Amount Of Photoinitiator Research Articles

Visible light photo-crosslinking of biomimetic gelatin-hyaluronic acid hydrogels for adipose tissue engineering

Tissue engineering (TE) of adipose tissue (AT) is a promising strategy that can provide 3D constructs to be used for in vitro modelling, overcoming the limitations of 2D cell cultures by closely replicating the complex breast tissue extracellular matrix (ECM), cell-cell, and cell-ECM interactions. However, the challenge in developing 3D constructs of AT resides in designing artificial matrices that can mimic the structural properties of native AT and support adipocytes biological functions. Herein, we developed photocrosslinkable hydrogels by employing gelatin methacrylate (GelMA) and hyaluronic acid methacrylate (HAMA) to mimic the collagenous and glycosaminoglycan components of AT microenvironment, respectively. The physico-mechanical properties of the hydrogels were tuned to target AT biomimetic properties by varying the hydrogel formulation (with or without hyaluronic acid), and the amount of photoinitiator (ruthenium/sodium persulfate) used to crosslink the hydrogels via visible light. The physical and mechanical properties of the developed hydrogels were tuned by varying the material formulation and the photoinitiator concentration. Preadipocytes were encapsulated inside the hydrogels and differentiated into mature adipocytes. Findings enlightened that HAMA addition in hybrid hydrogels boosted an increased lipid accumulation. The engineered biomimetic adipocyte-based constructs resulted promising as scaffolds or 3D in vitro models of AT.

Design of Dyes Based on the Quinoline or Quinoxaline Skeleton towards Visible Light Photoinitiators.

Dyes based on quinoline and quinoxaline skeletons were designed for application as visible light photoinitiators. The obtained compounds absorb electromagnetic radiation on the border between ultraviolet and visible light, which allows the use of dental lamps as light sources during the initiation of the photopolymerization reaction. Their another desirable feature is the ability to create a long-lived excited state, which enables the chain reaction to proceed through the mechanism of intermolecular electron transfer. In two-component photoinitiating systems, in the presence of an electron donor or a hydrogen atom donor, the synthesized compounds show excellent abilities to photoinitiate the polymerization of acrylates. In control tests, the efficiency of photopolymerization using modified quinoline and quinoxaline derivatives is comparable to that obtained using a typical, commercial photoinitiator for dentistry, camphorquinone. Moreover, the use of the tested compounds requires a small amount of photoinitiator (only 0.04% by weight) to initiate the reaction. The research also showed a significant acceleration of the photopolymerization process and shortening of the reaction time. In practice, this means that the new two-component initiating systems can be used in much lower concentrations without slowing down the speed of obtaining polymer materials. It is worth emphasizing that these two features of the new initiating system allow for cost reduction by reducing financial outlays on both materials (photoinitiators) and electricity.

3D printing of cyanate ester resins with interpenetration networks for enhanced thermal and mechanical properties

AbstractCyanate ester (PT‐30) resin possesses exceptional thermal and mechanical properties, including high heat distortion temperature, high glass transition temperature (Tg), and outstanding mechanical characteristics. Conversely, the Tg of the homopolymer of tris(2‐hydroxyethyl)isocyanurate triacrylate (T‐acrylate) surpasses that of other acrylates. The combination of PT‐30 and T‐acrylate results in the formation of an interpenetrating polymer network (IPN) through a dual curing mechanism. Furthermore, the combination of these two polymers enables the tuning of rheology for shear thinning behavior for Ink Extrusion 3D printing technology by adjusting the amount of photoinitiator and rheological modifier. Here, 3D printable ink was formulated using PT‐30, T‐acrylate with a higher Tg, a photoinitiator, and a powdered rheological additive. The printed structures underwent a dual‐curing process involving exposure to UV light and thermal curing. Thermomechanical properties of the printed samples were characterized using dynamic mechanical analysis, thermogravimetric analysis, and tensile testing. The successful formation of an IPN structure through the polymerization of T‐acrylate and PT‐30 was observed, resulting in improved mechanical properties and an elevated Tg. The Fourier transform infrared spectroscopy analysis verified the formation of cross‐linked samples. Overall, this study demonstrates the feasibility of Ink Extrusion 3D printing, using a cyanate ester resin and tris(2‐hydroxyethyl)isocyanurate triacrylate with a dual‐curing mechanism. The enhanced mechanical properties at elevated temperatures (~80% retention of room temperature tensile strength at 200°C for sample with 70/30 wt%) and high Tg of 349 ± 3°C for printed structures shown in this study make them suitable for high‐performance structural applications in industries such as aerospace, defense, and microelectronics.

Hydrogels based on poly(2-hydroxyethyl methacrylate) and nettle extract

New types of hydrogels based on linear poly(2-hydroxyethyl methacrylate) and poly(ethyleneglycol) diacrylate (PHEMA-PEGDA) and nettle extract were obtained. A solution of poly(2-hydroxyethylmethacrylate) in monomer (S-PHEMA) was obtained by bulk photopolymerization. Common nettle extractwas used as an ingredient that facilitates wound healing. The influence of the photoinitiator content(1-[4-(2-hydroxymethyl)-phenyl]-2-hydroxy-2-methylpropanone) on the photopolymerization kinetics,as well as the equilibrium swelling ratio (ESR), thermal and mechanical properties of the hydrogelswere examined. Complete HEMA conversion was achieved at the lowest photoinitiator dose. ReplacingHEMA with S-PHEMA causes an increase in ESR (24%) and Tg (50°C) and the amorphous phase content.At the same time, the tensile strength and Young’s modulus decrease. However, the addition of nettleextract (0.3 wt%) requires a significant increase in the amount of photoinitiator (up to 2.5 wt%). As theconcentration of the photoinitiator in the system increases, ESR and Tg decrease, but tensile strengthand Young’s modulus increase.

Investigation of Physicochemical Properties and Surface Morphology of Hydrogel Materials Incorporating Rosehip Extract.

Hydrogel materials are used in many fields of science and industry. They are of particular importance in biomedical applications. In this work, hydrogels were obtained that could act as a dressing for wounds, at the same time being a carrier of substances with antioxidant activity. The discussed materials were obtained in the field of UV radiation. The correlation between the amount of photoinitiator used and the physicochemical properties and surface morphology of the obtained materials was investigated. In addition, the hydrogels have been incorporated with wild rose extract, which is characterized by antioxidant and anti-inflammatory effects. The analysis of the sorption capacity confirmed that the obtained material is able to absorb significant amounts of incubation fluids, which, in terms of application, will enable the absorption of exudate from the wound. The highest stability of materials was noted for hydrogels obtained with the use of intermediate amounts of photoinitiator, i.e., 50 µL and 70 µL. In the case of using 20 µL or 100 µL, the photopolymerization process did not proceed properly and the obtained material was characterized by a lack of homogeneity and high brittleness. With the increase in the amount of photoinitiator, an increase in the surface roughness of hydrogel materials was confirmed. In turn, spectroscopic analysis ruled out the degradation of materials in incubation fluids, indicating the potential for their use in biomedical applications.

Thiol-Acrylate polyHIPEs via Facile Layer-by-Layer Photopolymerization.

A highly reactive thiol-ene high internal phase emulsion based on the monomers 1,6-hexanediol diacrylate and tris 2-(3-mercaptopropionyloxy)ethyl isocyanurate was developed for the purpose of light-driven additive manufacturing, resulting in highly porous customizable poly(high internal phase emulsion) materials. The formulation was specifically designed to facilitate short irradiation times and low amounts of photoinitiator. Furthermore, the developed emulsion does not rely on employing harmful solvents to make scale-up and industrial applications feasible. The selected thiol was added to the printing formulation as a chain-transfer agent, decreasing the brittleness of the acrylate-based system and potential of oxygen inhibition. The thickness of the printed layers lay <50 μm, and the average pore size of all samples was <5 μm.

The Blue‐LED‐Sensitive Naphthoquinone‐Imidazolyl Derivatives as Type II Photoinitiators of Free Radical Photopolymerization

AbstractIn this work, new naphthoquinone‐based photoinitiators are synthesized and applied for the first time in free radical photopolymerization. In the presence of acrylate monomers, these PIs display excellent photoinitiation capabilities under blue‐light LED@405 nm irradiation in a two‐component photoinitiating system in which the additive is a common iodonium salt (bis‐(4‐tert‐butylphenyl)iodonium hexafluorophosphate ‐ Iod) or a tertiary amine (ethyl 4‐dimethylaminobenzoate ‐ EDB). In controlled tests, the polymerization performance of dye4/Iod is equal to or better than that of common commercial Type II photoinitiators (2‐isopropylthioxanthone and benzophenone). Meanwhile, only a trace amount of photoinitiator is required (as low as 0.05%) to initiate the photopolymerization. It is worth noting that some of these compounds can also be used in one‐component photoinitiating system (monocomponent Type II behavior) and exhibit high photoinitiation ability. A series of complementary characterization analyses of two new naphthoquinone dyes (i.e. dye 1 and dye 4) with very similar chemical structures are carried out to investigate the relevant photochemical mechanism. Finally, 3D printing experiments are carried out by a simple and convenient Direct Laser Write (DLW) technique.

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.

Microstructural study of different thick dimethacrylate-based samples using different amounts of photoinitiator

The influence of the thickness and concentration of photoinitiator on the free volume properties of a dental material based on dimethacrylate was investigated in situ by positron annihilation lifetime spectroscopy.

Verification of the Influence of the 2-Hydroxy-2-methylpropiophenone (Photoinitiator) Content in Hydrogel Materials on Their Physicochemical Properties and Surface Morphology

Currently, hydrogel materials are being widely developed and investigated. Factors affecting their properties may be mentioned, such as the types and the amounts of the reagents used for the synthesis of the hydrogel matrix and modifiers; thus, the main aim of the investigations was to check the impact of the amount of photoinitiator applied during the UV-induced polymerization of polyvinylpyrrolidone-based hydrogels incorporated with vitamin C and Aloe vera juice. The experiments that were performed were focused on determining the hydrogels’ swelling capability, behavior in simulated body fluids, hydrophilicity, chemical structure (using FT-IR spectroscopy), as well as their surface morphology and roughness. It was proven that developed materials had relatively rough surfaces, they did not degrade in simulated physiological liquids, and their swelling ratios in these media were 2.0–3.0 g/g. The only change in the pH of the incubation media—a slight decrease—was caused by the release of the modifiers into the tested liquids. Subsequently, it was demonstrated that as the amount of the photoinitiator (2-hydroxy-2-methylpropiophenone) increased, the percentage elongation decreased, and the tensile strength increased. The content of the photoinitiator in the hydrogels also influenced their wettability. All samples showed hydrophilicity; the more photoinitiator in the hydrogel structure, the lower wetting angle for water. Moreover, the greater the amount of 2-hydroxy-2-methylpropiophenone, the smoother and more homogeneous the hydrogel surface; thus, considering the demonstrated physicochemical properties of developed materials, they seem to show application potential for more advanced research regarding the development of innovative dressing materials.

Can TPO as Photoinitiator Replace "Golden Mean" Camphorquinone and Tertiary Amines in Dental Composites? Testing Experimental Composites Containing Different Concentration of Diphenyl(2,4,6-trimethylbenzoyl)phosphine Oxide.

The aim of this research was to compare the biomechanical properties of experimental composites containing a classic photoinitiating system (camphorquinone and 2-(dimethylami-no)ethyl methacrylate) or diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) as a photoinitiator. The produced light-cured composites consisted of an organic matrix-Bis-GMA (60 wt.%), TEGDMA (40 wt.%) and silanized silica filler (45 wt.%). Composites contained 0.27; 0.5; 0.75 or 1 wt.% TPO. Vickers hardness, microhardness (in the nanoindentation test), diametral tensile strength, resistance to three-point bending and the CIE L* a* b* colorimetric analysis was performed with each composite produced. The highest average Vickers hardness values were obtained for the composite containing 1 wt.% TPO (43.18 ± 1.7HV). The diametral tensile strength remains on regardless of the type and amount of photoinitiator statistically the same level, except for the composite containing 0.5 wt.% TPO for which DTS = 22.70 ± 4.7 MPa and is the lowest recorded value. The highest average diametral tensile strength was obtained for the composite containing 0.75 wt.% TPO (29.73 ± 4.8 MPa). The highest modulus of elasticity characterized the composite containing 0.75 wt.% TPO (5383.33 ± 1067.1 MPa). Composite containing 0.75 wt.% TPO has optimal results in terms of Vickers hardness, diametral tensile strength, flexural strength and modulus of elasticity. Moreover, these results are better than the parameters characterizing the composite containing the CQ/DMAEMA system. In terms of an aesthetic composite containing 0.75 wt.%. TPO is less yellow in color than the composite containing CQ/DMAEMA. This conclusion was objectively confirmed by test CIE L* a* b*.

Studies on the Impact of the Photoinitiator Amount Used during the PVP-Based Hydrogels' Synthesis on Their Physicochemical Properties.

In recent times, a great interest is directed to developing biomaterials incorporated with various therapeutical substances which may enhance them with new properties and thus increase their application potential. In this work, polyvinylpyrrolidone (PVP)-based hydrogels modified with Aloe vera juice and vitamin C and differing in the amount of the photoinitiator used during their synthesis were developed. Analysis of hydrogels included characterization of their chemical structure via FT-IR spectroscopy, sorption properties, wettability, surface morphology, behavior in simulated physiological liquids and mechanical properties. Finally, hydrogels’ cytotoxicity towards L929 murine fibroblasts using MTT reduction assay was additionally verified. It was demonstrated that as the amount of the photoinitiator used during the synthesis of hydrogels increased, the smoother their surface and the higher their hydrophilicity. Next, the greater the amount of the photoinitiator, the lower is the percentage elongation of the hydrogel and the greater the hardness. In turn, the swelling ability of hydrogels depended strongly on the type of the absorbed liquid—swelling ratios of samples in distilled water were 24% higher than in SBF, 18% higher than in Ringer liquid, and 32% higher than in hemoglobin wherein the amount of the photoinitiator did not affect this property. Additionally, hydrogels were stable and did not degrade in simulated physiological liquids. The only changes in pH of the incubation media were probably caused by the active substances release from hydrogels which was also confirmed via a lesser intensity of the absorption band on FT-IR spectra corresponding to the functional group occurring in compounds included in Aloe vera juice. Importantly, the viability of fibroblasts incubated with developed materials was at least 86%. Thus the hydrogels, due to their properties, seem to show application potential to be used for biomedical purposes, e.g., as innovative dressing materials.

Room-Temperature Solid-State UV Cross-Linkable Vitrimer-like Polymers for Additive Manufacturing.

In this paper, a UV cross-linkable vitrimer-like polymer, ureidopyrimidinone functionalized telechelic polybutadiene, is reported. It is synthesized in two steps. First, 2(6-isocyanatohexylaminocarbonylamino)-6-methyl-4[1H]-pyrimidinone (UPy-NCO) reacts with hydroxy-functionalized polybutadiene (HTPB) to obtain UPy-HTPB-UPy, and then the resulted UPy-HTPB-UPy is cross-linked under 365 nm UV light (photo-initiator: bimethoxy-2-phenylacetophenone, DMPA). Further investigation reveals that the density of cross-linking and mechanical properties of the resulting polymers can be tailored via varying the amount of photo-initiator and UV exposure time. Before UV cross-linking, UPy-HTPB-UPy is found to be vitrimer-like due to the quadruple hydrogen-bonding interactions. The UPy groups at the end of the chain also enable for rapid solidification upon the evaporation of the solvent. The unsaturated double bonds in the HTPB chains enable UPy-HTPB-UPy to be UV cross-linkable in the solid state at room temperature. After cross-linking, the polymers have good shape memory effect (SME). Here, we demonstrate that this type of polymer can have many potential applications in additive manufacturing. In the cases of fused deposition modelling (FDM) and direct ink writing (DIW), not only the strength of the interlayer bonding but also the strength of the polymer itself can be enhanced via UV exposure (from thermoplastic to thermoset) either during printing or after printing. The SME after cross-linking further helps to achieve rapid volumetric additive manufacturing anytime and anywhere.

Photocurable Printed Piezocapacitive Pressure Sensor Based on an Acrylic Resin Modified with Polyaniline and Lignin

AbstractThe design of suitable materials for the manufacture of pressure sensors with high sensitivity and flexibility in wearable electronics is still a challenge. In this study, a flexible and portable pressure sensor is developed based on a photopolymeric formulation of polyaniline (PANI)/Lignin/acrylate. The amount of photoinitiator and the presence of lignin within the filler are investigated to obtain the best printability and capacitive response. Low PANI contents drastically increase the dielectric constant and 4 wt% photoinitiator improves the signal and sensitivity. A sensitivity of 0.012 kPa–1 is achieved in a linear range (0–10 kPa) with only 3.5 wt% PANI. Lignin improves both the dispersion of the filler within the matrix and the printability of the resin, due to lower absorptivity at the UV wavelength of the 3D printer. Thus, the PANI‐Lignin filler is selected for the fabrication of a piezocapacitive prototype transducer. The pressure transducer demonstrate its practical application by responding to a human footfall and transmitting its corresponding electrical signal. This study shows the enhanced properties of lignin modified PANI acrylate composites. Based on lignin, an abundant natural waste, a sustainable photocurable cost‐effective polymer is proposed for the fabrication of printable, wearable electronics.

Nano-Second Laser Interference Photoembossed Microstructures for Enhanced Cell Alignment

Photoembossing is a powerful photolithographic technique to prepare surface relief structures relying on polymerization-induced diffusion in a solventless development step. Conveniently, surface patterns are formed by two or more interfering laser beams without the need for a lithographic mask. The use of nanosecond pulsed light-based interference lithography strengthens the pattern resolution through the absence of vibrational line pattern distortions. Typically, a conventional photoembossing protocol consists of an exposure step at room temperature that is followed by a thermal development step at high temperature. In this work, we explore the possibility to perform the pulsed holographic exposure directly at the development temperature. The surface relief structures generated using this modified photoembossing protocol are compared with those generated using the conventional one. Importantly, the enhancement of surface relief height has been observed by exposing the samples directly at the development temperature, reaching approximately double relief heights when compared to samples obtained using the conventional protocol. Advantageously, the light dose needed to reach the optimum height and the amount of photoinitiator can be substantially reduced in this modified protocol, demonstrating it to be a more efficient process for surface relief generation in photopolymers. Kidney epithelial cell alignment studies on substrates with relief-height optimized structures generated using the two described protocols demonstrate improved cell alignment in samples generated with exposure directly at the development temperature, highlighting the relevance of the height enhancement reached by this method. Although cell alignment is well-known to be enhanced by increasing the relief height of the polymeric grating, our work demonstrates nano-second laser interference photoembossing as a powerful tool to easily prepare polymeric gratings with tunable topography in the range of interest for fundamental cell alignment studies.

The Effect of Type-I Photoinitiators on the Kinetics of the UV-Induced Cotelomerization Process of Acrylate Monomers and Properties of Obtained Pressure-Sensitive Adhesives.

A new method of solvent-free acrylic pressure-sensitive adhesives (PSAs) based on UV-induced cotelomerization products was presented. The key acrylic monomers (i.e., n-butyl acrylate and acrylic acid) with copolymerizable photoinitiator 4-acrylooxybenzophenone in the presence of a selected chain transfer agent (tetrabromomethane, TBM) were used in the UV-cotelomerization process. Moreover, two kinds of UV-photoinitiators (α-hydroxyalkylphenones, HPs and acylphosphine oxides, APOs) were tested. Photo-DSC, viscosity, thermogravimetric, and GPC measurements for cotelomers were performed. The kinetics study revealed that the systems with APOs, especially Omnirad 819 and Omnirad TPO, were characterized by a much higher reaction rate and greater initiation efficiency than HPs systems were. Additionally, the APO-based syrups exhibited a higher solid content (ca. 60–96 wt%), a higher dynamic viscosity (5–185 Pa·s), but slightly lower molecular weights (Mn and Mw) compared to HP syrups. However, better self-adhesive features (i.e., adhesion and tack) were observed for PSAs based on cotelomers syrups obtained using APOs with lower solid contents (55–80 wt%). It was found that as the solids content (i.e., monomers conversion) increased the adhesion, the tack and glass transition temperature decreased and the type and amount of photoinitiator had no effect on polydispersity. Most of the obtained PSAs were characterized by excellent cohesion, both at 20 °C and 70 °C.

Tuning Superfast Curing Thiol-Norbornene-Functionalized Gelatin Hydrogels for 3D Bioprinting.

Photocurable gelatin-based hydrogels have established themselves as powerful bioinks in tissue engineering due to their excellent biocompatibility, biodegradability, light responsiveness, thermosensitivityand bioprinting properties. While gelatin methacryloyl(GelMA) has been the gold standard for many years, thiol-ene hydrogel systems based on norbornene-functionalized gelatin (GelNB) and a thiolated crosslinker have recently gained increasing importance. In this paper, a highly reproducible water-based synthesis of GelNB is presented, avoiding the use of dimethyl sulfoxide (DMSO) as organic solvent and covering a broad range of degrees of functionalization (DoF: 20% to 97%). Mixing with thiolated gelatin (GelS) results in the superfast curing photoclick hydrogel GelNB/GelS. Its superior properties over GelMA, such as substantially reduced amounts of photoinitiator (0.03%(w/v)), superfast curing (1-2s), higher network homogeneity, post-polymerizationfunctionalization ability, minimal cross-reactivity with cellular components, and improved biocompatibility of hydrogel precursors and degradation products lead to increased survival of primary cells in 3D bioprinting. Post-printing viability analysis revealed excellent survival rates of >84% for GelNB/GelS bioinks of varying crosslinking density, while cell survival for GelMA bioinks is strongly dependent on the DoF. Hence, the semisynthetic and easily accessible GelNB/GelS hydrogel is a highly promising bioink for future medical applications and other light-based biofabrication techniques.

Investigation of the composite materials photopolymerization efficiency in the hree-dimensional 3D printing objects formation

The development and investigation of photopolymerization composite (PhPC) materials with improved photochemical and physical-mechanical properties, providing the possibility of using them during image formation processes in 3D printing technologies, have been carried out. The effect of the nature and amount the polymerization composition constituents on the photocuring of urethane methacrylate and etheracrylate oligomers with the inclusion of organosilicon modifiers, as well as tertiary aminemethacrylates in the process of their irradiation with LED lamps of different wavelengths in the presence of photoinitiators, has been investigated. The effect of the nature and amount of photoinitiators on the optical and polymerization properties of materials and coatings was studied using a PLAZMON-71 spectrometer. According to the results of the calculated photopolymerization kinetic parameters (rate, induction period), it was found that the composition containing the photoinitiators Irgacure 819 (2%), Darocur 1173 (1%), as well as tertiary aminemethacrylate (5%) provides a high polymerization rate and a slight induction period among the investigated compositions. The surface plasmon resonance method allows to determine and control the rate of composite materials photocuring during forming images in 3D printing technology. The possibility of regulating the photochemical and operational characteristics of the constructed nanocomposite materials with the inclusion of organosilicon modifiers in the composition according to their purpose in technological processes of stereolithographic recording of 3D information during printing volumetric images is demonstrated.

Influence of Vanillin Acrylate-Based Resin Composition on Resin Photocuring Kinetics and Antimicrobial Properties of the Resulting Polymers.

The investigation of the influence of vanillin acrylate-based resin composition on photocuring kinetics and antimicrobial properties of the resulting polymers was performed in order to find efficient photocurable systems for optical 3D printing of bio-based polymers with tunable rigidity, as well as with antibacterial and antifungal activity. Two vanillin derivatives, vanillin diacrylate and vanillin dimethacrylate, were tested in photocurable systems using phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide as a photoinitiator. The influence of vanillin acrylate monomer, amount of photoinitiator, presence and amount of dithiol, and presence of solvent on photocuring kinetics was investigated by real-time photoreometry. Polymers of different rigidity were obtained by changing the photocurable resin composition. The photocuring kinetics of the selected vanillin acrylate-based resins was comparable with that of commercial petroleum-based acrylate resins for optical 3D printing. Polymers based on both vanillin acrylates showed a significant antibacterial activity against Escherichia coli and Staphylococcus aureus. Vanillin diacrylate-based polymer films also demonstrated an antifungal activity in direct contact with Aspergillus niger and Aspergillus terreus. Vanillin diacrylate-based dual curing systems were selected as the most promising for optical 3D printing of bio-based polymers with antibacterial and antifungal activity.

Preparation and characterization of pH-sensitive hydrogels from photo-crosslinked poly(ethylene glycol) diacrylate incorporating titanium dioxide

Abstract The purpose of the present investigation was to prepare pH-sensitive hydrogels from photo-crosslinked poly(ethylene glycol) diacrylate (PEG-DA). Rutile titanium dioxide (TiO2) was employed to modify the PEG-DA hydrogels. The rutile titanium dioxide (TiO2) nanoparticles were prepared by direct oxidation of titanium in the presence of polyethylene glycol (PEG) at high temperature. The nanoparticles were characterized by FT-IR, XRD and SEM. The influence of experimental conditions, such as pH, type and amount of photoinitiators on the release profiles of donepezil hydrochloride (active pharmaceutical ingredient for Alzheimer disease) from modified PEG-DA hydrogels, was investigated. The drug release processes were analyzed kinetically using zero-order, first-order, Hixson-Crowell and Peppas models.