cell Trapping and Identification with Improved Performance.

Optical fiber tweezers have been gaining prominence in several applications in Biology and Medicine. Due to their outstanding focusing abilities, they are able to trap and manipulate microparticles, including cells, needing any physical contact and with a low degree of invasiveness to the trapped cell. Recently, we proposed a fiber tweezer configuration based on a polymeric micro-lens on the top of a single mode fiber, obtained by a self-guided photopolymerization process. This configuration is able to both trap and identify the target through the analysis of short-term portions of the back-scattered signal. In this paper, we propose a variant of this fabrication method, capable of producing more robust fiber tips, which produce stronger trapping effects on targets by as much as two to ten fold. These novel lenses maintain the capability of distinguish the different classes of trapped particles based on the back-scattered signal. This novel fabrication method consists in the introduction of a multi mode fiber section on the tip of a single mode (SM) fiber. A detailed description of how relevant fabrication parameters such as the length of the multi mode section and the photopolymerization laser power can be tuned for different purposes (e.g., microparticles trapping only, simultaneous trapping and sensing) is also provided, based on both experimental and theoretical evidences.

Photo Racemization and Polymerization of (R)-1,1'-Bi(2-naphthol).

(R)-1,1'-Bi(2-naphthol) ((R)-BINOL) in an acetonitrile solution lost optical activity upon irradiation with an Hg-Xe lamp. HPLC resolution of the product indicated that (R)-BINOL was racemized upon irradiation, and SEC analysis suggested that a polymeric product was formed in the course of racemization. It is proposed that polymerization of BINOL can occur before it is racemized and that a unit in a polymer derived from BINOL may lose its optical activity afterwards due to in-chain racemization and/or reduction. The polymeric products seem to consist not only of BINOL residues but also of residues derived from acetonitrile as well as those derived through reduction of BINOL.

Synthesis and evaluation of a novel co-initiator for dentin adhesives: polymerization kinetics and leachables study.

A new tertiary amine co-initiator (TUMA) containing three methacrylate-urethane groups was synthesized for application in dentin adhesives. The photopolymerization kinetics and leaching of unreacted components from methacrylate-based dental polymers formulated with this new co-initiator were determined. The newly synthesize co-initiator showed good chemical stability and decreased amine release from the initiator system. This study provides important information for the future development of biocompatible dentin adhesives/composites.

Rheological and Mechanical Characterization of 3D-Printable Solid Propellant Slurry.

This study delves into the rheological and mechanical properties of a 3D-printable composite solid propellant with 80% wt solids loading. Polybutadiene is used as a binder with ammonium sulfate, which is added as an inert replacement for the ammonium perchlorate oxidizer. Further additives are introduced to allow for UV curing. An in-house illumination system made of four UV-A LEDs (385 nm) is employed to cure the resulting slurry. Rheological and mechanical tests are conducted to evaluate the viscosity, ultimate tensile strength and strain, and compression behavior. Viscosity tests are performed for both pure resin and complete propellant composition. A viscosity reduction factor is obtained for the tested formulations when pre-heating slurry. Uniaxial tensile and compression tests reveal that the mechanical properties are consistent with previous research. Results emphasize the critical role of temperature and solid loading percentage. Pre-heating resin composites may grant a proper viscosity reduction while keeping mechanical properties in the applicability range. Overall, these findings pave the way for the development of a 3D printer prototype for composite solid propellants.

Influence of fluorescent dopants on the vat photopolymerization of acrylate-based plastic scintillators for application in neutron/gamma pulse shape discrimination.

Plastic scintillators, a class of solid-state materials used for radiation detection, were additively manufactured with vat photopolymerization. The photopolymer resins consisted of a primary dopant and a secondary dopant dissolved in a bisphenol A ethoxylate diacrylate-based matrix. The absorptive dopants significantly influence important print parameters, for example, secondary dopants decrease the light penetration depth by a factor > 12 ×. The primary dopant 2,5-diphenyloxazole had minimal impact on the printing process even when loaded at 25 % by mass of the resin. Working curve measurements, which relate energy dose to cure depth, were performed as a function of feature size to further assess the influence of dopants. Photopatterns smaller than 150 µm width had apparent increases in critical energy dose compared to larger photopatterns, while all resins maintained printed features in line gratings with 50 µm of separation. Printed scintillator monoliths were compared to scintillators cast by traditional molding, demonstrating that the layer-by-layer printing process does not decrease scintillation response. A maximum light output of 31 % of a benchmark plastic scintillator (EJ-200) and successful pulse shape discrimination were achieved with 20 % by mass 2,5-diphenyloxazole as the primary dopant and 0.1 % by mass 9,9-dimethyl-2,7-distyrylfluorene as the secondary dopant in printed scintillator samples.

Fabrication of 3D Printed Ceramic Part Using Photo-Polymerization Process.

Ceramics are high-strength and high-temperature resistant materials that are used in various functional parts. However, due to the high strength and brittleness properties, there are many difficulties in the fabrication of complex shapes. Therefore, there are many studies related to the fabrication of ceramic parts using 3D printing technology optimized for complex shapes. Among them, studies using photo-polymerization (PP) 3D printing technology with excellent dimensional accuracy and surface quality have received the most widespread attention. To secure the physical properties of sintered ceramic, the content and distribution of materials are important. This study suggests a novel 3D printing process based on a high-viscosity composite resin that maximizes the content of zirconia ceramics. For reliable printing, the developed 3D printers that can adjust the process environment were used. To minimize warpage and delamination, the divided micro square pattern images were irradiated in two separate intervals of 1.6 s each while maintaining the internal chamber temperature at 40 °C. This contributed to improved stability and density of the sintered structures. Ultimately, the ceramic parts with a Vickers hardness of 12.2 GPa and a relative density of over 95% were able to be fabricated based on a high-viscosity resin with 25,000 cps.

Solid Rocket Propellant Photo-Polymerization with an In-House LED-UV Prototype.

Composite solid propellants have used cast molding production technology for many decades, with intrinsic limitations on production flexibility, promptness, and grain geometry, as well as environmental implications on toxicity and global carbon footprint. This traditional method involves the use of toxic chemicals, has a long processing time, requires high temperature, and the products have limited geometries. To overcome those issues, different photo-curable resins have been evaluated as possible matrices. In fact, the UV-curing process is fast and has low energy consumption. The photocuring reaction parameters of six different pristine formulations were evaluated by Fourier transform infrared spectroscopy analysis. After finding the optimal curing parameters, different composites were prepared by adding 75 or 80 wt% ammonium sulfate particles used as an inert replacement for the oxidant. The thermomechanical properties and thermal resistance of the UV-cured composites were characterized via dynamic thermal-mechanical and thermogravimetric analysis. Subsequently, the mechanical properties of the inert propellants were investigated by tensile tests. The most promising resin systems for the production of solid rocket propellants were then 3D printed by an in-house developed illumination system and the obtained object micro-structure was evaluated by X-ray computed tomography.

Development of Photo-Polymerization-Type 3D Printer for High-Viscosity Ceramic Resin Using CNN-Based Surface Defect Detection.

Due to the high hardness and brittleness of ceramic materials, conventional cutting methods result in poor quality and machining difficulties. Additive manufacturing has also been tried in various ways, but it has many limitations. This study aims to propose a system to monitor surface defects that occur during the printing process based on high-viscosity composite resin that maximizes ceramic powder content in real time using image processing and convolutional neural network (CNN) algorithms. To do so, defects mainly observed on the surface were classified into four types by form: pore, minor, critical, and error, and the effect of each defect on the printed structure was tested. In order to improve the classification efficiency and accuracy of normal and defective states, preprocessing of images obtained based on cropping, dimensionality reduction, and RGB pixel standardization was performed. After training and testing the preprocessed images based on the DenseNet algorithm, a high classification accuracy of 98% was obtained. Additionally, for pore and minor defects, experiments confirmed that the defect surfaces can be improved through the reblading process. Therefore, this study presented a defect detection system as well as a feedback system for process modifications based on classified defects.

Synthesis, characterization, photo-polymerization, hydrolytic stability, and etching behavior of new self-etch adhesive monomers.

Considering the poor hydrolytic stability of the most methacrylate-based functional monomers of self-etch dental adhesives in acidic and aqueous conditions, in this study allyl-based photo-polymerizable self-etch monomers was synthesized in order to improve the hydrolytic stability. The new self-etch monomers based on phosphonic acid functional groups were synthesized through a two-step procedure. First, phosphoric anhydride, poly-phosphoric acid, and polyethylene glycol were reacted to produce phosphate ester precursor (P-PEG-P). Next, allyl 2, 3-epoxypropyl ether was reacted with P-PEG-P to synthesize allyl self-etch monomer. Glycidyl methacrylate was also reacted with P-PEG-P to synthesize a methacrylate self-etch analogue monomer. The monomers were characterized using FTIR and 1H-NMR spectroscopy. The viscosities of monomers were measured using a rheometer. The degree photopolymerization conversion of monomers was measured using FTIR spectroscopy. The pH assay was performed by a digital pH-meter. The etching behavior of the monomers on human teeth was studied using scanning electron microscopy (SEM). Thermo-gravimetric analysis (TGA) was performed to evaluate the possible interaction of the monomers with tricalcium phosphate (TCP). The solubility of synthesized monomers was examined in ethanol, acetone, and water. The hydrolytic stability of cured resins in artificial saliva during 4 months was also surveyed. The synthesis of new self-etching monomers was successfully confirmed by spectroscopy analyses. The results represented appropriate viscosity of self-etching monomers around 1 (Pa s). The resin containing methacrylate monomer exhibited its degree of conversion is more than that of allyl monomer (p < 0.05). The allyl and methacrylate self-etch monomers exhibited pH values of 1.2 and 1.3, respectively. SEM micrograph verified that the synthesized monomers were able to suitable etching of the enamel human premolar teeth. The data obtained from TGA tests revealed that thermal stability of (TCP) containing monomers is enhanced. Also, the monomers exhibited an excellent solubility in polar solvents, but when they are mixed with TCP, they are not, anymore, dissolved in these solvents. Furthermore, the allyl monomer showed higher hydrolytic stability than the methacrylate monomer. The new photo-polymerizable acidic monomer based on allyl functionality showed enhanced hydrolytic stability compared to methacrylate-based monomer. It may be considered as a promising monomer for self-etch dental adhesives.

Real-time measurement of transmittance changes during photo-polymerization of conventional and bulk-fill composites.

This study investigated transmittance changes during photo-polymerization of composites in real-time. The transmittance changes of one conventional micro-hybrid, three conventional nano-hybrid, and four bulk-fill composites were measured before, during, and after photo-polymerization, and the maximum rate of transmittance change was compared with that of polymerization shrinkage. A significant difference in transmittance of composite between before and after photo-polymerization was observed. The transmittance of composites except for one bulk-fill composite increased during photo-polymerization. There was a correlation between the maximum rate of transmittance change and the maximum rate of polymerization shrinkage. The transmittance analysis of composites gives very important information to know for the final aesthetic restoration and allows to evaluate polymerization kinetics.