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In native tissues, cells encounter a diverse range of stiffness, which can significantly affect their behavior and function. The ability of cells to sense and respond to these mechanical cues is essential for various physiological processes, including cell migration. Cell migration is a complex process influenced by multiple factors, with substrate stiffness emerging as a critical determinant. This study developed a technique to edit the stiffness of polyacrylamide (PAA) hydrogel substrates by adjusting the grayscale level of a photomask during photopolymerization. By analyzing cell morphologies on the hydrogel, we confirmed the development of a single PAA hydrogel substrate with continuous stiffness gradients. This method was used to explore the correlation between substrate stiffness and cell migration dynamics. The study found that cells typically migrated from softer to stiffer surfaces. When the cells initially located on stiffer surfaces, they were able to travel longer distances. Additionally, a continuous 2D stiffness gradient surface was fabricated to explore how cells migrate on smoother versus steeper stiffness gradients. The results showed that cells tended to migrate more readily on smoother stiffness gradient surfaces compared to steeper ones. This study provides valuable insights into cell migration dynamics on substrates with varying stiffness gradients. The results underscore the importance of the mechanical environment in cancer cell migration and offer promising directions for developing interventions to prevent cancer spread., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Polydopamine (PDA)-derived melanin-like materials exhibit significant photothermal conversion owing to their broad-spectrum light absorption. However, their low near-infrared (NIR) absorption and inadequate hydrophilicity compromise their utilization of solar energy. Herein, we developed metal-loaded poly(norepinephrine) nanoparticles (PNE NPs) by predoping metal ions (Fe 3+ , Mn 3+ , Co 2+ , Ca 2+ , Ga 3+ , and Mg 2+ ) with norepinephrine, a neuron-derived biomimetic molecule, to address the limitations of PDA. The chelation between catechol and metal ions induces a ligand-to-metal charge transfer (LMCT) through the formation of donor-acceptor pairs, modulating the light absorption behavior and reducing the band gap. Under 1 sun illumination, the Fe-loaded PNE coated wood evaporator achieved a high seawater evaporation rate and efficiency of 1.75 kg m -2 h -1 and 92.4%, respectively, owing to the superior hydrophilicity and photothermal performance of PNE. Therefore, this study offers a comprehensive exploration of the role of metal ions in enhancing the photothermal properties of synthetic melanins.

The simultaneous introduction of two new functionalities into the same polymeric substrate under mild reaction conditions is an interesting and important topic. Herein, dual-functional polydimethylsiloxane (PDMS) surfaces with antibacterial and antifouling properties were conveniently developed via a novel Y-shaped asymmetric dual-functional photoiniferter (Y-iniferter). The Y-iniferter was initially immobilized onto the PDMS surface by radical coupling under visible light irradiation. Afterwards, poly(2-hydroxyethyl methacrylate) (PHEMA) brushes and antibacterial ionic liquid (IL) fragments were simultaneously immobilized on the Y-iniferter-modified PDMS surfaces by combining the sulfur(VI)-fluoride exchange (SuFEx) click reaction and UV-photoinitiated polymerization. Experiments using E. coli as a model bacterium demonstrated that the modified PDMS surfaces had both the expected antibacterial properties of the IL fragments and the excellent antifouling properties of PHEMA brushes. Furthermore, the cytotoxicity of the modified PDMS surfaces to L929 cells was examined in vitro with a CCK-8 assay, which showed that the modified surfaces maintained excellent cytocompatibility. Briefly, this strategy of constructing an antibacterial and antifouling PDMS surface has the advantages of simplicity and convenience and might inspire the construction of diverse dual-functional surfaces by utilizing PDMS more effectively.

Surgical site infections constitute a major health concern that may be addressed by conferring antibacterial properties to surgical tools and medical devices via functional coatings. Bio-sourced polymers are particularly well-suited to prepare such coatings as they are usually safe and can exhibit intrinsic antibacterial properties or serve as hosts for bactericidal agents. The goal of this Review is to highlight the unique contribution of photochemistry as a green and mild methodology for the development of such bio-based antibacterial materials. Photo-generation and photo-activation of bactericidal materials are illustrated. Recent efforts and current challenges to optimize the sustainability of the process, improve the safety of the materials and extend these strategies to 3D biomaterials are also emphasized.

Biochemical networks interconnect, grow and evolve to express new properties as different chemical pathways are selected during a continuous cycle of energy consumption and transformation. In contrast, synthetic systems that push away from equilibrium usually return to the same self-assembled state, often generating waste that limits system recyclability and prevents the formation of adaptable networks. Here we show that annealing by slow proton dissipation selects for otherwise inaccessible morphologies of fibres built from DNA and cyanuric acid. Using single-molecule fluorescence microscopy, we observe that proton dissipation influences the growth mechanism of supramolecular polymerization, healing gaps within fibres and converting highly branched, interwoven networks into nanocable superstructures. Just as the growth kinetics of natural fibres determine their structural attributes to modulate function, our system of photoacid-enabled depolymerization and repolymerization selects for healed materials to yield organized, robust fibres. Our method provides a chemical route for error-checking, distinct from thermal annealing, that improves the morphologies and properties of supramolecular materials using out-of-equilibrium systems., (© 2021. The Author(s), under exclusive licence to Springer Nature Limited.)

Hydrogel patches with high toughness, stretchability, and adhesive properties are critical to healthcare applications including wound dressings and wearable devices. Gelatin methacryloyl (GelMA) provides a highly biocompatible and accessible hydrogel platform. However, low tissue adhesion and poor mechanical properties of cross-linked GelMA patches ( i.e ., brittleness and low stretchability) have been major obstacles to their application for sealing and repair of wounds. Here, we show that adding dopamine (DA) moieties in larger quantities than those of conjugated counterparts to the GelMA prepolymer solution followed by alkaline DA oxidation could result in robust mechanical and adhesive properties in GelMA-based hydrogels. In this way, cross-linked patches with ∼140% stretchability and ∼19 000 J/m 3 toughness, which correspond to ∼5.7 and ∼3.3× improvement, respectively, compared to that of GelMA controls, were obtained. The DA oxidization in the prepolymer solution was found to play an important role in activating adhesive properties of cross-linked GelMA patches (∼4.0 and ∼6.9× increase in adhesion force under tensile and shear modes, respectively) due to the presence of reactive oxidized quinone species. We further conducted a parametric study on the factors such as UV light parameters, the photoinitiator type ( i.e ., lithium phenyl-2,4,6-trimethylbenzoylphosphinate, LAP, versus 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, Irgacure 2959), and alkaline DA oxidation to tune the cross-linking density and thereby hydrogel compliance for better adhesive properties. The superior adhesion performance of the resulting hydrogel along with in vitro cytocompatibility demonstrated its potential for use in skin-attachable substrates.

Two-photon polymerization of a three-dimensional (3D) hydrogel structure has been widely applied in biological tissue engineering. For improving the biocompatibility of hydrogel structures, a new kind of ionic carbazole water-soluble photoinitiator was prepared to realize the fabrication of a 3D hydrogel structure in aqueous phase. 3,6-Bis[2-(1-methyl-pyridinium)vinyl]-9-methyl-carbazole diiodide (BMVMC) and cucurbit[7]uril (CB7) have been employed to generate a complex with better water solubility by host-guest interactions. The binding ratio of the complex was demonstrated to be 1:1 through the characterization of isothermal titration calorimetry (ITC). The two-photon absorption (TPA) cross section of the complex increases to 2500 GM compared with the 750 GM of the BMVMC molecule. Then, an aqueous-phase photoresist was obtained using the CB7/BMVMC complex as the photoinitiator and poly(ethylene glycol) diacrylate (PEGda) as the hydrogel monomer. Two-photon fabrication capability in aqueous phase has been studied using the as-prepared photoresist. A low laser threshold of 3.7 mW as well as a high resolution of 180 nm are achieved. Benefiting from the fluorescence properties of the photoinitiator, we can achieve the confocal fluorescence images without any assistance of fluorescent probes. Subsequently, a 3D engineered hydrogel scaffold microstructure was fabricated by the two-photon polymerization technology, whose biocompatibility was demonstrated by culturing the structure with living cells of L929. The BMVMC-CB7 complex and the as-prepared photoresist are demonstrated to have good biocompatibility, which is prospective for further application in tissue engineering.

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 (H 2 S) in mitigating cellular toxicity of photo-polymerization caused to resident cells during the process of hydrogel formation. H 2 S, 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 H 2 S 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 H 2 S 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 H 2 S treatment of cells is a promising approach to enhance cell survival in tissue engineering applications requiring photo-polymerized hydrogel scaffolds.

The modification of medical devices is an area that has attracted a lot of attention in recent years; particularly, those developments which search to modify existing devices to render them antimicrobial. Most of these modifications involve at least two stages (modification of the base material with a polymer graft and immobilization of an antimicrobial agent) which are both time-consuming and complicate synthetic procedures; therefore, as an improvement, this project sought to produce antimicrobial silicone (PDMS) in a single step. Using gamma radiation as both an energy source for polymerization initiation and as a source of reducing agents in solution, PDMS was simultaneously grafted with acrylic acid and ethylene glycol dimethacrylate (AAc:EGDMA) while producing antimicrobial silver nanoparticles (AgNPs) onto the surface of the material. To obtain reproducible materials, experimental variables such as the effect of the dose, the intensity of radiation, and the concentration of the silver salt were evaluated, finding the optimal reaction conditions to obtain materials with valuable properties. The characterization of the material was performed using electronic microscopy and spectroscopic techniques such as 13 C-CPMAS-SS-NMR and FTIR. Finally, these materials demonstrated good antimicrobial activity against S. aureus while retaining good cell viabilities (above 90%) for fibroblasts BALB/3T3.

In coordination-based supramolecular materials such as metallogels, simultaneous temporal and spatial control of their assembly remains challenging. Here, we demonstrate that the combination of light with acids as stimuli allows for the spatiotemporal control over the architectures, mechanical properties, and shape of porous soft materials based on metal-organic polyhedra (MOPs). First, we show that the formation of a colloidal gel network from a preformed kinetically trapped MOP solution can be triggered upon addition of trifluoroacetic acid (TFA) and that acid concentration determines the reaction kinetics. As determined by time-resolved dynamic light scattering, UV-vis absorption, and 1 H NMR spectroscopies and rheology measurements, the consequences of the increase in acid concentration are (i) an increase in the cross-linking between MOPs; (ii) a growth in the size of the colloidal particles forming the gel network; (iii) an increase in the density of the colloidal network; and (iv) a decrease in the ductility and stiffness of the resulting gel. We then demonstrate that irradiation of a dispersed photoacid generator, pyranine, allows the spatiotemporal control of the gel formation by locally triggering the self-assembly process. Using this methodology, we show that the gel can be patterned into a desired shape. Such precise positioning of the assembled structures, combined with the stable and permanent porosity of MOPs, could allow their integration into devices for applications such as sensing, separation, catalysis, or drug release.

The purpose of our study was to obtain new wound dressings in the form of hydrogels that promote wound healing taking advantage of the broad activities of elastin (ELT) in physiological processes. The hydrogel of ELT and polyvinylpyrrolidone (PVP; ELT-PVP) was obtained by cross-linking induced by gamma irradiation at a dose of 25 kGy. The physicochemical changes attributed to cross-linking were analyzed through scanning electron microscopy (SEM), infrared spectroscopy analysis with Fourier transform (FTIR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Furthermore, we performed a rheological study to determine the possible changes in the fluidic macroscopic properties produced by the cross-linking method. Finally, we accomplished viability and proliferation analyses of human dermal fibroblasts in the presence of the hydrogel to evaluate its biological characteristics. The hydrogel exhibited a porous morphology, showing interconnected porous with an average pore size of 16 ± 8.42 µm. The analysis of FTIR, DSC, and TGA revealed changes in the chemical structure of the ELT-PVP hydrogel after the irradiation process. Also, the hydrogel exhibited a rheological behavior of a pseudoplastic and thixotropic fluid. The hydrogel was biocompatible, demonstrating high cell viability, whereas ELT presented low biocompatibility at high concentrations. In summary, the hydrogel obtained by gamma irradiation revealed the appropriate morphology to be applied as a wound dressing. Interestingly, the hydrogel exhibited a higher percentage of cell viability compared with ELT, suggesting that the cross-linking of ELT with PVP is a suitable strategy for biological applications of ELT without generating cellular damage.

The limited number of commercially available photocrosslinkable resins for stereolithography has often been considered the main limitation of this technique. In this manuscript, a photocrosslinkable poly-ε-caprolactone (PCL) has been synthesized by a two-step method starting from ring opening polymerization (ROP) of ε-caprolactone. Hydroxyethyl vinyl ether (HEVE) has been used both as the initiator of ROP and as photo-curable functional group to obtain a vinyl poly-ε-caprolactone (VPCL). The following reaction of VPCL with fumaryl chloride (FuCl) results in a divinyl-fumarate polycaprolactone (VPCLF). Moreover, a catalyst based on Al, instead of the most popular Tin(II) 2-ethylhexanoate, has been employed to reduce the cytotoxicity of the material. VPCLF has been successfully used, in combination with N-vinyl-pyrrolidone (NVP), to fabricate 3D porous scaffolds by micro-stereolithography (μ-SL) with mathematically defined architectures.

The aim of the present study was to characterize nanohybrid and nanofilled composites in terms of degree of conversion (DC), rate of cure (RC), microhardness (Vickers hardness number; VHN), depth of cure, and contraction stress (CS). Ceram.X® universal- A3, duo enamel E2, and duo dentin D3 composites were compared to Tetric EvoCeram® and FiltekTMSupreme XTE composites of equivalent dentin and enamel shades under a 40 s photopolymerization protocol. DC was measured by infrared spectroscopy, calculating RC from the kinetic curve. Top and bottom VHN were determined using a Vickers indenter, and bottom/top surface ratio (Vickers hardness ratio; VHR) calculated. CS vs. time was assessed by a universal testing machine and normalized for the specimen bonding area. All materials showed DC  < 60%, Ceram.X® composites reaching higher values than the other composites of corresponding shades. RC at 5 s of photopolymerization was always higher than that at 10 s. All the Ceram.X® composites and the lighter-shaded Tetric EvoCeram® and FiltekTMSupreme XTE composites reached the RC plateau after 25 s, the remaining materials showed a slower kinetic trend. Tetric EvoCeram® and FiltekTMSupreme XTE composites displayed the softest and the hardest surfaces, respectively. Differently from darker-shaded materials, the universal and the three enamel-shaded composites resulted optimally cured (VHR >  80%). The tested composites differed in CS both during and after light cure, Tetric EvoCeram® and FiltekTMSupreme XTE composites displaying the highest and the lowest CS, respectively. Only the Ceram.X® universal-A3 reached a CS plateau value. The tested composites exhibited material-dependent chemo-mechanical properties. Increasing the curing time and/or reducing the composite layer thickness for dentin-shaded composites appears advisable.

Natural musculoskeletal systems have been widely recognized as an advanced robotic model for designing robust yet flexible microbots. However, the development of artificial musculoskeletal systems at micro-nanoscale currently remains a big challenge, since it requires precise assembly of two or more materials of distinct properties into complex 3D micro/nanostructures. In this study, we report femtosecond laser programmed artificial musculoskeletal systems for prototyping 3D microbots, using relatively stiff SU-8 as the skeleton and pH-responsive protein (bovine serum albumin, BSA) as the smart muscle. To realize the programmable integration of the two materials into a 3D configuration, a successive on-chip two-photon polymerization (TPP) strategy that enables structuring two photosensitive materials sequentially within a predesigned configuration was proposed. As a proof-of-concept, we demonstrate a pH-responsive spider microbot and a 3D smart micro-gripper that enables controllable grabbing and releasing. Our strategy provides a universal protocol for directly printing 3D microbots composed of multiple materials.

Free radical polymerization upon near-infrared (NIR) light is still the subject of intense research efforts and remains a huge challenge particularly for long wavelengths (>1000 nm). In this study, a NIR sensitizer operating upon long wavelength (1064 nm) is proposed for an efficient polymerization of acrylate monomers. A new three-component photoinitiating system is developed comprising the NIR sensitizer in combination with an Iodonium salt (Iod) and an amine. Remarkably, the NIR sensitizer (IR 1064) absorbing strongly in all the near infrared region (700-1200 nm) offers the possibility to use a broad range of irradiation wavelengths, i.e., examples are provided at 785 and 1064 nm. Such long wavelengths are characterized by many advantages such as a deeper penetration of light and therefore a better curing of the monomer but it is also much safer than UV light. Excellent performance is observed for the three-component IR 1064/Iod/Amine system under air: high conversion of acrylate functions associated with a fast polymerization time. The use of IR 1064 as NIR sensitizer with a broad NIR absorption is-to the best of current knowledge-never proposed in the literature. The photoinitiating performances are studied using real-time Fourier transform infrared spectroscopy., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

3D printing technology has been applied to various fields and its medical applications are expanding. Here, we fabricated implantable 3D bio-printed hydrogel patches containing a nanomedicine as a future tailored cancer treatment. The patches were prepared using a semi-solid extrusion-type 3D bioprinter, a hydrogel-based printer ink, and UV-LED exposure. We focused on the composition of the printer ink and semi-synthesized fish gelatin methacryloyl (F-GelMA), derived from cold fish gelatin, as the main component. The low viscosity of F-GelMA due to its low melting point was remarkably improved by the addition of carboxymethyl cellulose sodium (CMC), a pharmaceutical excipient. PEGylated liposomal doxorubicin (DOX), as a model nanomedicine, was incorporated into the hydrogel and liposome stability after photo-polymerization was evaluated. The addition of CMC inhibited particle size increase. Three types of 3D-designed patches (cylinder, torus, gridlines) were produced using a 3D bioprinter. Drug release was dependent on the shape of the 3D-printed patches and UV-LED exposure time. The current study provides useful information for the preparation of 3D printed nanomedicine-based objects.

The effect of terahertz (THz) radiation on deep tissues of human body has been considered negligible due to strong absorption by water molecules. However, we observed that the energy of THz pulses transmits a millimeter thick in the aqueous solution, possibly as a shockwave, and demolishes actin filaments. Collapse of actin filament induced by THz irradiation was also observed in the living cells under an aqueous medium. We also confirmed that the viability of the cell was not affected under the exposure of THz pulses. The potential of THz waves as an invasive method to alter protein structure in the living cells is demonstrated.

Photopolymerizable poly(ethylene glycol) (PEG) hydrogels are a promising platform for chondrocyte encapsulation and cartilage tissue engineering. This study demonstrates that during the process of encapsulation, chondrocytes alter the formation of PEG hydrogels leading to a reduction in the bulk and local hydrogel crosslink density. Freshly isolated chondrocytes were shown to interact with hydrogel precursors, in part through thiol-mediated events between dithiol crosslinkers and cell surface free thiols, depleting crosslinker concentration and causing a reduction in the bulk hydrogel crosslink density. This effect was more pronounced with increasing cell density at the time of encapsulation. Encapsulation of chondrocytes in fluorescently labeled hydrogels exhibited a gradient in hydrogel density around the cell, which was abrogated by treatment of the cells with the antioxidant estradiol prior to encapsulation. This gradient led to spatial variations in the degradation behavior of a hydrolytically degradable PEG hydrogel, creating regions devoid of hydrogel surrounding cells. Collectively, findings from this study indicate that the antioxidant defense mechanisms in chondrocytes alter the resultant properties of PEG hydrogels formed by free-radical polymerizations. These interactions will have a significant impact on tissue engineering, affecting the local microenvironment around cells and how tissue grows within the hydrogels. STATEMENT OF SIGNIFICANCE: Cell encapsulations in synthetic hydrogels formed by free-radical polymerizations offer numerous benefits for tissue engineering. Herein, we studied cartilage cells and identified that during encapsulation, cells interfered with hydrogel formation through two distinct mechanisms. Thiol-mediated events between monomers led to monomer depletion and a lower crosslinked hydrogel. Cells' antioxidant defense mechanisms interfered with free-radicals and inhibited hydrogel formation near the cell. These cell-mediated effects led to softer hydrogels and created unique hydrogel degradations patterns causing rapid degradation around the cells. The latter has benefits for tissue engineering, where these regions provide space for tissue growth. Overall, this study demonstrates that cells play a key role in how the hydrogel structure forms when cells are present., Competing Interests: Declaration of Competing Interest None., (Copyright © 2020. Published by Elsevier Ltd.)

Halloysite nanotubes (HNTs) are a kind of aluminosilicate clay with a unique hollow tubular structure that has been intensively explored for various applications especially in biomedical fields owing to their excellent biocompatibility, biodegrading potential and low cost. Surface modification of HNTs with functional polymers will greatly improve their properties and endow new functions for biomedical applications. In this work, a light-induced reversible addition-fragmentation chain transfer (RAFT) polymerization was introduced to successfully prepare HNTs based fluorescent HNTs/poly(PEGMA-Fl) composites in the presence of oxygen using diacrylate-fluorescein and poly (ethylene glycol) methyl ether methacrylate (PEGMA) as the monomers. Without other catalysts, heating, and deoxygenation procedure, the polymerization process can take place under mild conditions. Besides, owing to the introduction of fluorescein and PEGMA on the surface of HNTs, the resultant HNTs/poly(PEGMA-Fl) composites display high water dispersibility and stable fluorescence. The results from cell viability examination and confocal laser scanning microscopy also demonstrated that HNTs/poly(PEGMA-Fl) composites could be internalized by L929 cells with bright fluorescence and low cytotoxicity. Taken together, we developed a novel photo-initiated RAFT polymerization method for the fabrication of HNTs based fluorescent polymeric composites with great potential for biomedical applications. More importantly, many other multifunctional HNTs based polymer composites could also be fabricated through a similar strategy owing to good designability of RAFT polymerization., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Immunocytochemistry (ICC), or immunofluorescence microscopy, is an essential biological technique for phenotyping cells in both research and diagnostic applications. Standard ICC methods often do not work well when the cell sample contains a small number of cells (<10 000) because of the significant cell loss that occurs during washing, staining, and centrifugation steps. Cell loss is particularly relevant when working with rare cells, such as circulating tumor cells, where such losses could significantly bias experimental outcomes. In order to eliminate cell loss in ICC protocols, we present a method to encapsulate the cell sample in a photo-polymerized hydrogel thin-film. The hydrogel thin-film is permeable to antibodies and other ICC reagents, thereby allowing the use of standard ICC protocols without modification. The cell sample is physically constrained by the hydrogel at the bottom surface of a standard (unmodified) imaging microtiter plate, thereby enabling the acquisition of high-quality micrographs regardless of the properties of the cell sample or staining reagents. Furthermore, while standard ICC requires several centrifugation steps during staining and washing, our hydrogel encapsulation method requires only a single centrifugation step. This property greatly reduces the time required to perform ICC protocols and is more compatible with robotic platforms. In this study, we show that standard ICC and Cytospin protocols are extremely lossy (>70% loss) when the sample contains less than 10 000 cells, while encapsulating the cells using a permeable hydrogel thin-film results in a lossless ICC process.

In a significant breakthrough from classical molecular (i.e., nonpolymeric) iodonium salts in light-induced photochemistry, the synthesis and use of new safer polymeric iodonium salts are reported here. They are shown to be involved in charge transfer complexes (CTCs) while in interaction with a safe amino acid derivative (N-phenylglycine). Also, this study demonstrates i) the formation of CTCs between the iodonium (acceptor) and an aryl/alkyl amine (donor) through UV-vis measurements of the monomer, ii) the formation of radicals in electron spin resonance spin trapping experiments when the CTCs are irradiated by visible light (405 nm), and iii) their efficiency as a photoinitiator to polymerize three different acrylic monomers under LED irradiation at 405 nm under air and their application to 3D resolved laser writing of thick samples (3 mm). High reactivity for polymeric iodonium salts comparable with molecular ones is exhibited with the advantage of potential lower migration. To the best of the authors' knowledge, this is the first reported instance of polymeric iodonium salts acting as polymerization initiators., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Lytic polysaccharide (mono)oxygenases (LPMOs) perform oxidative cleavage of polysaccharides, and are key enzymes in biomass processing and the global carbon cycle. It has been shown that LPMO reactions may be driven by light, using photosynthetic pigments or photocatalysts, but the mechanism behind this highly attractive catalytic route remains unknown. Here, prompted by the discovery that LPMOs catalyze a peroxygenase reaction more efficiently than a monooxygenase reaction, we revisit these light-driven systems, using an LPMO from Streptomyces coelicolor (ScAA10C) as model cellulolytic enzyme. By using coupled enzymatic assays, we show that H 2 O 2 is produced and necessary for efficient light-driven activity of ScAA10C. Importantly, this activity is achieved without addition of reducing agents and proportional to the light intensity. Overall, the results highlight the importance of controlling fluxes of reactive oxygen species in LPMO reactions and demonstrate the feasibility of light-driven, tunable enzymatic peroxygenation to degrade recalcitrant polysaccharides.

Herein, it is reported for the first time that when mixed with choline chloride, itaconic acid (IA), normally a low-reactive vinyl monomer, undergoes initiator-free radical polymerization under normal daylight. Furthermore, the process results in the formation of abnormally high-molecular-weight poly(itaconic acid) derivatives with M w greater than ≈800 000 g mol -1 . Detailed 1D/2D NMR studies indicate that the polymers have two types of ionizable moieties, that is, anionic carboxylic and cationic choline ester groups in an average molar ratio of 12:1. Potentiometric titration shows polyampholyte behavior of the polymers. Tentative mechanistic studies reveal that the daylight-induced polymerization is initiated by species generated via interactions of near UV light with IA. However, EPR findings show that choline also participates in secondary radical reactions. The obtained polyampholytes are useful bio-based materials for fast and straightforward fabrication of polymer-clay nanocomposite hydrogels with excellent mechanical properties., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The present research work was aimed to synthesize neem gum-based site-specific drug delivery device for anticancer drug methotrexate at different pH condition. The hydrogel-based drug delivery device was synthesized by optimizing reaction parameters using a factorial design approach response surface method. This model comprised of various sets of reactions with varying concentrations of solvent, crosslinker, initiator and monomer under microwave radiation. Characterization of the candidate hydrogel was done using UV-visible spectrophotometer, FTIR, SEM, Raman, and XRD techniques. The release profile of the hydrogels network was studied through a methotrexate under different pH conditions. The drug encapsulation capacity was found to be around 93% and 90% in pH 7.4 and 6.8. Drug release through the synthesized hydrogel matrix was found to show non-Fickian behaviour at each medium. The hydrogel network showed less release in pH 6.8 than pH 7.4, suggesting that hydrogels may be suitable drug carriers for release of anticancer drug delivery system. Hemolysis testing was also done to check the compatibility of the synthesized drug delivery device with the four different blood samples. Hemolysis was found to be less than 1% in the case of all blood groups, which indicates that the synthesized candidate polymers are biocompatible with all blood groups., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Objectives: The aim was to assess the influence of polymerization duration, method and resin manipulation techniques on the biaxial flexural strength (BFS) and degree of conversion (DC) of bulk fill resin composites (BFRC)., Methods: One hundred and eighty disc specimens were fabricated using MultiCore (MC) and Core-It (CI) bulk fill resin composite. Each material group, specimens were divided into nine subgroups based on curing methods (Light cure for 10 and 20 s; and auto-cure) and mixing techniques (first auto-mix, second automix, and hand mix). BFS was tested with a ball indenter at a crosshead speed of 0.50 mm/min. DC was assessed for MC and CI materials for 10 s and 20 s light cure; and auto cure specimens using Fourier Transform-Infrared Spectroscopy (FTIR). Statistical data comparisons were performed using ANOVA, Bonferroni and Tukey-Kramer tests., Results: For MC and CI, BFS was highest in 10 s light cure specimens, however comparable to specimens cured for 20 s ( p > 0.05). Auto cure specimens showed lower BFS than light cured samples for both materials ( p < 0.05). Hand mixed specimens showed significantly compromised BFS compared to automix technique for MC and CI. DC % was comparable for 10 s and 20 s light cure methods for both materials ( p > 0.05), which was higher than DC % of auto cure bulk fill resins ( p < 0.05). CI showed higher DC % and BFS compared to MC bulk fill resin composite., Conclusion: Photo-polymerization duration of 10 and 20 s showed similar outcomes for BFS and DC %; and BFS for auto-mixed resins (MC and CI) was significantly higher than hand mixed resin. BFS and DC was higher in photopolymerized groups as compared to auto-cured resin regardless of the manipulation technique for both materials (MultiCore and Core it).

Stereolithography (SLA) 3D bioprinting has emerged as a prominent bioprinting method addressing the requirements of complex tissue fabrication. This chapter addresses the advancement in SLA 3D bioprinting in concurrent with the development of novel photocrosslinkable biomaterials with enhanced physical and chemical properties. We discuss the cytocompatible photoinitiators operating in the wide spectrum of the ultraviolet (UV) and the visible light and high-resolution dynamic mask projection systems with a suitable illumination source. The potential of SLA 3D bioprinting has been explored in various themes, like bone and neural tissue engineering and in the development of controlled microenvironments to study cell behavior. The flexible design and versatility of SLA bioprinting makes it an attractive bioprinting process with myriad possibilities and clinical applications.

Three-dimensional (3D) printing of human tissues and organs has been an exciting area of research for almost three decades [Bonassar and Vacanti. J Cell Biochem. 72(Suppl 30-31):297-303 (1998)]. The primary goal of bioprinting, presently, is achieving printed constructs with the overarching aim toward fully functional tissues and organs. Technology, in hand with the development of bioinks, has been identified as the key to this success. As a result, the place of computer-aided systems (design and manufacturing-CAD/CAM) cannot be underestimated and plays a significant role in this area. Unlike many reviews in this field, this chapter focuses on the technology required for 3D bioprinting from an initial background followed by the exciting area of medical imaging and how it plays a role in bioprinting. Extraction and classification of tissue types from 3D scans is discussed in addition to modeling and simulation capabilities of scanned systems. After that, the necessary area of transferring the 3D model to the printer is explored. The chapter closes with a discussion of the current state-of-the-art and inherent challenges facing the research domain to achieve 3D tissue and organ printing.

The development of metal-organic frameworks (MOFs) has had a significant impact on various fields of chemistry and materials science. Naturally, polymer science also exploited this novel type of material for various purposes, which is due to the defined porosity, high surface area, and catalytic activity of MOFs. The present review covers various topics of MOF/polymer research beginning with MOF-based polymerization catalysis. Furthermore, polymerization inside MOF pores as well as polymerization of MOF ligands is described, which have a significant effect on polymer structures. Finally, MOF/polymer hybrid and composite materials are highlighted, encompassing a range of material classes, like bulk materials, membranes, and dispersed materials. In the course of the review, various applications of MOF/polymer combinations are discussed (e.g., adsorption, gas separation, drug delivery, catalysis, organic electronics, and stimuli-responsive materials). Finally, past research is concluded and an outlook toward future development is provided., (© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Exploring a suitable immobilization strategy to improve catalytic efficiency and reusability of cellulase is of great importance to lowering the cost and promoting the industrialization of cellulose-derived bioethanol. In this work, a layered structure with a thin PEG hydrogel as the inner layer and sodium polyacrylate (PAANa) brush as the outer layer was fabricated on low density polyethylene (LDPE) film by visible-light-induced graft polymerization. Two enzymes, β-glucosidase (BG) and cellulase, were separately coimmobilized onto this hierarchical film. As supplementary to cellulase for improving catalytic efficiency, BG was in situ entrapped into the inner PEG hydrogel layer during the graft polymerization from the LDPE surface. After graft polymerization of sodium acrylate on the PEG hydrogel layer was reinitiated, cellulase was covalently attached on the outer PAANa brush layer. Owing to the mild reaction condition (visible-light irradiation and room temperature), the immobilized BG could retain a high activity after the graft polymerization. The immobilization did not alter the optimal pH and temperature of BG or the optimal temperature of cellulase. However, the optimal pH of cellulase shifts to 5.0 after immobilization. Compared with the original activity of single cellulase system and isolated BG/cellulase immobilization system, the dual-enzyme system exhibited 82% and 20% increase in catalytic activity, respectively. The dual-enzyme system could maintain 93% of carboxymethylcellulose sodium salt (CMC) activity after repeating 10 cycles of hydrolysis and 89% of filter paper activity after 6 cycles relative to original activity, exhibiting excellent reusability. This layer coimmobilization system of BG and cellulase on the polymer film displays tremendous potential for practical application in a biorefinery.

Photochemical processes offer the possibility of preparing functional hydrogels under green conditions that are compatible with both synthetic and natural polymers. In this study, chitosan-based poly(ethylene) glycol (PEG) were successfully synthesized under light irradiation in aqueous medium. Kinetic studies under irradiation showed that less than 2 min were necessary to obtain fully cross-linked networks. Thermomechanical analyses and swelling experiments indicated that introduction of chitosan overall weakens the hydrogel network but can create domains of higher thermal stability than the PEG-alone structure. The resulting chitosan-PEG hydrogels demonstrated a tremendous inhibition (100%) of bacterial growth (Escherichia coli and Staphylococcus aureus). After 6 months' ageing, one of the hydrogels preserved a high antifouling activity against Escherichia coli. This interesting result, which could be correlated with the network features, demonstrates the strong potential of these photochemical methods to obtain robust bio-functional materials.

Production of aqueous dispersions of polymeric nanoparticles via heterogeneous radical polymerization in emulsion-type systems is of enormous commercial importance. The ability to reversibly destabilize such a latex is highly desirable, for example, to save transportation costs. Herein, a method for synthesis of photo-responsive polymer latexes that can be destabilized (leading to sedimentation) by only using UV irradiation (no addition of chemicals or change in the experimental conditions) and subsequently redispersed by stirring under visible light irradiation is described. The destabilization/redispersion mechanism relies on photoinduced trans-cis isomerization of the cationic diazene surfactant 2-(4-(4-butylphenyl)diazenylphenoxy)ethyltrimethylammonium bromide (C4AzoTAB) used in conjunction with the anionic surfactant sodium dodecyl sulfate. It is demonstrated that reversible destabilization can be achieved very rapidly (90 s residence time) employing continuous flow technology., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Finely tuning the photodegradation behavior of the layer-by-layer (LbL) film from the view of controlling the chemical structure of the film-building polymer is still a challenge in related fields. To meet this requirement, a photodegradable polymer (P1) is rationally designed for assembling a visible-light-degradable multilayer film with polystyrene sulfonate (PSS). Compared with similar photopolymers (P2 and P3), this asymmetric picolinium-containing polymer can significantly enhance the degradation rate of as-prepared LbL films; under the same degradation condition, the degradation rate of (P1/PSS)10 is 3 and 6.6 times that of (P2/PSS)10 and (P3/PSS)10, respectively. Moreover, near-infrared light (NIR) is available for triggering the degradation of this film with the assistance of upconversion nanoparticles of YbTm@Lu. The cell cytotoxicity and cell proliferation experiments reveal that P1 is nontoxic and favorable for cell proliferation at concentrations of up to 500 μg mL -1 . As for (PSS/P1)10 films, the ratio of cell number of these two samples ((PSS/P1)10 modified: photodegraded) increases dramatically and reaches about 1.67:1 after 72 h incubation. On the basis of these results, it is anticipated that P1 and this LbL film is an exceptional candidate for visible-light/NIR degradable materials in materials and biological science, medicine, and optics., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In order to improve the flame retardancy of polyacrylonitrile (PAN) fabrics, glycidyl methacrylate (GMA) was first grafted onto the surface of PAN fabric (PAN-g-GMA) by means of UV-induced photo grafting polymerization process. Then, PAN-g-GMA was chemically grafted with chitosan to obtain a bigrafted PAN fabric (PAN-g-GMA-g-CS). Finally, the flame-retardant PAN fabric (FR-PAN) was prepared by phosphorylation. The structure and elemental analysis of the samples were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The thermal degradation properties and combustion characteristics of the fabrics were accessed by thermogravimetric analysis (TG), differential scanning calorimetry (DSC), and cone calorimeter (CC). The results show that the onset thermal decomposition temperature of FR-PAN fabric is lower than that of the control sample due to the degradation of the grafting groups. The combustion test indicates that the FR-PAN fabric has an excellent flame-retardant property and the combustion rate is significantly reduced. In addition, the char residue of the burned FR-PAN fabric is over 97%, indicating excellent char-forming ability., Competing Interests: The authors declare no conflict of interest.

Water-soluble copolymers were obtained by graft copolymerization of N-vinylcaprolactam and 2-hydroxyethyl acrylate on polyvinyl alcohol. The chemical composition of the obtained graft copolymers was determined by IR spectroscopy. Cross-linked films were obtained by radiation treatment of water-soluble copolymers. To estimate the efficiency of the radiation crosslinking of films, the dependence of the yield of gel fraction on the absorbed dose was studied at different proportions of the initial components. It was established that the yield of the crosslinked fraction increases and the swelling capacity of polymer mesh decreases with increasing 2-hydroxyethyl acrylate content in graft copolymer and absorbed dose.

Objective: The aim of this study is to evaluate the microhardness and surface roughness of two different bulk-fill composites polymerized with light-curing unit (LCU) with different polymerization times before and after the application of a home bleaching agent., Materials-Methods: For both microhardness and surface roughness tests, 6 groups were prepared with bulk-fill materials (SonicFill, Filtek Bulk Fill) according to different polymerization times (10, 20, and 30 s). 102 specimens were prepared using Teflon molds (4 mm depth and 5 mm diameter) and polymerized with LCU. 30 specimens ( n = 5) were assessed for microhardness. Before home bleaching agent application, the bottom/top (B/T) microhardness ratio was evaluated. After bleaching agent application, the microhardness measurements were performed on top surfaces. Roughness measurements were performed in 72 specimens ( n = 12) before and after bleaching application. Additionally, for SEM analyses, two specimens from all tested groups were prepared before and after bleaching agent application. The data B/T microhardness ratio before bleaching was analyzed by two-way ANOVA and Tukey's HSD test. The data from the top surface of specimens' microhardness before and after bleaching were analyzed using Wilcoxon signed-rank test, Kruskal-Wallis, Mann-Whitney U tests. The data from surface roughness tests were statistically analyzed by multivariate analysis of variance and Bonferroni test ( p < 0.05)., Results: The B/T microhardness ratio results revealed no significant differences between groups ( p > 0.05). Comparing the microhardness values of the composites' top surfaces before and after bleaching, a significant decrease was observed exclusively in FB30s ( p < 0.05). No significant differences in surface roughness values were observed when the groups were compared based on bulk-fill materials ( p > 0.05) while the polymerization time affected the surface roughness of the SF20s and SF30s groups ( p < 0.05). After bleaching, surface roughness values were significantly increased in the SF20s and SF30s groups ( p < 0.05)., Conclusion: The clinicians should adhere to the polymerization time recommended by the manufacturer to ensure the durability of the composite material in the oral environment.

In this study, the cyto-compatibility and cellular functionality of cell-laden gelatin-methacryloyl (Gel-MA) hydrogels fabricated using a set of photo-initiators which absorb in 400-450 nm of the visible light range are investigated. Gel-MA hydrogels cross-linked using ruthenium (Ru) and sodium persulfate (SPS), are characterized to have comparable physico-mechanical properties as Gel-MA gels photo-polymerized using more conventionally adopted photo-initiators, such as 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Irgacure 2959) and lithium phenyl(2,4,6-trimethylbenzoyl) phosphinate (LAP). It is demonstrated that the Ru/SPS system has a less adverse effect on the viability and metabolic activity of human articular chondrocytes encapsulated in Gel-MA hydrogels for up to 35 days. Furthermore, cell-laden constructs cross-linked using the Ru/SPS system have significantly higher glycosaminoglycan content and re-differentiation capacity as compared to cells encapsulated using I2959 and LAP. Moreover, the Ru/SPS system offers significantly greater light penetration depth as compared to the I2959 system, allowing thick (10 mm) Gel-MA hydrogels to be fabricated with homogenous cross-linking density throughout the construct. These results demonstrate the considerable advantages of the Ru/SPS system over traditional UV polymerizing systems in terms of clinical relevance and practicability for applications such as cell encapsulation, biofabrication, and in situ cross-linking of injectable hydrogels., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Challenges especially in the minimal invasive restorative treatment of teeth require further developments of composite polymerization techniques. These include, among others, the securing of a complete polymerization with moderate thermal stress for the pulp. The aim of this study is to compare current light curing sources with a blue diode laser regarding curing depth and heat generation during the polymerization process. A diode laser (445 nm), a LED, and a halogen lamp were used for polymerizing composite resins. The curing depth was determined according to the norm ISO 4049. Laser output powers of 0.1, 0.5, 1, and 2 W were chosen. The laser beam diameter was adapted to the glass rod of the LED and the halogen lamp (8 mm). The irradiation time was fixed at 40 s. To ascertain ΔT values, the surface and ground area temperatures of the cavities were simultaneously determined during the curing via a thermography camera and a thermocouple. The curing depths for the LED (3.3 mm), halogen lamp (3.1 mm) and laser (0.5/1 W) (3/3.3 mm) showed no significant differences (p < 0.05). The values of ΔT surface as well as ΔT ground also showed no significant differences among LED, halogen lamp, and laser (1 W) . The ΔT surface values were 4.1 LED , 4.3 halogen lamp , and 4.5 °C for the laser while the ΔT ground values were 2.7 LED , 2.6 halogen lamp , and 2.9 °C for the laser. The results indicate that the blue diode laser (445 nm) is a feasible alternative for photopolymerization of complex composite resin restorations in dentistry by the use of selected laser parameters.

Polymerization reactions conducted inside cells must be compatible with the complex intracellular environment, which contains numerous molecules and functional groups that could potentially prevent or quench polymerization reactions. Here we report a strategy for directly synthesizing unnatural polymers in cells through free radical photopolymerization using a number of biocompatible acrylic and methacrylic monomers. This offers a platform to manipulate, track and control cellular behaviour by the in cellulo generation of macromolecules that have the ability to alter cellular motility, label cells by the generation of fluorescent polymers for long-term tracking studies, as well as generate a variety of nanostructures within cells. It is remarkable that free radical polymerization chemistry can take place within such complex cellular environments. This demonstration opens up a multitude of new possibilities for how chemists can modulate cellular function and behaviour and for understanding cellular behaviour in response to the generation of free radicals.

A facile and convenient approach for the preparation of interconnected multiwalled carbon nanotube (MWCNT) monolithic sorbents in recycled plastic caps has been developed. The method, which was based on the photopolymerization of the individual MWCNTs via the formation of a W/O medium internal phase emulsion (40/60 w/w%), provides control over the size of pores, rigidity, and the mechanical stability of the final solid. Pluronic L121 was used as a surfactant containing the water phase inside it and, consequently, the organic and non-polar phase, in which the MWCNTs and the cross-linker were trapped, remained on the outside of the droplets. Optical microscopy and scanning electron microscopy (SEM) were employed to characterize the morphology of both the emulsions and the final solids, respectively. In addition, nitrogen intrusion porosimetry was performed in order to study how the specific surface area of the final monolithic solid changed (from 19.6 to 372.2 m 2  g -1 ) with the variables involved in the polymerization step. To exemplify the great sorbent potential of the synthesized material, a colorimetric assay based on the retention of methylene blue within the interconnected MWCNT monolithic structure was carried out. Finally, following the positive results, the carbon nanotube-monolithic stirred caps were applied for the determination of chlorophenols in a biological matrix such as human urine, obtaining excellent recovery values (91-98%) and good precision (5.4-9.1%) under optimized extraction conditions. Graphical abstract.

New polymeric films with antibacterial activity have been prepared, by simple UV-induced copolymerization of readily available ω-(acryloyloxy)- N , N , N -triethylalcan-1-aminium bromides (or acryloyloxyalkyltriethylammonium bromides, AATEABs) with commercially available 2-hydroethyl methacrylate (HEMA), at different relative amounts. In particular, the antibacterial activity of polymeric films derived from 11-(acryloyloxy)- N , N , N -triethylundecan-1-aminium bromide (or acryloyloxyundecyltriethylammonium bromide, AUTEAB; bearing a C-11 alkyl chain linker between the acrylate polymerization function and the quaternary ammonium moiety) and 12-(acryloyloxy)- N , N , N -triethyldodecan-1-aminium bromide (or acryloyldodecyltriethylammonium bromide, ADTEB, bearing a C-12 alkyl chain linker) has been assessed against Gram-negative Escherichia Coli and Gram-positive Staphylococcus aureus cells. The results obtained have shown a clear concentration-dependent activity against both bacterial strains, the films obtained from homopolymerization of pure AUTEAB and ADTEAB being the most effective. Moreover, ADTEAB-based films showed a higher antibacterial activity with respect to the AUTEAB-based ones. Interestingly, however, both types of films presented a significant activity not only toward Gram-positive S. aureus , but also toward Gram-negative E. Coli cells., Competing Interests: The authors declare no conflict of interest.

Uncontrollable bleeding is a major problem in surgical procedures and after major trauma. Existing hemostatic agents poorly control hemorrhaging from traumatic arterial and cardiac wounds because of their weak adhesion to wet and mobile tissues. Here we design a photo-reactive adhesive that mimics the extracellular matrix (ECM) composition. This biomacromolecule-based matrix hydrogel can undergo rapid gelling and fixation to adhere and seal bleeding arteries and cardiac walls after UV light irradiation. These repairs can withstand up to 290 mm Hg blood pressure, significantly higher than blood pressures in most clinical settings (systolic BP 60-160 mm Hg). Most importantly, the hydrogel can stop high-pressure bleeding from pig carotid arteries with 4~ 5 mm-long incision wounds and from pig hearts with 6 mm diameter cardiac penetration holes. Treated pigs survived after hemostatic treatments with this hydrogel, which is well-tolerated and appears to offer significant clinical advantage as a traumatic wound sealant.

Solid organs transport fluids through distinct vascular networks that are biophysically and biochemically entangled, creating complex three-dimensional (3D) transport regimes that have remained difficult to produce and study. We establish intravascular and multivascular design freedoms with photopolymerizable hydrogels by using food dye additives as biocompatible yet potent photoabsorbers for projection stereolithography. We demonstrate monolithic transparent hydrogels, produced in minutes, comprising efficient intravascular 3D fluid mixers and functional bicuspid valves. We further elaborate entangled vascular networks from space-filling mathematical topologies and explore the oxygenation and flow of human red blood cells during tidal ventilation and distension of a proximate airway. In addition, we deploy structured biodegradable hydrogel carriers in a rodent model of chronic liver injury to highlight the potential translational utility of this materials innovation., (Copyright © 2019 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

Olefin metathesis is now one of the most efficient ways to create new carbon-carbon bonds. While most efforts focused on the development of ever-more efficient catalysts, a particular attention has recently been devoted to developing latent metathesis catalysts, inactive species that need an external stimulus to become active. This furnishes an increased control over the reaction which is crucial for applications in materials science. Here, we report our work on the development of a new system to achieve visible-light-controlled metathesis by merging olefin metathesis and photoredox catalysis. The combination of a ruthenium metathesis catalyst bearing two N-heterocyclic carbenes with an oxidizing pyrylium photocatalyst affords excellent temporal and spatial resolution using only visible light as stimulus. Applications of this system in synthesis, as well as in polymer patterning and photolithography with spatially resolved ring-opening metathesis polymerization, are described.

One of the concerns of parents in the first days of their baby's birth is the baby's risk of jaundice/hyperbilirubinemia. This is because more than 60% of babies are born with jaundice that, if not timely diagnosed and subsequently treated, can lead to serious damage to their health. On the other hand, despite recent progress in sensor technology for clinical applications, the development of easy-to-use, cost-effective, sensitive, specific, and portable diagnostic devices, which use nontoxic and biodegradable materials in their design and fabrication, is still in high demand. Herein we present an easy-to-use, cost-effective, selective, nontoxic, and disposable photoluminescent nanopaper-based assay kit with a smartphone readout for easy diagnosis of neonatal jaundice through visual determination of Bilirubin (BR) in infants' blood samples. The developed BR assay kit comprises highly photoluminescent carbon dot (CD) sensing probes embedded in a bacterial cellulose (BC) nanopaper substrate (CDBN). The photoluminescence (PL) of the developed BR sensor is quenched in the presence of BR as a PL quencher and then selectively recovered upon blue light (λ = 470 nm) exposure, due to conversion of the unconjugated BR to the colorless oxidation products (non-PL quencher) through BR photoisomerization and photooxidation, that subsequently leads to selective PL enhancement of CDBN. The recovered PL intensity of the developed BR assay kit, which was monitored by integrated smartphone camera, was linearly proportional to the concentration of BR in the range of 2-20 mg dL -1 . The feasibility of real application of the fabricated smartphone-based BR assay kit was also confirmed via comparing the results of our method with a clinical reference method for determination of BR concentration in infant's blood samples. With the advantages of nontoxicity and the extraordinary physicochemical properties of photoluminescent BC nanopaper as the sensing substrate, along with those of smartphone technology, we believe that our developed smartphone-based BR assay kit, as an easy-to-use, cost-effective (∼0.01 Euro per test), portable and novel sensing bioplatform, can be potentially exploited for sensitive, specific, rapid, and easy BR detection and jaundice diagnosis at the point of care (POC) and in routine clinical laboratories as well.

In this study we evaluated dual-cure polyurethanes (PUs) as dental adhesives and investigated their effect on the durability of the resin-dentin bonding interface. Different novel photopolymerizable and moisture-curable PUs based on polyester polyol, polyether polyol, and hydroxyethyl methacrylates (HEMAs) were prepared, and their structural characteristics were evaluated by Fourier transform infrared spectroscopy. The tensile strength, elongation at break, and water sorption/solubility of the PU adhesives and the application for bonding with dentin were evaluated. The water sorption and solubility of the PU adhesives were significantly lower than those of two commercial control groups. The bond strength of the PU adhesives after 30 days of storage increased compared with their immediate bond strength, and the microleakage detection of Class V restorations showed less occurrence of marginal leakage compared with the commercial control groups. Cytotoxicity testing has shown that the PU adhesives have low toxicity to pulp cells. The results of this study may shift the future research focus of composite resin dental restoratives from original rigid bonding of the interface to a flexible bonding based on the use of PU adhesives. This may become a new strategy for decreasing the occurrence of microleakage and improving the durability of the bonding interface.

The foreign body response (FBR) to implantable materials can negatively impact performance of medical devices such as the cochlear implant. Engineering surfaces that resist the FBR could lead to enhanced functionality including potentially improving outcomes for cochlear implant recipients through reduction in fibrosis. In this work, we coat poly(dimethylsiloxane) (PDMS) surfaces with two zwitterionic polymers, poly(sulfobetaine methacrylate) (pSBMA) and poly(carboxybetaine methacrylate) (pCBMA), using a simultaneous photografting/photo-cross-linking process to produce a robust grafted zwitterionic hydrogel. reduce nonspecific protein adsorption, the first step of the FBR. The coating process uses benzophenone, a photografting agent and type II photoinitiator, to covalently link the cross-linked zwitterionic thin film to the PDMS surface. As the concentration of benzophenone on the surface increases, the adhesive strength of the zwitterionic thin films to PDMS surfaces increases as determined by shear adhesion. Additionally, with increased concentration of the adsorbed benzophenone, failure of the system changes from adhesive delamination to cohesive failure within the hydrogel, demonstrating that durable adhesive bonds are formed from the photografting process. Interestingly, antifouling properties of the zwitterionic polymers are preserved with significantly lower levels of nonspecific protein adsorption on zwitterion hydrogel-coated samples compared to uncoated controls. Fibroblast adhesion is also dramatically reduced on coated substrates. These results show that cross-linked pSBMA and pCBMA hydrogels can be readily photografted to PDMS substrates and show promise in potentially changing the fibrotic response to implanted biomaterials.

A novel composite monolithic column based on graphene oxide-trimethyl-2-methacroyloxyethylammonium chloride-titania (GO-META-TiO 2 ) was developed for the enrichment of phosphopeptides. META was proposed as a "bridge" to connect GO and TiO 2 species to prepare GO-META-TiO 2 composite. This high surface area composite (surface area = 196.93 m 2 g -1 ) was fixed in the monolithic column via an in situ UV polymerization process. In-tube solid phase microextraction (IT-SPME) using this composite was coupled with matrix-assisted laser desorption ionization time-of-flight-mass spectrometry (MALDI-TOF-MS) for the enrichment and detection of phosphorylated peptides from a digestion mixture of α-casein, β-casein, and bovine serum albumin (BSA) in molar ratios of 1:1:1, 1:1:10, and 1:1:100. The key factors affecting the IT-SPME of the phosphopeptides, such as the elution solution concentrations, the extraction flow rate, and the elution flow rate were comprehensively investigated. For further demonstration, this method was employed for the enrichment and detection of phosphorylated peptides from digested chicken egg white. The obtained results indicated that the GO-META-TiO 2 composite monolithic column rapidly and efficiently captured the phosphopeptides present in these complex biological samples, even in the 10 fmol β-casein tryptic digest. We therefore propose that the reported GO-META-TiO 2 composite monolithic column possesses a suitable affinity for the selective extraction of phosphopeptides from biological samples. This method paves a way in extending the application of nanomaterials., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Currently, there is no consensus in terms of defining the minimum radiant exposure values necessary for achieving adequate properties of composite resin. In addition, the long-term influence that radiant exposure has on the properties of composite resins is still questionable., Objective: The objective of this study was to evaluate the effect of radiant exposure and UV accelerated aging on the physico-chemical and mechanical properties of micro-hybrid and nanofilled composite resins., Material and Methods: A nanofilled (Filtek Supreme; 3M ESPE) and a micro-hybrid composite resin (Filtek Z250; 3M ESPE) were investigated under different radiant exposures (3.75, 9, and 24 J/cm2) and UV accelerated aging protocols (0, 500, 1000, and 1500 aging hours). The degree of conversion (DC), flexural strength (FS), modulus (M), water sorption (WS), and solubility (WL) were evaluated. The results obtained were analyzed using two-way ANOVA and Tukey's test. Comparisons were performed using a significance level of α=0.05., Results: The DC, FS, and M were found to be significantly influenced by both radiant exposure and accelerated aging time. The DC and EM increased with radiant exposure in the no-aging group (0-hour aging) for both micro-hybrid and nanofilled composites, whereas no correlation was found after accelerated aging protocols. WS and WL of micro-hybrid and nanofilled composite resins were scarcely affected by radiant exposure (p>0.05), whereas they were significantly reduced by accelerated aging (p<0.001)., Conclusions: Although increasing radiant exposure affected the degree of conversion and mechanical properties of micro-hybrid and nanofilled composites, no influence on the hydrolytic degradation of the material was observed. In contrast, UV accelerated aging affected both the physico-chemical and mechanical properties of the composites.

Objective: Many in vivo procedures to repair chondral defects use ultraviolet (UV)-photoinitiated in situ polymerization within the cartilage matrix. Chemical species that absorb UV light might reduce the effectiveness of these procedures by acting as light absorption barriers. This study evaluated whether any of the individual native biochemical components in cartilage and synovial fluid interfered with the absorption of light by common scaffolding photosensitizers., Materials: UV-visible spectroscopy was performed on each major component of cartilage in solution, on bovine synovial fluid, and on four photosensitizers, riboflavin, Irgacure 2959, quinine, and riboflavin-5'-phosphate. Molar extinction and absorption coefficients were calculated at wavelengths of maximum absorbance and 365 nm. Intact articular cartilage was also examined., Results: The individual major biochemical components of cartilage, Irgacure 2959, and quinine did not exhibit a significant absorption at 365 nm. Riboflavin and riboflavin-5'-phosphate were more effectual light absorbers at 365 nm, compared with the individual native species. Intact cartilage absorbed a significantly greater amount of UV light in comparison with the native species., Conclusion: Our results indicate that none of the individual native species in cartilage will interfere with the absorption of UV light at 365 nm by these commonly used photoinitiators. Intact cartilage slices exhibited significant light absorption at 365 nm, while also having distinct absorbance peaks at wavelengths less than 300 nm. Determining the UV absorptive properties of the biomolecules native to articular cartilage and synovial fluid will aid in optimizing scaffolding procedures to ensure sufficient scaffold polymerization at a minimum UV intensity.

The use of an in situ, one-pot polymerization-induced self-assembly method to synthesize light-responsive pyrene-containing nanoparticles is reported. The strategy is based on the chain extension of a hydrophilic macromolecular chain transfer agent, poly(oligo(ethylene glycol) methyl ether methacrylate), using a light-responsive monomer, 1-pyrenemethyl methacrylate (PyMA), via a reversible addition-fragmentation chain transfer dispersion polymerization; yielding nanoparticles of various morphologies (spherical micelles and worm-like micelles). In this process, addition of comonomers, such as butyl methacrylate (BuMA) or methyl methacrylate (MMA), are required to obtain high PyMA monomer conversion (>80% in 24 h). The addition of comonomers reduces the π-π stacking of the pyrene moieties, which facilitates the diffusion of monomers in the nanoparticle core. The addition of BuMA (as a comonomer) offers P(PyMA-co-BuMA) core-forming chains with high mobility that enables the reorganization of chains and then the evolution of morphology to form vesicles. In contrast, when MMA comonomer is used, kinetically trapped spheres are obtained; this is due to the low mobility of the core-forming chains inhibiting in situ morphological evolution. Finally, the UV-light-induced dissociation of these light-responsive nanoparticles due to the gradual cleavage of the pyrene moieties and the subsequent hydrophobic-to-hydrophilic transitions of the core-forming blocks is demonstrated., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)