Long-Lasting Antibacterial PDMS Surfaces Constructed from Photocuring of End-Functionalized Polymers.

A challenge remains in the development of anti-infectious coatings for the inert surfaces of biomedical devices that are prone to bacterial colonization and biofilm formation. Here, a facile photocuring method to construct functionalized polymeric coatings on inert polydimethylsiloxane (PDMS) surfaces, is developed. Using atom transfer radical polymerization (ATRP) initiator bearing thymol group, hydrophilic DMAEMA and benzophenone (BP)-containing monomers are copolymerized to form polymers with end functional groups. An end-functionalized biocidal coating is then constructed on the inert PDMS surface in one step using a photocuring reaction. The functionalized PDMS surfaces show excellent antibacterial and antifouling properties, are capable of completely eradiating MRSA within ≈6 h, and effectively inhibit the growth of biofilms. In addition, they have good stability and long-lasting antibacterial activity in body fluid environments such as 0.9% saline and urine. According to bladder model experiments, the catheter's lifespan can be extended from ≈7 to 35 days by inhibiting the growth and migration of bacteria along its inner surface. The photocuring technique is therefore very promising in terms of surface functionalization of inert biomedical devices in order to minimize the spread of infection.

New Insights into the Application of Biocompatible (Un)Modified TiO2 and TiO2-ZrO2 Oxide Fillers in Light-Curing Materials.

A novel UV-light-curable poly(ethylene glycol) diacrylate matrix composite material with unmodified and methacryloxyl-grafted TiO2 and TiO2-ZrO2 systems was developed and tested as a potential coating material for medical components. The main goal of the research was to evaluate how the addition of (un)modified inorganic oxide fillers affects the properties of the composition (viscosity, UV/Vis spectra), the kinetics of photocuring (photo-DSC), and the morphological (SEM), physicochemical, and thermal properties (DSC, TGA) of the resulting composites. The applied filler functionalization process decreased their polarity and changed their size, BET surface area, and pore volume, which influenced the viscosity and kinetics of the photocurable system. In addition, the addition of synthesized fillers reduced the polymer's glass transition temperature and increased its thermal stability. It was also observed that additional UV irradiation of the tested composite changed its surface, resulting in hydrophobic properties (with the addition of 7 wt.% filler, an increase in the contact angle by more than 45% was observed).

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.

Photo-Curable 3D Printing of Circularly Polarized Afterglow Metal-Organic Framework Monoliths.

Developing coordination complexes (such as metal-organic frameworks, MOFs) with circularly polarized luminescence (CPL) is currently attracting tremendous attention and remains a significant challenge in achieving MOF with circularly polarized afterglow. Herein, MOFs-based circularly polarized afterglow is first reported by combining the chiral induction approach and tuning the afterglow times by using the auxiliary ligands regulation strategy. The obtained chiral R/S-ZnIDC, R/S-ZnIDC(bpy), and R/S-ZnIDC(bpe)(IDC = 1H-Imidazole-4,5-dicarboxylate, bpy = 4,4'-Bipyridine, bpe = trans-1,2-Bis(4-pyridyl) ethylene) containing a similar structure unit display different afterglow times with 3, 1, and <0.1 s respectively which attribute to that the longer auxiliary ligand hinders the energy transfer through the hydrogen bonding. The obtained chiral complexes reveal a strong chiral signal, obvious photoluminescence afterglow feature, and strong CPL performance (glum up to 3.7 × 10-2). Furthermore, the photo-curing 3D printing method is first proposed to prepare various chiral MOFs based monoliths from 2D patterns to 3D scaffolds for anti-counterfeiting and information encryption applications. This work not only develops chiral complexes monoliths by photo-curing 3D printing technique but opens a new strategy to achieve tunable CPL afterglow in optical applications.

Spatial Trueness Evaluation of 3D-Printed Dental Model Made of Photopolymer Resin: Use of Special Structurized Dental Model.

(1) Background: Various 3D printers are available for dental practice; however, a comprehensive accuracy evaluation method to effectively guide practitioners is lacking. This in vitro study aimed to propose an optimized method to evaluate the spatial trueness of a 3D-printed dental model made of photopolymer resin based on a special structurized dental model, and provide the preliminary evaluation results of six 3D printers. (2) Methods: A structurized dental model comprising several geometrical configurations was designed based on dental crown and arch measurement data reported in previous studies. Ninety-six feature sizes can be directly measured on this original model with minimized manual measurement errors. Six types of photo-curing 3D printers, including Objet30 Pro using the Polyjet technique, Projet 3510 HD Plus using the Multijet technique, Perfactory DDP and DLP 800d using the DLP technique, Form2 and Form3 using the SLA technique, and each printer's respective 3D-printable dental model materials, were used to fabricate one set of physical models each. Regarding the feature sizes of the simulated dental crowns and dental arches, linear measurements were recorded. The scanned digital models were compared with the design data, and 3D form errors (including overall 3D deviation; flatness, parallelism, and perpendicularity errors) were measured. (3) Results: The lowest overall 3D deviation, flatness, parallelism, and perpendicularity errors were noted for the models printed using the Objet30 Pro (overall value: 45 µm), Form3 (0.061 ± 0.019 mm), Objet30 Pro (0.138 ± 0.068°), and Projet 3510 HD Plus (0.095 ± 0.070°), respectively. In color difference maps, different deformation patterns were observed in the printed models. The feature size proved most accurate for the Objet30 Pro fabricated models (occlusal plane error: 0.02 ± 0.36%, occlusogingival direction error: -0.06 ± 0.09%). (4) Conclusions: The authors investigated a novel evaluation approach for the spatial trueness of a 3D-printed dental model made of photopolymer resin based on a structurized dental model. This method can objectively and comprehensively evaluate the spatial trueness of 3D-printed dental models and has a good repeatability and generalizability.

Synthesis of Bio-Based Polyester Resins for Vat Photopolymerization 3D Printing.

Driven by environmental considerations, the scientific community has directed great effort towards the synthesis of new materials derived from renewable resources. However, for photocurable resins, most commercially available building blocks still rely on petroleum-based precursors. Herein, we present a simple synthesis route for bio-based acrylate-modified polyester resins, whose viscosity is sufficiently low for processing them with vat photopolymerization 3D printing. The established synthesis route enables the gradual substitution of fossil-based raw materials with bio-based alternatives. The acid number, color and viscosity of the bio-based acrylic resins are characterized and photocurable formulations are prepared by adding a radical photoinitiator. The photopolymerization kinetics, and thermomechanical and mechanical properties of the photopolymers are investigated as a function of the resin structure and benchmarked against a commercially available petroleum-based counterpart. Finally, the processability of the new bio-based resins via digital light processing 3D printing is demonstrated and test specimens are successfully 3D printed with a resolution in the millimeter range.

Glycerol Acrylate-Based Photopolymers with Antimicrobial and Shape-Memory Properties.

In this paper, for the first time, photopolymers were synthesized from glycerol acrylates with different numbers of functional groups, 2-hydroxy-3-phenoxypropyl acrylate, glycerol dimethacrylate or glycerol trimethacrylate, without and with the addition of vanillin styrene. The photocuring kinetics were monitored by real-time photorheometry. The mechanical, rheological, thermal, antimicrobial and shape-memory properties of the photopolymers were investigated. All polymers synthesized demonstrated antibacterial activity against Escherichia coli and Staphylococcus aureus, as well as antifungal activity against Aspergillus flavus and Aspergillus niger. 2-Hydroxy-3-phenoxypropyl acrylate-based polymers showed thermoresponsive shape-memory behavior. They were able to maintain their temporary shape below the glass transition temperature and return to their permanent shape above the glass transition temperature. Synthesized photopolymers have potential to be used as sustainable polymers in a wide range of applications such as biomedicine, photonics, electronics, robotics, etc.

Chemical Modification of Dental Dimethacrylate Copolymer with Tetramethylxylylene Diisocyanate-Based Quaternary Ammonium Urethane-Dimethacrylates-Physicochemical, Mechanical, and Antibacterial Properties.

In this study, two novel quaternary ammonium urethane-dimethacrylates (QAUDMAs) were designed for potential use as comonomers in antibacterial dental composite restorative materials. QAUDMAs were synthesized via the reaction of 1,3-bis(1-isocyanato-1-methylethyl)benzene with 2-(methacryloyloxy)ethyl-2-decylhydroxyethylmethylammonium bromide (QA10+TMXDI) and 2-(methacryloyloxy)ethyl-2-dodecylhydroxyethylmethylammonium bromide (QA12+TMXDI). Their compositions with common dental dimethacrylates comprising QAUDMA 20 wt.%, urethane-dimethacrylate monomer (UDMA) 20 wt.%, bisphenol A glycerolate dimethacrylate (Bis-GMA) 40 wt.%, and triethylene glycol dimethacrylate (TEGDMA) 20 wt.%, were photocured. The achieved copolymers were characterized for their physicochemical and mechanical properties, including their degree of conversion (DC), glass transition temperature (Tg), polymerization shrinkage (S), water contact angle (WCA), flexural modulus (E), flexural strength (FS), hardness (HB), water sorption (WS), and water leachability (WL). The antibacterial activity of the copolymers was characterized by the minimum bactericidal concentration (MBC) and minimum inhibitory concentration (MIC) against Staphylococcus aureus and Escherichia coli. The achieved results were compared to the properties of a typical dental copolymer comprising UDMA 40 wt.%, Bis-GMA 40 wt.%, and TEGDMA 20 wt.%. The introduction of QAUDMAs did not deteriorate physicochemical and mechanical properties. The WS and WL increased; however, they were still satisfactory. The copolymer comprising QA10+TMXDI showed a higher antibacterial effect than that comprising QA12+TMXDI and that of the reference copolymer.

Photocurable and Temperature-Sensitive Bioadhesive Hydrogels for Sutureless Sealing of Full-Thickness Corneal Wounds.

Penetrating corneal wounds can cause severe vision impairment and require prompt intervention to restore globe integrity and minimize the risk of infection. Tissue adhesives have emerged as a promising alternative to suturing for mitigating postoperative complications. However, conventional water-soluble adhesives suffer formidable challenges in sealing penetrating corneal wounds due to dilution or loss in a moist environment. Inspired by the robust adhesion of mussels in aquatic conditions, an injectable photocurable bioadhesive hydrogel (referred to as F20HD5) composed of polyether F127 diacrylate and dopamine-modified hyaluronic acid methacrylate is developed for sutureless closure of corneal full-thickness wounds. F20HD5 exhibits high transparency, wound-sealing ability, proper viscosity, biodegradability, and excellent biocompatibility. It allows in situ cross-linking via visible light, thereby providing sufficient mechanical strength and adhesiveness. In vivo, the adhesive hydrogel effectively closed penetrating linear corneal incisions and corneal injuries with minimal tissue loss in rabbits. During the 56-day follow-up, the hydrogel facilitates the repair of the injured corneas, resulting in more symmetrical curvatures and less scarring in distinction to the untreated control. Thus, bioinspired hydrogel holds promise as an effective adhesive for sealing full-thickness corneal wounds.

Influence of Photoinitiator Type and Curing Conditions on the Photocuring of Soft Polymer Network.

The presented work deals with the photocuring of telechelic macromonomers derived from plant-based fatty acids to obtain a soft polymer network. Compositions were made by mixing macromonomers with three different concentrations (0.5, 1, and 2%) of two type I photoinitiators (Omnirad 2022 and Omnirad 819). All formulations were then subjected to photopolymerization studies by applying UV-assisted differential scanning calorimetry (UV-DSC) measurements at isothermal conditions at 37 °C with a narrow light source wavelength of 365 nm and irradiation (light intensity) of 20 and 50 mW/cm2. The percentage conversions, reaction orders, and constants were estimated based on autocatalytic Sestak-Berggen and Avrami models. In this work, for the first time, the influence of the curing conditions on the photopolymerization process, such as the photoinitiator concentration, light intensity, and oxygen presence/absence, were investigated for these novel systems. The results indicated significant differences between the two commercially available photoinitiators and their effects on photopolymerization kinetics. The maximum reaction rate was found to be considerably higher for Omnirad 2022 (which is a blend of three different compounds), especially at a lower light intensity, i.e., 20 mW/cm2, compared to Omnirad 819. However, it led to lower maximum conversion in an air atmosphere. The dynamic thermomechanical analysis (DMTA) revealed that light intensity, photoinitiator concentration, and oxygen presence had a strong effect on the storage modulus and loss modulus values. It was concluded that the chemical structure of the photoinitiator and curing conditions had a strong effect on the photopolymerization kinetics and properties of the prepared soft polymer networks.

Photocurable Carbon Nanotube/Polymer Nanocomposite for the 3D Printing of Flexible Capacitive Pressure Sensors.

A photocurable resin/carbon nanotube (CNT) nanocomposite was fabricated from aligned CNTs in an acrylic matrix. The conductivity of the nanocomposite increased rapidly and then stabilized when the CNT content was increased up to and beyond the percolation threshold. Various structures were created using a digital light processing (DLP) 3D printer. Various polymeric dispersants (SMA-amide) were designed and synthesized to improve the CNT dispersion and prevent aggregation. The benzene rings and lone electron pairs on the dispersant interacted with aromatic groups on the CNTs, causing the former to wrap around the latter. This created steric hindrance, thereby stabilizing and dispersing the CNTs in the solvent. CNT/polymer nanocomposites were created by combining the dispersant, CNTs, and a photocurable resin. The CNT content of the nanocomposite and the 3D printing parameters were tuned to optimize the conductivity and printing quality. A touch-based human interface device (HID) that utilizes the intrinsic conductivity of the nanocomposite and reliably detects touch signals was fabricated, enabling the free design of sensors of various styles and shapes using a low-cost 3D printer. The production of sensors without complex circuitry was achieved, enabling novel innovations.

Rapidly Synthesized Single-Ion Conductive Hydrogel Electrolyte for High-Performance Quasi-Solid-State Zinc-ion Batteries.

Single-ion conductive electrolytes can largely eliminate electrode polarization, reduce the proportion of anion migration and inhibit side reactions in batteries. However, they usually suffer from insufficient ion conductivity due to the strong interaction between cations and cationic receptors. Here we report an ultrafast light-responsive covalent organic frameworks (COF) with sulfonic acid groups modification as the acrylamide polymerization initiator. Benefiting from the reduced electrostatic interaction between Zn2+ and sulfonic acid groups through solvation effects, the as-prepared COF-based hydrogel electrolyte (TCOF-S-Gel) receives an ion conductivity of up to 27.2 mS/cm and Zn2+ transference number of up to 0.89. In addition, sufficient hydrogen bonds endow the single-ion conductive TCOF-S-Gel electrolyte to have good water retention and superb mechanical properties. The assembled Zn||TCOF-S-Gel||MnO2 full zinc-ion battery exhibits high discharge capacity (248 mAh/g at 1C), excellent rate capability (90 mAh/g at 10C) and superior cycling performance. These enviable results enlist the instantaneously photocured TCOF-S-Gel electrolyte to be qualified to large-scaled flexible high-performance quasi-solid-state zinc-ion batteries.

Initiator-Free Photocuring 3D-Printable PVA-Based Hydrogel with Tunable Mechanical Properties and Cell Compatibility.

Poly(vinyl alcohol) (PVA)-based hydrogels have attracted great attention and been widely used in biological tissue engineering. With the development of modern medicine, precision medicine requires the customization of medical materials. However, lacking of photocurable functional groups or the performance of rapid phase transition makes PVA-based hydrogels difficult to be customizable molded through photocuring 3D printing technique. In this research, customizable PVA-based hydrogels with high performance through 3D photocurable printing and freezing-thawing (F-T) process are obtained. The ability of 3D-printable is endowed by the introduction of polyvinyl alcohol-styrylpyridine (PVA-SBQ), which can be photo-crosslinked quickly without photoinitiator. Meanwhile, the tunable mechanical properties are achieved by adjusting the mass ratio of PVA-SBQ to PVA, and PVA can offer the physical crosslinking points through freezing-thawing (F-T) process. The hydrogels with high resolution are prepared by digital light procession 3D printing with the mass ratio 1:1 of PVA-SBQ to PVA solution. Attributed to the absence of initiator, and no small molecule residues inside the hydrogels, the hydrogels have good biocompatibility and have the potential to be applicated in the field of biological tissue engineering.

Progress in Photocurable 3D Printing of Photosensitive Polyurethane: A Review.

In recent years, as a class of advanced additive manufacturing (AM) technology, photocurable 3D printing has gained increasing attention. Based on its outstanding printing efficiency and molding accuracy, it is employed in various fields, such as industrial manufacturing, biomedical, soft robotics, electronic sensors. Photocurable 3D printing is a molding technology based on the principle of area-selective curing of photopolymerization reaction. At present, the main printing material suitable for this technology is the photosensitive resin, a composite mixture consisting of a photosensitive prepolymer, reactive monomer, photoinitiator, and other additives. As the technique research deepens and its application gets more developed, the design of printing materials suitable for different applications is becoming the hotspot. Specifically, these materials not only can be photocured but also have excellent properties, such as elasticity, tear resistance, fatigue resistance. Photosensitive polyurethanes can endow photocured resin with desirable performance due to their unique molecular structure including the inherent alternating soft and hard segments, and microphase separation. For this reason, this review summarizes and comments on the research and application progress of photocurable 3D printing of photosensitive polyurethanes, analyzing the advantages and shortcomings of this technology, also offering an outlook on this rapid development direction.

Synergistic Effect of Thermoresponsive and Photocuring Methacrylated Chitosan-Based Hybrid Hydrogels for Medical Applications.

The thermoresponsive drug-loaded hydrogels have attracted widespread interest in the field of medical applications due to their ease of delivery to structurally complex tissue defects. However, drug-resistant infections remain a challenge, which has prompted the development of new non-antibiotic hydrogels. To this end, we prepared chitosan-methacrylate (CTSMA)/gelatin (GEL) thermoresponsive hydrogels and added natural phenolic compounds, including tannic acid, gallic acid, and pyrogallol, to improve the efficacy of hydrogels. This hybrid hydrogel imparted initial crosslinking at physiological temperature, followed by photocuring to further provide a mechanically robust structure. Rheological analysis, tensile strength, antibacterial activity against E. coli, S. aureus, P. gingivalis, and S. mutans, and L929 cytotoxicity were evaluated. The experimental results showed that the hybrid hydrogel with CTSMA/GEL ratio of 5/1 and tannic acid additive had a promising gelation temperature of about 37 °C. The presence of phenolic compounds not only significantly (p < 0.05) enhanced cell viability, but also increased the tensile strength of CTSMA/GEL hybrid hydrogels. Moreover, the hydrogel containing tannic acid revealed potent antibacterial efficacy against four microorganisms. It was concluded that the hybrid hydrogel containing tannic acid could be a potential composite material for medical applications.

Ability of short exposures from laser and quad-wave curing lights to photo-cure bulk-fill resin-based composites.

OBJECTIVE: This study investigated the ability of a laser, and a 'quad-wave' LCU, to photo-cure paste and flowable bulk-fill resin-based composites (RBCs). METHODS: Five LCUs and nine exposure conditions were used. The laser LCU (Monet) used for 1 s and 3 s, the quad-wave LCU (PinkWave) used for 3 s in the Boost and 20 s in the Standard modes, the the multi-peak LCU (Valo X) used for 5 s in the Xtra and 20 s in the Standard modes, were compared to the polywave PowerCure used in the 3 s mode and for 20 s in the Standard mode, and to the mono-peak SmartLite Pro used for 20 s. Two paste consistency bulk-fill RBCs: Filtek One Bulk Fill Shade A2 (3 M), Tetric PowerFill Shade IVA (Ivoclar Vivadent), and two flowable RBCs: Filtek Bulk Fill Flowable Shade A2 (3 M), Tetric PowerFlow Shade IVA (Ivoclar Vivadent) were photo-cured in 4-mm deep x 4-mm diameter metal molds. The light received by these specimens was measured using a spectrometer (Flame-T, Ocean Insight), and the radiant exposure delivered to the top surface of the RBCs was mapped. The immediate degree of conversion (DC) at the bottom, and the 24-hour Vickers Hardness (VH) at the top and bottom of the RBCs were measured and compared. RESULTS: The irradiance received by the 4-mm diameter specimens ranged from 1035 mW/cm2 (SmartLite Pro) to 5303 mW/cm2 (Monet). The radiant exposures between 350 and 500 nm delivered to the top surface of the RBCs ranged from 5.3 J/cm2 (Monet in 1 s) to 26.4 J/cm2 (Valo X), although the PinkWave delivered 32.1 J/cm2 in 20 s 350 to 900 nm. All four RBCs achieved their maximum DC and VH values at the bottom when photo-cured for 20 s. The Monet used for 1 s and the PinkWave used for 3 s on the Boost setting delivered the lowest radiant exposures between 420 and 500 nm (5.3 J/cm2 and 3.5 J/cm2 respectively), and they produced the lowest DC and VH values. CONCLUSIONS: Despite delivering a high irradiance, the short 1 or 3-s exposures delivered less energy to the RBC than 20-s exposures from LCUs that deliver> 1000 mW/cm2. There was an excellent linear correlation (r > 0.98) between the DC and the VH at the bottom. There was a logarithmic relationship between the DC and the radiant exposure (Pearson's r = 0.87-97) and between the VH and the radiant exposure (Pearson's r = 0.92-0.96) delivered in the 420-500 nm range.

Off-Stoichiometry Thiol-Ene Polymers: Inclusion of Anchor Groups Using Allylsilanes.

The use of polymers in silicon chips is of great importance for the development of microelectronic and biomedical industries. In this study, new silane-containing polymers, called OSTE-AS polymers, were developed based on off-stoichiometry thiol-ene polymers. These polymers can bond to silicon wafers without pretreatment of the surface by an adhesive. Silane groups were included in the polymer using allylsilanes, with the thiol monomer as the target of modification. The polymer composition was optimized to provide the maximum hardness, the maximum tensile strength, and good bonding with the silicon wafers. The Young's modulus, wettability, dielectric constant, optical transparency, TGA and DSC curves, and the chemical resistance of the optimized OSTE-AS polymer were studied. Thin OSTE-AS polymer layers were obtained on silicon wafers via centrifugation. The possibility of creating microfluidic systems based on OSTE-AS polymers and silicon wafers was demonstrated.

Thermoresponsive Shape-Memory Biobased Photopolymers of Tetrahydrofurfuryl Acrylate and Tridecyl Methacrylate.

A series of thermoresponsive shape-memory photopolymers have been synthesized from the mixtures of two biobased monomers, tetrahydrofurfuryl acrylate and tridecyl methacrylate, with the addition of a small amount of 1,3-benzendithiol (molar ratio of monomers 0-10:0.5:0.03, respectively). Ethyl (2,4,6 trimethylbenzoyl) phenylphosphinate was used as photoinitiator. The calculated biorenewable carbon content of these photopolymers was in the range of (63.7-74.9)%. The increase in tetrahydrofurfuryl acrylate content in the photocurable resins resulted in a higher rate of photocuring, increased rigidity, as well as mechanical and thermal characteristics of the obtained polymers. All photopolymer samples showed thermoresponsive shape-memory behavior when reaching their glass transition temperature. The developed biobased photopolymers can replace petroleum-derived thermoresponsive shape-memory polymer analogues in a wide range of applications.

Water-Resistant Photo-Crosslinked PEO/PEGDA Electrospun Nanofibers for Application in Catalysis.

Catalysts are used for producing the vast majority of chemical products. Usually, catalytic membranes are inorganic. However, when dealing with reactions conducted at low temperatures, such as in the production of fine chemicals, polymeric catalytic membranes are preferred due to a more competitive cost and easier tunability compared to inorganic ones. In the present work, nanofibrous mats made of poly(ethylene oxide), PEO, and poly(ethylene glycol) diacrylate, PEGDA, blends with the Au/Pd catalyst are proposed as catalytic membranes for water phase and low-temperature reactions. While PEO is a water-soluble polymer, its blending with PEGDA can be exploited to make the overall PEO/PEGDA blend nanofibers water-resistant upon photo-crosslinking. Thus, after the optimization of the blend solution (PEO molecular weight, PEO/PEGDA ratio, photoinitiator amount), electrospinning process, and UV irradiation time, the resulting nanofibrous mat is able to maintain the nanostructure in water. The addition of the Au6/Pd1 catalyst (supported on TiO2) in the PEO/PEGDA blend allows the production of a catalytic nanofibrous membrane. The reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP), taken as a water phase model reaction, demonstrates the potential usage of PEO-based membranes in catalysis.

Impact of the Chemical Structure of Photoreactive Urethane (Meth)Acrylates with Various (Meth)Acrylate Groups and Built-In Diels-Alder Reaction Adducts on the UV-Curing Process and Self-Healing Properties.

A series of UV-curable urethane (meth)acrylates were obtained by copolymerization of the Diels-Alder adduct (HODA), isophorone diisocyanate, PEG1000, and various hydroxy (meth)acrylates. The aim of the present work was to determine the influence of the chemical structure of the introduced (meth)acrylic groups, i.e., hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate, on the UV-curing process and self-healing properties of cured coatings. The chemical structure of prepolymers was characterized by FTIR and NMR spectroscopy, whereas the UV-curing process was monitored in real time using FTIR and photo-DSC. In turn, the self-healing properties were characterized in relation to the thermally reversible mechanism, which was tested using the following methods: an FTIR spectroscope equipped with a heating attachment; DSC and TG apparatus; and an optical microscope equipped with a stage with programmable heating. The result of comprehensive research on the self-healing of photocurable coatings in the context of the presence of various photoreactive groups and the course of the curing process allows one to control the self-healing process by reducing the effective healing temperature. The self-healing properties, taken together with the fast UV curing of the coatings and excellent properties of cured coatings, make the material attractive for a variety of applications, in particular in cases where coatings are not repaired, e.g., for economic reasons or when it is not possible, such as in flexible electronic screens, car paint film, and aircraft interior finishes.