Photopolymerization Rate Research Articles

Employing Singlet-Singlet Energy Transfer for Boosting the Reactivity of Type I Photoinitiators in Radical Photopolymerization.

A remarkable and unexpected increase in the photopolymerization efficiency of an acrylic resin by a bisacylphosphine oxide photoinitiator was observed when an optical brightener was present in the medium. High values for the maximal rates of photopolymerization were obtained by RT-FTIR at 365 nm under a very low irradiance of 1 mW/cm2. Fluorescence studies revealed that the quenching process occurs through singlet-singlet energy transfer between the first singlet excited state of the optical brightener and the ground state photoinitiator. This mechanism acts as an additional pathway for the excitation of the photoinitiator, thereby increasing the total amount of initiating radicals. Using the Förster resonance energy transfer model, we calculated the relative efficiency of the photosensitization process with respect to the direct excitation efficiency of the photoinitiator. The results demonstrate that the photosensitization process can be predicted, paving the way for further improvements in photoinitiating systems.

Employing Singlet‐Singlet Energy Transfer for Boosting the Reactivity of Type I Photoinitiators in Radical Photopolymerization

AbstractA remarkable and unexpected increase in the photopolymerization efficiency of an acrylic resin by a bisacylphosphine oxide photoinitiator was observed when an optical brightener was present in the medium. High values for the maximal rates of photopolymerization were obtained by RT‐FTIR at 365 nm under a very low irradiance of 1 mW/cm2. Fluorescence studies revealed that the quenching process occurs through singlet‐singlet energy transfer between the first singlet excited state of the optical brightener and the ground state photoinitiator. This mechanism acts as an additional pathway for the excitation of the photoinitiator, thereby increasing the total amount of initiating radicals. Using the Förster resonance energy transfer model, we calculated the relative efficiency of the photosensitization process with respect to the direct excitation efficiency of the photoinitiator. The results demonstrate that the photosensitization process can be predicted, paving the way for further improvements in photoinitiating systems.

Photocurable vitrimers with malleable and self-healing trade-off enabled by manipulating dynamic boronic ester bonds

Although numerous strategies refer to dynamic covalent bond exchanges of small molecules for self-repairing thermosets, it remains a critical challenge to be able to jointly tune the malleability and dynamic properties of photocurable materials via extending dynamical small molecule bridging chains with tunable kinetic features. Herein, we successfully synthesized two typical diboronic ester molecules (diboronic ester dithiol/diacid) with variable dioxaborolane metathesis kinetics, which acted as dynamical interlinking segments constructing simple hydrogenated bisphenol A (HBA) epoxy backbone to achieve dynamically cross-linking feature. Subsequently, the acrylate- and anhydride-modified HBA vitrimers bearing diboronic ester-extending segment variants and photocuring traits are successfully synthesized by a one-pot reaction. Consequently, it is demonstrated that the embedded amounts of dynamic diboronic ester bonds in the backbone play a key role in the photopolymerization rate of photocurable vitrimers. The photopolymerization rate decreases significantly as more diboronic ester segments. Moreover, the diboronic ester dithiol-mediated photocurable vitrimer (HBA-S) exhibits enhanced malleability (strain at break of 26.6 %), desirable photo-crosslinked network, and accelerated thermal-triggered self-healing ability (scratch self-healing efficiency of closing to 100 % at 150 °C), compared to those of the diboronic ester diacid-mediated vitrimer (HBA-O) under identical conditions. This work validates the probability of transferring the dioxaborolane metathesis of small molecules to dynamic properties of bulk UV-curing materials, which provides valuable guidance for the rational design and fabrication of tunable dynamic photocurable materials.

Synthesis and Properties of Photocurable Polymers Derived from the Polyesters of Glycerol and Aliphatic Dicarboxylic Acids.

The rapid development of 3D printing technology and the emerging applications of shape memory elastomer have greatly stimulated the research of photocurable polymers. In this work, glycerol (Gly) was polycondensed with sebacic, dodecanedioic, or tetradecanedioic acids to provide precursor polyesters with hydroxyl or carboxyl terminal groups, which were further chemically functionalized by acryloyl chloride to introduce sufficient, photocurable, and unsaturated double bonds. The chemical structures of the acrylated polyesters were characterized by FT IR and NMR spectroscopies. The photoinitiated crosslinking behavior of the acrylated polyesters under ultraviolet irradiation without the addition of any photoinitiator was investigated. The results showed that the precursor polyesters that had a greater number of terminated hydroxyls and a less branched structure obtained a relatively high acetylation degree. A longer chain of aliphatic dicarboxylic acids (ADCAs) and higher ADCA proportion lead to a relatively lower photopolymerization rate of acrylated polyesters. However, the photocured elastomers with a higher ADCA proportion or longer-chain ADCAs resulted in better mechanical properties and a lower degradation rate. The glass transition temperature (Tg) of the elastomer increased with the alkyl chain length of the ADCAs, and a higher Gly proportion resulted in a lower Tg of the elastomer due to its higher crosslinking density. Thermal gravimetric analysis (TGA) showed that the chain length of the ADCAs and the molar ratio of Gly to ADCAs had less of an effect on the thermal stability of the elastomer. As the physicochemical properties can be adjusted by choosing the alkyl chain length of the ADCAs, as well as changing the ratio of Gly:ADCA, the photocurable polyesters are expected to be applied in multiple fields.

Multi-material 3D printed eutectogel microneedle patches integrated with fast customization and tunable drug delivery

Microneedle patches are emerging multifunctional platforms for transdermal diagnostics and drug delivery. However, it still remains challenging to develop smart microneedles integrated with customization, sensing, detection and drug delivery by 3D printing strategy. Here, we present an innovative but facile strategy to rationally design and fabricate multifunctional eutectogel microneedle (EMN) patches via multi-material 3D printing. Polymerizable deep eutectic solvents (PDES) were selected as printing inks for rapid one-step fabrication of 3D printing functional EMN patches due to fast photopolymerization rate and ultrahigh drug solubility. Moreover, stretchable EMN patches incorporating rigid needles and flexible backing layers were easily realized by changing PDES compositions of multi-material 3D printing. Meanwhile, we developed multifunctional smart multi-material EMN patches capable of performing wireless monitoring of body movements, painless colorimetric glucose detection, and controlled transdermal drug delivery. Thus, such multi-material EMN system could provide an effective platform for the painless diagnosis, detection, and therapy of a variety of diseases.

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 22.5mm h-1, (ii) excellent feature resolution (≈20µm), 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.

Triphenylamine-substituted BODIPY dye based photoinitiators for free radical and cationic photopolymerization under visible LED irradiation and application in 3D printing

Until now the photopolymerization process is largely dependent on the hazardous UV or near UV light irradiation. Herein this work, a series of boron dipyrromethene (BODIPY) derivatives substituted by electron-donating triphenylamine moiety on different positions were introduced and investigated thoroughly. Markedly, their photoinitiation abilities under mild conditions, e.g. visible LEDs irradiation and room temperature, were examined for the first time. In combination with an iodonium salt and an amine as the co-initiators, these BODIPY dyes could form three-component photoinitiating systems (PISs) for the purpose to initiate both the free radical polymerization of acrylate monomers and cationic polymerization of epoxy monomers. Interestingly, under the irradiation of LED@405 nm, LED@530 nm or LED@660 nm, some of these BODIPYs-based PISs could conduct high monomeric conversion and rapid photopolymerization rates, as reflected by the relevant photopolymerization kinetics. Then the notable photochemical reactivity of these BODIPY dyes was examined by both steady state photolysis and fluorescence quenching experiments, and theoretical calculation was also performed on them in details. Finally, photocuring 3D printing technique was applied to the acrylate/epoxy mixture resin, as the result the BODIPYs-based PISs demonstrated great potential to fabricate truly three-dimensional objects in macroscopic scale with excellent spatial resolution.

Radiation Curing of Phosphorus Telomer-Based Coatings Using UV LEDs or Medium-Pressure Mercury Lamp

In the presented study, UV LEDs (365 nm) or a medium-pressure mercury lamp (UV-ABC) were verified as UV radiation sources initiating the photocrosslinking process of varnishes based on novel photopolymerizable phosphorus (meth)acrylate oligomers. Coating formulations were composed of (meth)acrylic/styrene telomers with terminal P-atoms (prepared via a UV phototelomerization process) and different photoinitiators (HAPs, APOs, or APO blends). The kinetics of the UV crosslinking process of the coating formulations depending on UV irradiation and the UV range was investigated by the photo-DSC method. Moreover, the hardness of the varnishes and the conversion of double bonds using the FTIR method were tested. The photopolymerization rate and the photoinitiation index, depending on the type of photoinitiator, were as follows: APOs < APO blends < HAPs. However, the highest coating hardness results were obtained using the least reactive photoinitiator from the APO group, i.e., Omnirad TPOL, or a mixture of three different types of acylphosphine (Omnirad BL 750). The greater effectiveness of the above-mentioned APOs over HAP was also demonstrated when using a UV LED lamp at 365 nm with a low UV dose and UV irradiance, thanks to the presence of phosphoric acid diester in the coating composition, acting as both a telogen and an antioxidant.

Preparation and Mechanical Properties of UV-Curable Epoxy Acrylate/Modified Aramid Nanofiber Nanocomposite Films.

In order to enhance the mechanical properties of UV-curable epoxy acrylate (EA)-based coatings, 3-(trimethoxysilyl)propyl methacrylate modified aramid nanofibers (T-ANFs) were synthesized and used as nanofillers to prepare EA/T-ANF nanocomposite films. The morphology of T-ANFs was characterized by transmission electron microscopy. The chemical structure of T-ANFs was analyzed via infrared spectroscopy, confirming successful grafting of methyl methacryloyloxy groups onto the surface of aramid nanofibers (ANFs). Real-time infrared spectroscopy was employed to investigate the influence of ANFs and T-ANFs on the photopolymerization kinetics of the EA film. The results revealed that the addition of ANFs and T-ANFs led to a decrease in the photopolymerization rate during the initial stage but had little impact on the final double bond conversion, with all samples exhibiting a conversion rate of over 83%. The incorporation of ANFs improved the tensile strength of the films while significantly reducing their Young's modulus. In contrast, the addition of T-ANFs led to a substantial increase in both tensile stress and Young's modulus of the films. For instance, the tensile strength and Young's modulus of the 0.1 wt% of T-ANF film increased by 52.7% and 41.6%, respectively, compared to the pure EA film. To further study the dispersion morphology and reinforcement mechanism, the cross-sectional morphology of the films was characterized by scanning electron microscopy.

Catalyst-free and visible light-induced RAFT alternating polymerization of 1,3-pentadiene isomers and maleic anhydride

Visible light-mediated photoinduced reversible addition-fragmentation chain transfer polymerization (RAFT) copolymerization of 1,3-pentadiene isomers and maleic anhydride (MAH) in the absence of photocatalysts or photoinitiators was realized in tetrahydrofuran (THF) solvent at r.t. under various visible wavelengths. The well-defined alternating copolymers were successfully and efficiently synthesized by directly using O-ethyl-S-benzoic thioanhydride (EBT) as chain transfer agent activated by blue light (460 nm). The conventional thermal-initiated radical copolymerization of 1,3-pentadiene (PD) isomers (except cis-1,3-pentadiene (CP)) and MAH gave both DA cycloaddition products and alternating sequence copolymers. In contrast, the alternating copolymer was the only isolated product in this photoinitiated polymerization system, in which the DA reaction was completely suppressed. Moreover, both trans-1,3-pentadiene (TP) and PD isomers can be copolymerized with MAH to give alternating copolymers with high yields up to 100%, although the photopolymerization rates are in the order: PD > CP > TP. And the copolymerization can be implemented by simply switching the light source ON/OFF. We supposed that the donor–acceptor interaction between the PD and MAH (similar to St (styrene)/MAH system) plays an important role in this novel light-induced RAFT alternating copolymerization behavior.

Pore Structure Tuning of Poly-EGDMA Biomedical Material by Varying the O-Quinone Photoinitiator.

Porous polymer monoliths with thicknesses of 2 and 4 mm were obtained via polymerization of ethylene glycol dimethacrylate (EGDMA) under the influence visible-light irradiation in the presence of a 70 wt% 1-butanol porogenic agent and o-quinone photoinitiators. The o-quinones used were: 3,5-di-tret-butyl-benzoquinone-1,2 (35Q), 3,6-di-tret-butyl-benzoquinone-1,2 (36Q), camphorquinone (CQ), and 9,10-phenanthrenequinone (PQ). Porous monoliths were also synthesized from the same mixture but using 2,2'-azo-bis(iso-butyronitrile) (AIBN) at 100 °C instead o-quinones. According to the results of scanning electron microscopy, all the resulting samples were conglomerates of spherical, polymeric particles with pores between them. Use of mercury porometry showed that the interconnected pore systems of all the polymers were open. The average pore size, Dmod, in such polymers strongly depended on both the nature of the initiator and the method of initiation of polymerization. For polymers obtained in the presence of AIBN, the Dmod value was as low as 0.8 μm. For polymers obtained via photoinitiation in the presence of 36Q, 35Q, CQ, and PQ, the Dmod values were significantly greater, i.e., 9.9, 6.4, 3.6, and 3.7 μm, respectively. The compressive strength and Young's modulus of the porous monoliths increased symbatically in the series PQ < CQ < 36Q < 35Q < AIBN with decreasing proportions of large pores (over 12 μm) in their polymer structures. The photopolymerization rate of the EGDMA and 1-butanol, 30:70 wt% mixture was maximal for PQ and minimal for 35Q. All polymers tested were non-cytotoxic. Based on the data from MTT testing, it can be noted that the polymers obtained via photoinitiation were characterized by their positive effect on the proliferative activity of human dermal fibroblasts. This makes them promising osteoplastic materials for clinical trials.

Enhanced Schlieren System for In Situ Observation of Dynamic Light–Resin Interactions in Projection-Based Stereolithography Process

Abstract Digital maskless lithography is gaining popularity due to its unique ability to quickly fabricate high-resolution parts without the use of physical masks. By implementing controlled grayscaling and exposure control, it has the potential to replace conventional lithography altogether. However, despite the existence of a theoretical foundation for photopolymerization, observing the voxel growth process in situ is a significant challenge. This difficulty can be attributed to several factors, including the microscopic size of the parts, the low refractive index difference between cured and uncured resin, and the rapid rate of photopolymerization once it crosses a certain threshold. As such, there is a pressing need for a system that can address these issues. To tackle these challenges, the paper proposes a modified Schlieren-based observation system that utilizes confocal magnifying optics to create a virtual screen at the camera's focal plane. This system allows for the visualization of the minute changes in refractive indices made visible by the use of Schlieren optics, specifically the deflection of light by the changing density-induced refractive index gradient. The use of focusing optics provides the system with the flexibility needed to position the virtual screen and implement optical magnification. The researchers employed single-shot binary images with different pixel numbers to fabricate voxels and examine the various factors affecting voxel shape, including chemical composition and energy input. The observed results were then compared against simulations based on Beer–Lambert's law, photopolymerization curve, and Gaussian beam propagation theory. The physical experimental results validated the effectiveness of the proposed observation system. The paper also briefly discusses the application of this system in fabricating microlenses and its advantages over theoretical model-based profile predictions.

Vat photopolymerization 3D printing of transparent, mechanically robust, and self-healing polyurethane elastomers for tailored wearable sensors

As flexible sensors are soft and prone to damage in practical applications, stretchable conductors with self-healing capacity can extend their service life. However, existing vat photopolymerization (VP) 3D-printed self-healing elastomers generally have a tensile strength of less than 1 MPa, which limits the load-bearing capacity and application range of the flexible sensors. Herein, a photocurable oligomer comprising dynamic hindered urea bonds (HUBs) was synthesized to prepare self-healing elastomers. By using a surface-functionalized spherical nano-silica (Nano-SiO2) for reinforcement modification, the tensile strength and elongation at break of the 3D-printed elastomer were enhanced by 73.7% and 111.3%, respectively, without compromising the transparency and photopolymerization rate. The fractured elastomer exhibited a high tensile strength of 5.44 MPa and a stretchability of 372% after self-healing. Subsequently, a stretchable ionic conductive elastomer (SICE) with high transparency and self-healing properties was developed by incorporating ionic liquids into the 3D-printed elastomer. The high resolution of VP-based 3D printing allowed the construction of pyramid-Kelvin lattice microstructures in the pressure sensor, which enhanced the pressure sensitivity of the sensor several times compared to the pyramid structure. In addition, combining Voronoi tessellation and kirigami art to fabricate tailored wearable sensors with smart structures, broadens the application range and improves the wearing comfort of the sensors.

Theoretical study of the reaction–diffusion model of a three-component photopolymerizable system taking into account the shrinking effect

We present a further development of theoretical modeling of photo-induced lens formation in polymerizable matrix containing quantum dots (QDs), to take into account also the shrinkage effect by advancing the model of void formation. The intensity dependence of the photopolymerization rate is considered along with the induced diffusion of monomers and QDs, as well as the change of the concentration of voids. The monomer, polymer, and QDs concentrations as well as the effective refractive index of the resulting composite material are calculated subject to the formation of voids in the cell. The challenges, related to this approach, are outlined, and the focal power of the photoinduced lens is calculated.

Influence of Methacrylate and Vinyl Monomers on Radical Bulk Photopolymerization Process and Properties of Epoxy-Acrylate Structural Adhesives

In this paper, epoxy-acrylate structural adhesives tapes (SATs) were obtained from Bisphenol A-based liquid epoxy resin and epoxy acrylic resins (EARs). A new method of EARs preparation, i.e., the free radical bulk photopolymerization process (FRBP), was studied in detail. The influence of methacrylic monomers (methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, (2-acetoacetoxy)ethyl methacrylate) and vinyl monomers (N-vinylpyrrolidone and styrene) on the FRBP process of base monomers (i.e., butyl acrylate, glycidyl methacrylate and 2-hydroxyethyl acrylate) was investigated. The kinetics of photopolymerization process was monitored by photo-differential scanning calorimetry method. The properties of the obtained EARs (viscosity and average molecular weights), as well as monomers conversion using 1H NMR, were determined. It was revealed that styrene significantly decreases the photopolymerization rate and increases the final monomers conversion (+27%). However, the resulting tetrapolymers BA-co-GMA-co-HEA-co-STY have low molecular weights and low polydispersity (2.2). Methacrylate monomers with shorter aliphatic chains (<C4) also decrease the rate of photopolymerization due to the length of the aliphatic chain increasing. Surprisingly, the best results of adhesion to steel and shear strength were obtained for SAT based on epoxy acrylate resin with styrene (11 N/25 mm and 20.8 MPa, respectively). However, the thermomechanical properties of SAT with styrene were weaker than those with methacrylates.

Influence of Luminescent Properties of Powders on the Fabrication of Scintillation Ceramics by Stereolithography 3D Printing

Luminescent and scintillation ceramic materials with complex shapes, which can be created by stereolithography 3D printing, are of interest for special phosphor and detector applications. Starting powders for such ceramics may possess UV absorption bands; therefore, it is important to study the possible influence of the powders’ luminescent properties on the printing process. This paper deals with complex garnet oxides, Y3Al5O12 and Gd3Al2Ga3O12—well-known hosts for luminescent materials. The photopolymerization rates of slurries based on the luminescent powders produced by various chemical routes are studied, as well as available printing regimes. The slurries containing Ce-doped powders with a broad absorption band in UV have significantly lower photopolymerization rates compared to the undoped ones; a high Ce doping virtually hinders printing with layers thicker than 25–50 μm. Furthermore, the choice of powder synthesis method is shown to influence the printing process. Slurries with Tb-doped powder, with absorption lines at shorter wavelengths, have good photopolymerization activity, close to that of the undoped powder, and can be printed with layer thicknesses of 25–100 μm.

Efficient synthesis of superabsorbent beads using photopolymerization with a low-cost method

Superabsorbent polymers are widely used in hygiene, agriculture, and contamination removal products. The preparation of superabsorbent beads has been reported in the literature from thermal and photopolymerizations of hydrophilic monomers. The rate of photopolymerization is normally faster than thermal polymerization. Our study aimed to test whether the fast photopolymerization technique would work with cheap, easily accessible monomers, and simple equipment that is affordable to high school students within a typical chemistry lab setting. We also evaluated the water absorbance of polymers prepared from hydrophilic monomers. We chose two hydrophilic monomers, N,N’-dimethylacrylamide (DMAA) and N-hydroxyethyl acrylamide (HEAA), and employed LED UV/Vis light as the light source to break photoinitiator molecules, with silicone oil as the polymerization medium. We hypothesized that superabsorbent beads could be prepared from DMAA and HEAA using the fast photopolymerization technique at room temperature using silicone oil. Our experiments demonstrated the synthesis of superabsorbent beads from a mixture of DMAA, HEAA, and photoinitiator in 60 seconds at ambient conditions. We also discovered that water absorbance increased with the increase of DMAA when its concentration was equal to or less than 25% by weight in the monomer mixture. Beads were completely soluble in water when the concentration of DMAA was equal to or over 50% by weight. Beads with a 25:75 DMAA:HEAA weight ratio demonstrated the highest efficiency among the six compositions tested. Our research also paves the way for high school students to investigate advanced polymerizations in a very simple way.

Effect of metal/dielectric substrates on photopolymerization of BITh thin films

We have studied effects of metal–dielectric substrates on photopolymerization of [2,2ʹ-Bi-1H-indene]-1,1ʹ-dione-3,3ʹ-diyl diheptanoate (BITh) monomer. We synthetized BITh and spin-coated it onto a variety of dielectric, metallic, and metal–dielectric substrates. The films were exposed to radiation of a UV–Visible Xe lamp, causing photo-polymerization of monomer molecules. The magnitude and the rate of the photo-polymerization were monitored by measuring the strength of the ~ 480 nm absorption band, which existed in the monomer but not in the polymer. Expectedly, the rate of photo-polymerization changed nearly linearly with the change of the pumping intensity. In contrast with our early study of photo-degradation of semiconducting polymer P3HT, the rate of photo-polymerization of BITh is getting modestly higher if the monomer film is deposited on top of silver separated from the monomer by a thin insulating MgF2 layer preventing a charge transfer. This effect is partly due to a constructive interference of the incident and reflected light waves, as well as known in the literature effects of metal/dielectric substrates on a variety of spectroscopic and energy transfer parameters. At the same time, the rate of photopolymerization is getting threefold larger if monomer is deposited on Ag film directly and charge transfer is allowed. Finally, Au substrates cause modest (~ 50%) enhancement of both monomer film absorption and the rate of photo-polymerization.

Indigo carmine: A base and neutral electrolyte-mediated photoinitiator for 3D printing in high fidelity

Volumetric additive manufacturing with light is an advanced technology in diverse conventional fields. However, with the raising awareness of environmental concerns and the growing interest in biomedical applications, the safety and water solubility of the existing photoinitiators are challenged. Herein, we developed a photoinitiating system based on a blue food colorant, i.e., indigo carmine. The indigo carmine-based photoinitiating system induced a rapid photochemical reaction and photobleaching under blue and green LEDs in the alkaline medium. The unprecedented photoinitiation ability of the indigo carmine-based photoinitiating system in terms of rate of photopolymerization and the final monomer conversion was achieved under the irradiation of low-intensity light sources. Subsequently, a sophisticated 3D printing in high fidelity was carried out and a 2D seashell was designed and printed with the function of 2D–3D reversible switching. These findings demonstrated that the indigo carmine-based photoinitiating system could resolve the safety and water solubility challenges and be involved in the 3D printing of biomedical materials.

Photochemically Driven Polymeric Biocompatible and Antimicrobial Thiol-Acrylate Nanocomposite Suitable for Dental Restoration.

The development a photochemically driven polymeric composite for dental restorative materials to restore tooth cavities with antibacterial, biocompatibility, and outstanding mechanical properties is an urgent need for clinical application in stomatology. Herein, a series of polyurethane acrylate (PUA) prepolymers and antibacterial polyurethane acrylate quaternary ammonium salts (PUAQASs) were synthesized, and their mechanical and biological properties were explored. The unique secondary mercaptan with a long shelf life and low odor was used to reduce oxygen inhibition and increase cross-linking density; meanwhile, modified photocurable nano zirconia (nano ZrO2) enhances mechanical properties of the nanocomposites and possesses preeminent dispersion in the matrix. The results show that minimal inhibitory concentrations (MICs) of PUAQASs are 200 and 800 μg/mL for Staphylococcus aureus and Escherichia coli, respectively. The addition of secondary thiols significantly increases the photopolymerization rate and monomer conversion. The highest hardness and modulus reach 1.8 and 8.7 GPa compared to 1.8 and 8.3 GPa for commercial resin. The lap shear stress on the pig bone is 912 MPa, and that on commercial resin is 921 MPa. Most importantly, the photochemically driven polymeric composite has excellent biocompatibility and significantly better antimicrobial properties than commonly used commercial resins.