Search Results (14)

Background: This study aimed to assess the impact of methacrylate-functionalized polyhedral oligomeric silsesquioxanes dispersed in nanosilica (MA/Ns-POSS) on the mechanical properties of light-curable dental resins and composites. The primary goal was to evaluate how different concentrations of MA/Ns-POSS (0.5–20 wt.%) affect the hardness, flexural strength, modulus, diametral tensile strength, polymerization shrinkage stress, and degree of conversion of these materials. Methods: A mixture of Bis-GMA, UDMA, TEGDMA, HEMA, and camphorquinone, with a tertiary amine as the photoinitiator, was used to create resin and composite samples, incorporating 45 wt.% silanized silica for the composites. Hardness (Vickers method, HV), flexural strength (FS), and flexural modulus (E_f) were assessed using three-point bending tests, while diametral tensile strength (DTS) polymerization shrinkage stresses (PSS), and degree of conversion (DC) analysis were analyzed for the composites. Results: The results showed that resins with 10 wt.% MA/Ns-POSS exhibited the highest E_f and FS values. Composite hardness peaked at 20 wt.% MA/Ns-POSS, while DTS increased up to 2.5 wt.% MA/Ns-POSS but declined at higher concentrations. PSS values decreased with increasing MA/Ns-POSS concentration, with the lowest values recorded at 15–20 wt.%. DC analysis also showed substantial improvement for 15–20 wt.% Conclusion: Incorporating MA/Ns-POSS improves the mechanical properties of both resins and composites, with 20 wt.% showing the best results. Further studies are needed to explore the influence of higher additive concentrations. Full article

Background/Objectives: Glioblastoma is the most common and lethal primary brain tumor. Patients often suffer from tumor- and treatment induced vasogenic edema, with devastating neurological consequences. Intracranial edema is effectively treated with dexamethasone. However, systemic dexamethasone requires large doses to surpass the blood brain barrier in therapeutic quantities, which is associated with significant side effects. The aim of this study was to investigate a biodegradable, dextran-hydroxyethyl methacrylate (dex-HEMA) based hydrogel, containing polymeric micelles loaded with dexamethasone and liposomes encapsulating dexamethasone phosphate for localized and prolonged delivery. Methods: Poly(ethylene glycol)-b-poly(N-2-benzoyloxypropyl methacrylamide (mPEG-b-p(HPMA-Bz)) micelles were loaded with dexamethasone and characterized. The dexamethasone micelles, together with dexamethasone phosphate liposomes, were dispersed in an aqueous dex-HEMA solution followed by radical polymerization using a photoinitiator in combination with light. The kinetics and mechanisms of drug release from this hydrogel were determined. Results: The diameter of the nanoparticles was larger than the mesh size of the hydrogel, rendering them immobilized in the polymer network. The micelles immediately released free dexamethasone from the hydrogel for two weeks. The dexamethasone phosphate loaded in the liposomes was not released until the gel degraded and intact liposomes were released, starting after 15 days. The different modes of release result in a biphasic and sequential release profile of dexamethasone followed by dexamethasone phosphate liposomes. Conclusions: The results show that this hydrogel system loaded with both dexamethasone polymeric micelles and dexamethasone phosphate loaded liposomes has potential as a local delivery platform for the sequential release of dexamethasone and dexamethasone phosphate, for the intracranial treatment of glioblastoma associated edema. Full article

The miniaturization and high-power density of modern electronic devices pose significant thermal management issues, particularly affecting their performance and lifetime. Ladder-like polysilsesquioxanes (LPSQs) offer a promising solution due to their remarkable thermal, mechanical, and chemical properties. By incorporating thermally conductive fillers, LPSQ composites can achieve high thermal conductivity (TC), making them ideal for thermal management in advanced electronic applications. In this study, LPSQ-based nanocomposites containing functionalized alumina nanoparticles were prepared by solution casting and UV curing, and the effects of varying amounts of Irgacure-184 photoinitiator on their structural and thermal properties were investigated. Three sets of samples were prepared with a fixed amount of LPSQs, 80 wt.% of nanoparticles, and 1, 5, or 10 wt.% of photoinitiator with respect to the matrix. TC was evaluated from the measured values of heat capacity, density, and thermal diffusivity. TC values increased by 60%, 71.2%, and 93.1% for the three samples, respectively, compared to the neat matrix. Results indicate that an intermediate amount of photoinitiator (5%) preserved LPSQs’ structural integrity, namely the presence of long linear silsesquioxane chains, and provided good filler dispersion and distribution, high polymerization degree, thermal stability, and high TC. Full article

In this work, the surfaces of poly (ethylene terephthalate) track-etched membranes (PET TeMs) with pore sizes of 670–1310 nm were hydrophobized with 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate (DFHA) by photoinitiated graft polymerization. Attenuated total reflection FTIR spectroscopy (ATR-FTIR), scanning electron microscopy (SEM) coupled to an energy-dispersive X-ray spectrometer (EDX), and contact angle measurements were used to identify and characterize the TeMs. The optimal parameters for graft polymerization were determined as follows: polymerization time of 60 min, monomer concentration of 30%, and distance from the UV source of 7 cm. The water contact angle of the modified membranes reached 97°, which is 51° for pristine membranes. The modified membranes were tested for water desalination using direct contact membrane distillation (DCMD) method. The effects of membrane pore size, the degree of grafting, and salt concentration on the performance of membrane distillation process were investigated. According to the results obtained, it has been concluded that large pore size hydrophobic TeMs modified by using DFHA could be used for desalinating water. Full article

Polymer systems induced by the reaction between monomers and photo-initiators play a crucial role in the formation of volume-phase gratings. In this paper, we fabricated a dual-photo-initiator photopolymer by doping EY (Eosin Yellow) molecules into a TI (Titanocene, Irgacure 784@BASF) dispersed PMMA (poly-[methyl methacrylate]) substrate system, with the aim of promoting the diffusion and polymerization processes in volume holographic storage. The two-wave interference system is adopted to record a permanent grating structure in our materials. The temporal diffraction variations of photopolymerization (during the interference exposure) and dark diffusion (after the interference exposure) processes have been investigated and analyzed. Aiming to analyze the influence of EY doping ratios on holographic performances, some key parameters were examined in the experiment. We first measured the temporal evolution of diffraction efficiency, then an exponential fitting was adopted to obtain the response time. Finally, the angular selectivity was evaluated by the Bragg condition after holographic recording. Also, the temporal evolution of each component is described by the nonlocal polymerization-driven diffusion model with a dual-photo-initiator composition, theoretically. Furthermore, we experimentally achieved the holographic grating enhancement in both the dark diffusion and photopolymerization processes by doping appropriate EY concentrations, respectively. This work provides a foundation for the acceptability of TI&EY/PMMA polymers in further holographic storage research. Full article

A series of poly(vinyl acetate-co-2-hydroxyethylmethacrylate)/acyclovir drug carrier systems (HEMAVAC) containing different acyclovir contents was prepared through bulk free radical polymerization of 2-hydroxyethyl methacrylate with vinyl acetate (VAc) in presence of acyclovir (ACVR) as the drug using a LED lamp in presence of camphorquinone as the photoinitiator. The structure of the drug carrier system was confirmed by FTIR and ¹HNMR analysis, and the uniform dispersion of the drug particles in the carrier was proved by DSC and XRD analysis. The study of the physico-chemical properties of the prepared materials, such as the transparency, swelling capacity, wettability and optical refraction, was carried out by UV–visible analysis, a swelling test and measurement of the contact angle and the refractive index, respectively. The elastic modulus and the yield strength of the wet prepared materials were examined by dynamic mechanical analysis. The cytotoxicity of the prepared materials and cell adhesion on these systems were studied by LDH assay and the MTT test, respectively. The results obtained were comparable to those of standard lenses with a transparency of 76.90–89.51%, a swelling capacity of 42.23–81.80% by weight, a wettability of 75.95–89.04°, a refractive index of 1.4301–1.4526 and a modulus of elasticity of 0.67–1.50 MPa, depending on the ACVR content. It was also shown that these materials exhibit no significant cytotoxicity; on the other hand, they show significant cell adhesion. The in vitro dynamic release of ACVR in water revealed that the HEMAVAC drug carrier can consistently deliver uniformly adequate amounts of ACVR (5.04–36 wt%) over a long period (7 days) in two steps. It was also found that the solubility of ACVR obtained from the release process was improved by 1.4 times that obtained by direct solubility of the drug in powder form at the same temperature. Full article

The use of sustainable raw materials is now a necessity in all industries, including the production of porous microparticles. Cyrene™ is a cellulose-derived compound that is readily prepared through the reduction of the α,β-unsaturation of levoglucosenone (LGO)—a wood-based platform molecule. In this work, the importance of Cyrene™ as a potential bio-based molecule to produce sustainable porous microparticles is demonstrated. First, a methacrylic derivative of Cyrene™ (m-Cyrene) was synthesized. A microfluidic co-flow device was then established to produce m-Cyrene-based oil-in-water (O/W) controlled-size emulsions and to polymerize them by ultraviolet (UV) radiation in a vial. The continuous phase was a sodium dodecyl sulfate aqueous solution, and the dispersed phase was a mixture of m-Cyrene with methacrylic anhydride (MAN) at two different mass concentrations (i.e., 1 wt.% MAN and 92 wt.% MAN) and 2,2-dimethoxy-2-phenylacetophenone (DMPA) as a photoinitiator. The process used the lowest possible quantity of raw materials and avoided excessive purifications to produce homogeneous porous m-Cyrene-MAN microparticles. The controlled size and homogeneous size distribution of the produced polymer microparticles were confirmed by scanning electron microscope (SEM) images. The 3D microstructure as well as the porosity were determined using X-ray microtomography. The high-resolution 3D images produced indicate that the pores of the microparticles are homogeneous and that their porosity is controllable through the concentration of MAN in the monomer mixture (porosity of 30% for a 1 wt.% MAN ratio and 2% for a 92 wt.% MAN ratio). Such porosity control is very important for future potential encapsulation processes that require precise release control. Full article

We describe a method of partial moments devised for accurate simulation of the time/conversion evolution of polymer composition and molar mass. Expressions were derived that enable rigorous evaluation of the complete molar mass and composition distribution for shorter chain lengths (e.g., degree of polymerization, X_n = N < 200 units) while longer chains (X_n ≥ 200 units) are not neglected, rather they are explicitly considered in terms of partial moments of the molar mass distribution, ${\mu }_x^N(\mathrm{P})={\displaystyle \sum _{n=N+1}^{\infty }{n}^x[{\mathrm{P}}_n]}$ (where P is a polymeric species and n is its’ chain length). The methodology provides the exact molar mass distribution for chains X_n < N, allows accurate calculation of the overall molar mass averages, the molar mass dispersity and standard deviations of the distributions, provides closure to what would otherwise be an infinite series of differential equations, and reduces the stiffness of the system. The method also allows for the inclusion of the chain length dependence of the rate coefficients associated with the various reaction steps (in particular, termination and propagation) and the various side reactions that may complicate initiation or initialization. The method is particularly suited for the detailed analysis of the low molar mass portion of molar mass distributions of polymers formed by radical polymerization with reversible addition-fragmentation chain transfer (RAFT) and is relevant to designing the RAFT-synthesis of sequence-defined polymers. In this paper, we successfully apply the method to compare the behavior of thermally initiated (with an added dialkyldiazene initiator) and photo-initiated (with a RAFT agent as a direct photo-iniferter) RAFT-single-unit monomer insertion (RAFT-SUMI) and oligomerization of N,N-dimethylacrylamide (DMAm). Full article

The use of smart nanocarriers that can modulate therapeutic release aided by biological cues can prevent undesirable cytotoxicity caused by the premature release of cytotoxic drugs during nanocarrier circulation. In this report, degradable nanocarriers based on pH/reduction dual-responsive nanogels were synthesized to encapsulate doxorubicin hydrochloride (DOX) and specifically boost the release of DOX in conditions characteristic of the cancer microenvironment. Nanogels containing anionic monomer 2-carboxyethyl acrylate (CEA) and N,N′-bis(acryloyl)cystamine (CBA) as a degradable crosslinker have been successfully synthesized via photoinitiated free radical polymerization. The loading process was conducted after polymerization by taking advantage of the electrostatic interaction between the negatively charged nanogels and the positively charged DOX. In this case, a high drug loading capacity (DLC) of up to 27.89% was achieved. The entrapment of DOX into a nanogel network could prevent DOX from aggregating in biological media at DOX concentrations up to ~160 µg/mL. Anionic nanogels had an average hydrodynamic diameter (d_H) of around 90 nm with a negative zeta (ζ) potential of around −25 mV, making them suitable for targeting cancer tissue via the enhanced permeation effect. DOX-loaded nanogels formed a stable dispersion in different biological media, including serum-enriched cell media. In the presence of glutathione (GSH) and reduced pH, drug release was enhanced, which proves dual responsivity. An in vitro study using the HCT 116 colon cancer cell line demonstrated the enhanced cytotoxic effect of the NG-CBA/DOX-1 nanogel compared to free DOX. Taken together, pH/reduction dual-responsive nanogels show promise as drug delivery systems for anticancer therapy. Full article

Blue light-initiated alcoholic reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) using bis (acyl) phosphane oxide (BAPO) as the photo-initiator is developed to prepare diblock copolymer nano-objects. High monomer conversion (95%) was achieved within 2 h of blue light irradiation in an isopropanol/water mixture. Effects of solvent, light intensity, and reaction temperature on the polymerization kinetics were evaluated. Finally, the effect of reaction temperature on the morphologies of diblock copolymer nano-objects was investigated and two morphological phase diagrams were constructed at 25 and 70 °C. Transmission electron microscopy (TEM) measurement confirmed that increasing the reaction temperature promoted the evolution of higher order morphology. We believe this study will provide more mechanistic insights into alcoholic RAFT dispersion polymerization for the creation of diblock copolymer nano-objects with well-defined structures. Full article

Photopolymerization of nanocomposite materials using near infrared light is one of the unique technologies based on the luminescent properties of lanthanide-doped upconversion nanoparticles (UCNPs). We explored the UCNP-triggered radical polymerization both in oligomer bulk and on the nanoparticle surface in aqueous dispersion. Core/shell UCNPs NaYF₄:Yb³⁺ and Tm³⁺/NaYF₄ with emitting lines in the ultraviolet and blue regions were used to activate a photoinitiator. The study of the bulk photopolymerization in an initially homogeneous reaction mixture showed the UCNP redistribution due to gradient density occurring in the volume, which led to formation of UCNP superlattices and spheres “frozen” in a polymer matrix. We also developed a strategy of “grafting from” the surface, providing polymer shell growth directly on the nanoparticles. The photosensitization of the endogenous water-soluble photoinitiator riboflavin by the resonance energy transfer from UCNPs was demonstrated in the course of monomer glycidyl methacrylate polymerization followed by photocrosslinking with poly(ethylene glycol) diacrylate on the nanoparticle surface. Full article

Herein, we report a photoinitiated reversible addition-fragmentation chain transfer (RAFT) dispersion copolymerization of methyl methacrylate (MMA) and methyl methacrylic (MAA) for the preparation of highly monodisperse carboxyl-functionalized polymeric microspheres. High rates of polymerization were observed, with more than 90% particle yields being achieved within 3 h of UV irradiation. Effects of reaction parameters (e.g., MAA concentration, RAFT agent concentration, photoinitiator concentration, and solvent composition) were studied in detail, and highly monodisperse polymeric microspheres were obtained in most cases. Finally, silver (Ag) composite microspheres were prepared by in situ reduction of AgNO₃ using the carboxyl-functionalized polymeric microspheres as the template. The obtained Ag composite microspheres were able to catalyze the reduction of methylene blue (MB) with NaBH₄ as a reductant. Full article

Photocrosslinked hydrogels reinforced by microfibrillated cellulose (MFC) were prepared from a methacrylate-functionalized fish elastin polypeptide and MFC dispersed in dimethylsulfoxide (DMSO). First, a water-soluble elastin peptide with a molecular weight of ca. 500 g/mol from the fish bulbus arteriosus was polymerized by N,N′-dicyclohexylcarbodiimide (DCC), a condensation reagent, and then modified with 2-isocyanatoethyl methacrylate (MOI) to yield a photocrosslinkable fish elastin polypeptide. The product was dissolved in DMSO and irradiated with UV light in the presence of a radical photoinitiator. We obtained hydrogels successfully by substitution of DMSO with water. The composite gel with MFC was prepared by UV irradiation of the photocrosslinkable elastin polypeptide mixed with dispersed MFC in DMSO, followed by substitution of DMSO with water. The tensile test of the composite gels revealed that the addition of MFC improved the tensile properties, and the shape of the stress–strain curve of the composite gel became more similar to the typical shape of an elastic material with an increase of MFC content. The rheology measurement showed that the elastic modulus of the composite gel increased with an increase of MFC content. The cell proliferation test on the composite gel showed no toxicity. Full article

An innovative photopolymerizable microgel modified UV-cured acrylic-silica hybrid formulation was developed and characterized for possible use as protective coating for different substrates. A deep investigation, aiming at providing a strong scientific basis for the production of organic-inorganic (O-I) hybrids exhibiting phase co-continuity, was firstly carried out. The O-I hybrid first proposed in this study was obtained from organic precursors with a high siloxane content, which are mixed with tetraethoxysilane (TEOS) in such a way to produce co-continuous silica nanodomains dispersed within the crosslinked organic phase, as a result of the sol-gel process. The first part of the research deals with the selection and optimization of suitable systems through appropriate chemical modifications, in order to ensure that curing reactions can be carried out at room temperature and in the presence of UV radiation. Firstly, the silica domains are formed, followed by crosslinking reactions of the acrylic groups in the oligomer via a free radical polymerization. The crosslinking reaction was controlled with the use of a suitable photoinitiator. Most of the experimental work was devoted to understanding the morphology of the hybrid system, both in uncured and cured states, and to assess its final thermal and optical properties, using different experiential techniques. Full article