Photon Harvesting in Sunscreen-Based Functional Nanoparticles.

The ultraviolet light component in the solar spectrum is known to cause several harmful effects, such as allergy, skin ageing, and skin cancer. Thus, current research attention has been paid to the design and fundamental understanding of sunscreen-based materials. One of the most abundantly used sunscreen molecules is Avobenzone (AB), which exhibits two tautomers. Here, we highlight the preparation of spherically shaped nanoparticles from the sunscreen molecule AB as well as from sunscreen-molecule-encapsulated polymer nanoparticles in aqueous media and study their fundamental photophysical properties by steady-state and time-resolved spectroscopy. Steady-state studies confirm that the AB molecule is in the keto and enol forms in tetrahydrofuran, whereas the enol form is stable in the case of both AB nanoparticles and AB-encapsulated poly(methyl methacrylate) (PMMA) nanoparticles. Thus, the keto-enol transformation of AB molecules is restricted to a nanoenvironment. An enhancement of photostability in both the nanoparticle and PMMA-encapsulated forms under UV light irradiation is observed. The efficient excited energy transfer (60 %) from AB to porphyrin molecules opens up further prospects in potential applications as light-harvesting systems.

The effect of repeated microwave irradiation on the dimensional stability of a specific acrylic denture resin.

PURPOSE: To determine the dimensional stability of a poly(methyl methacrylate) (PMMA) acrylic resin when subjected to multiple sessions of repeated microwave irradiation at power settings of 700 and 420 W. MATERIALS AND METHODS: Twenty standardized denture bases were fabricated using a PMMA resin. Points of measurement were marked on each denture base with a standardized template, and the distances between points were recorded using a digital microscope. The denture bases were randomly placed into two experimental groups of 10 bases each. Individual denture bases were placed into a glass beaker containing 200 ml of room temperature deionized water and then exposed to either 700 or 420 W of microwave radiation for 3 minutes. The denture bases were allowed to cool to room temperature, and measurements between points were recorded. This process was carried out for two microwave periods with measurements being completed after each period. The data were then analyzed for any significant changes in distances between points using a Student's t-test. RESULTS: All denture bases experienced 1.0 to 2.0 mm or approximately 3% linear dimensional change after each period of microwaving. Results were significant with all t-tests having values of p < 0.05. CONCLUSION: This report showed that the denture bases deformed significantly under experimental conditions at either 700 W for 3 minutes in 200 ml of water or 420 W for 3 minutes in 200 ml of water.

Femtosecond laser high-efficiency drilling of high-aspect-ratio microholes based on free-electron-density adjustments.

We studied the micromachining of high-aspect-ratio holes in poly(methylmethacrylate) using a visible double-pulse femtosecond laser based on free-electron-density adjustments. Hole depth and aspect ratio increased simultaneously upon decreasing the wavelength in the visible-light zone. When the pulse energy reached a high level, the free-electron density was adjusted by using a double-pulse laser, which induced fewer free electrons, a lower reflectivity plasma plume, and more pulse energy deposition in the solid bottom. Thus, the aspect ratio of the hole was improved considerably. At a moderate pulse energy level, a 1.3-1.4 times enhancement of both the ablation depth and the aspect ratio was observed when the double-pulse delay was set between 100 and 300 fs, probably due to an enhanced photon-electron coupling effect through adjusting the free-electron density. At a lower pulse energy level, this effect also induced the generation of a submicrometer string. In addition, the ablation rate was improved significantly by using visible double pulses.

Outcome of long-axis percutaneous sacroplasty for the treatment of sacral insufficiency fractures with a radiofrequency-induced, high-viscosity bone cement.

Our goal was to assess the technical results in patients who underwent long-axis sacroplasty for the treatment of sacral insufficiency fractures (SIF) by radiofrequency-induced high-viscosity bone cement augmentation. Twelve patients with bilateral sacral fractures were treated by augmentation with radiofrequency-activated, high-viscosity polymethylmethacrylate (PMMA) bone cement under local anesthesia. CT-guided sacroplasty was performed by using a long-axis approach through a single entry point. Thirty-six vertebrae were treated in 12 sessions under a combination of CT and fluoroscopic guidance using a bilateral access and a cavity-creating osteotome prior to remote-controlled, hydraulically driven cement injection. The visual analogue scale (VAS) score before sacroplasty and at 1 and 3 months after the treatment was obtained. PMMA leaks were evaluated retrospectively using the post-interventional CT. The mean amount of high-viscosity PMMA injected per patient was 7.8 ml. No major adverse events were observed. In the first 4 days after the procedure, the mean VAS score decreased from 8.1 ± 1.9 to mean 3.1 ± 1.2 and was followed by a gradual but continuous decrease throughout the rest of the follow-up period at 24 weeks (mean 2.2 ± 1.1) and 48 weeks (mean 2.1 ± 1.4). CT fluoroscopy-guided sacral augmentation was safe and effective in all 12 patients with osteoporotic SIF.

Improved osteoblast response to UV-irradiated PMMA/TiO2 nanocomposites with controllable wettability.

Osteoblast response was evaluated with polymethylmethacrylate (PMMA)/titanium dioxide (TiO2) nanocomposite thin films that exhibit the controllable wettability with ultraviolet (UV) treatment. In this study, three samples of PMMA/TiO2 were fabricated with three different compositional volume ratios (i.e., 25/75, 50/50, and 75/25) followed by UV treatment for 0, 4, and 8 h. All samples showed the increased hydrophilicity after UV irradiation. The films fabricated with the greater amount of TiO2 and treated with the longer UV irradiation time increased the hydrophilicity more. The partial elimination of PMMA on the surface after UV irradiation created a durable hydrophilic surface by (1) exposing higher amount of TiO2 on the surface, (2) increasing the hydroxyl groups on the TiO2 surface, and (3) producing a mesoporous structure that helps to hold the water molecules on the surface longer. The partial elimination of PMMA on the surface was confirmed by Fourier transform infrared spectroscopy. Surface profiler and atomic force microscopy demonstrated the increased surface roughness after UV irradiation. Both scanning electron microscopy and energy-dispersive X-ray spectroscopy demonstrated that particles containing calcium and phosphate elements appeared on the 8 h UV-treated surface of PMMA/TiO2 25/75 samples after 4 days soaking in Dulbecco's Modified Eagle Medium. UV treatment showed the osteoblast adhesion improved on all the surfaces. While all UV-treated hydrophilic samples demonstrated the improvement of osteoblast cell adhesion, the PMMA/TiO2 25/75 sample after 8 h UV irradiation (n = 5, P value = 0.000) represented the best cellular response as compared to other samples. UV-treated PMMA/TiO2 nanocomposite thin films with controllable surface properties represent a high potential for the biomaterials used in both orthopedic and dental applications.

Shear bond strength of denture teeth to two chemically different denture base resins after various surface treatments.

PURPOSE: Debonding of acrylic teeth from the denture base remains a major problem in prosthodontics. The objective of this study was to evaluate the effect of various surface treatments on the shear bond strength of the two chemically different denture base resins-polymethyl methacrylate (PMMA) and urethane dimethacrylate (UDMA). MATERIALS AND METHODS: Two denture base resins, heat-cured PMMA (Meliodent) and light-activated UDMA (Eclipse), were used in this study. A total of 60 molar acrylic denture teeth were randomly separated into four groups (n = 15), according to surface treatment: acrylic untreated (group AC), Eclipse untreated (group EC), treated with eclipse bonding agent (group EB), and Er:YAG laser-irradiated eclipse (group EL). Shear bond strength test specimens were prepared according to the manufacturers' instructions. Specimens were subjected to shear bond strength test by a universal testing machine with a 1 mm/min crosshead speed. The data were analyzed with one-way ANOVA and post hoc Tukey-Kramer multiple comparison tests (α = 0.05). RESULTS: The highest mean bond strength was observed in specimens of group EB, and the lowest was observed in group EC specimens. A statistically significant difference in shear bond strength was found among all groups (p < 0.001), except between groups EC and EL (p = 0.61). CONCLUSION: The two chemically different denture base polymers showed different shear bond strength values to acrylic denture teeth. Laser-irradiation of the adhesive surface was found to be ineffective on improving bond strength of acrylic denture teeth to denture base resin. Eclipse bonding agent should be used as a part of denture fabrication with the Eclipse Resin System.

Femtosecond laser induced surface swelling in poly-methyl methacrylate.

We show that surface swelling is the first step in the interaction of a single femtosecond laser pulse with PMMA. This is followed by perforation of the swollen structure and material ejection. The size of the swelling and the perforated hole increases with pulse energy. After certain energy the swelling disappears and the interaction is dominated by the ablated hole. This behaviour is independent of laser polarization. The threshold energy at which the hole size coincides with size of swelling is 1.5 times that of the threshold for surface swelling. 2D molecular dynamics simulations show surface swelling at low pulse energies along with void formation below the surface within the interaction region. Simulations show that at higher energies, the voids coalesce and grow, and the interaction is dominated by material ejection.

Sub-100nm pattern generation by laser direct writing using a confinement layer.

A novel technique is introduced that dramatically increases the quality and spatial resolution of directly ablated periodic nanostructures on materials. The presented method utilizes a PMMA confinement layer spin coated on the surface of the ablated material reducing the violence and speed of expansion of the molten material. As a result, droplet formation deteriorating the achievable resolution can be completely avoided. Moreover, motion control of the molten material leads to structural details with dimensions well below the irradiation wavelength.

On-demand killing of adherent cells on photo-acid-generating culture substrates.

As a powerful tool of cell screening and cell purification, we developed a novel method to kill adherent cells as cultured on a substrate by micro-projection of incoherent visible light. To kill the cells by the mild light irradiated by electrically controllable micro-projection systems currently available, we introduced the assist of the photo-responsive culture substrates functionalized with a photo-acid-generating polymer. In clear contrast to the existing laser-based methods requiring point scanning, areal micro-projection of blue light with the wavelength 436 nm killed many CHO-K1 cells at a time in the irradiated area on the substrate. The effect of the photo-generated acid was so confined that selective killing of targeted cells was achieved without critical damage to the neighboring cells. Further, we demonstrated the photo-selective killing of the adherent cells after preliminarily patterning through the photo-induced removal of cell adhesion-inhibiting polymer.

The effects of therapeutic x-ray doses on mechanical, chemical and physical properties of poly methyl methacrylate.

AIM: The aim of this study was to investigate the effect of radiation doses very close to the human dose for oral cancers on mechanical, chemical and physical properties for poly methyl-methacrylate (PMMA). METHODS: PMMA samples were divided into four different groups: no irradiated group, 25-Gy irradiated group, 50-Gy irradiated group and 75-Gy irradiated group. Each group contained nine samples. After 24 h, a three-point loading test was applied to each PMMA groups. The transverse strength and the elastic modulus were calculated using the test results. The results were analyzed statistically by using one-way analysis of variance. The structural characterizations of the PMMA samples were carried out by a Fourier Transform Infrared (FTIR) spectrophotometer to evaluate the chemical structure differences. RESULTS: The transverse strength values of 25-Gy, 50-Gy and 75-Gy radiation groups were significantly higher than that of the no radiation group (p < 0.05). There was no significant difference among the elastic modulus values of the study groups (p > 0.05). The FTIR findings demonstrated that the irradiation process did not change the chemical structure of the PMMA polymeric materials. CONCLUSION: The therapeutic radiation doses increase the mechanical properties of the PMMA; however, the chemical and structural properties have no effect. When the findings of this study are taken into account, it can be said that patients can wear dentures during the radiotherapy.

Adding denture cleanser to microwave disinfection regimen to reduce the irradiation time and the exposure of dentures to high temperatures.

BACKGROUND: The microwave energy is an efficient disinfection method; however, it can generate high temperatures that can result in distortion of the dentures. OBJECTIVES: To evaluate whether the addition of an enzymatic cleanser to microwave disinfection regimen would disinfect dentures with shorter irradiation time. MATERIALS AND METHODS: Seven resin discs colonized with Candida albicans biofilm were placed on the palatal surface of sterile dentures to be randomly assigned to the following treatments: immersion in distilled water for 3 min with 0 (DW), 1 (DW + M1), 2 (DW + M2), or 3 min (DW + M3) of microwave irradiation; or immersion in denture cleanser for 3 min with 0 (DC), 1 (DC + M1), 2 (DC + M2) or 3 min (DC + M3) of irradiation. After the treatments, the viable cells were counted by a blinded examiner. The temperature was measured immediately after irradiation. The data were analyzed by ANOVA and Tukey post hoc tests (α = 0.05). RESULTS: No viable cells were found after DC + M2, DC + M3, and DW + M3 treatments, of which DC + M2 achieved the lowest temperature. No significant difference was found between the effectiveness of DW, DW + M1 and DC treatments (p > 0.05). CONCLUSION: Within the limits of this study, the association of a denture cleanser and microwave energy is efficient to disinfect dentures in lower irradiation time and temperature.

The effect of long-term disinfection procedures on hardness property of resin denture teeth.

OBJECTIVE: The aim of the study was to evaluate the effect of long-term disinfection procedures on the Vickers hardness (VHN) of acrylic resin denture teeth. MATERIAL AND METHODS: Five acrylic resin denture teeth (Vipi Dent Plus-V, Trilux-T, Biolux-B, Postaris-P and Artiplus-A) and one composite resin denture teeth (SR-Orthosit-O) were embedded in heat-polymerised acrylic resin within polyvinylchloride tubes. Specimens were stored in distilled water at 37°C for 48 h. Measurements of hardness were taken after the following disinfection procedures: immersion for 7 days in 4% chlorhexidine gluconate or in 1% sodium hypochlorite (CIm and HIm group, respectively) and seven daily cycles of microwave sterilisation at 650 W for 6 min (MwS group). In the WIm group, specimens were maintained in water during the time used to perform the disinfection procedures (7 days). Data were analysed with anova followed by the Bonferroni procedure (α = 0.01). RESULTS: Microwave disinfection decreased the hardness of all acrylic resin denture teeth (p < 0.001). Immersion for 7 days in 4% chlorhexidine gluconate or distilled water had significant effect on the hardness of the acrylic resin denture teeth A (p < 0.01), and 1% sodium hypochlorite on teeth T (p < 0.01). All disinfection procedures decrease the hardness of the composite resin denture teeth (p < 0.01). Teeth O exhibited the highest and teeth V the lowest hardness values in the control group (p < 0.01). CONCLUSIONS: Disinfection procedures changed the hardness of resin denture teeth.

Microwave disinfection: cumulative effect of different power levels on physical properties of denture base resins.

PURPOSE: This study evaluated the cumulative effects of different microwave power levels on the physical properties of two poly(methylmethacrylate) (PMMA) denture base resins. MATERIALS AND METHODS: Eight sets of four PMMA specimens each (two polymerized in a water bath and two using microwave energy) were immersed in beakers containing 200 ml of distilled water. Each beaker was subjected to microwave irradiation for 3 minutes at a power level of 450,630, or 900 W. The surface roughness, surface hardness, linear stability, flexural strength, elastic modulus, impact strength, and fractographic properties were evaluated after either 6 or 36 simulated disinfection cycles. The data were statistically analyzed using ANOVA and the Tukey post hoc test (α= 0.05). RESULTS: The polymerization method did not influence any property (p > 0.05) except linear stability. The surface roughness (p < 0.001) and hardness (p= 0.011) increased after 36 irradiation cycles at 630 or 900 W. The resin polymerized using microwave energy exhibited greater linear distortion (p= 0.012), and there was a cumulative effect on linear stability for both resins (p < 0.001). No significant change (p > 0.05) was observed in flexural strength; however, the elastic modulus decreased (p= 0.008) after 36 disinfection cycles. The impact strength and crack propagation angles displayed no significant differences (p > 0.05). CONCLUSION: Within the limitations of this study, it can be concluded that microwave disinfection at 450 W to 630 W for 3 minutes is safe for PMMA.

Photo-mechanical effect in luminescent polymeric materials.

The photomechanical effect was found for the first time in a polymer composition on the basis of polymethylmethacrylate with embedded molecules of the luminophor dibenzoylmethanate of boron difluoride incapable of undergoing photochemical isomerization, unlike other compounds. A thermal mechanism of photochemical displacement was suggested.

Optimization of 3-hole-assisted PMMA optical fiber with double cladding for UV-induced FBG fabrication.

We propose a new hole-assisted polymer optical fiber design to eliminate the influence of dopant diffusion and to increase the UV writing efficiency in fiber Bragg grating inscription. The optical waveguide is formed inside a solid core surrounded by a ring of 3 large air holes in enhanced UV photosensitive PMMA with double-cladding. We determined a map of the single-mode and multi-mode phase transitions using a finite-element- based vectorial optical mode solver. We obtained a wide range of geometrical configuration for the single-transverse-mode (HE11) propagation in the visible. The design is optimized to operate at the minimum optical loss wavelengths of 580 nm and 770 nm.

The formation of hollow poly(methyl methacrylate)/multiwalled carbon nanotube nanocomposite cylinders by microwave irradiation.

Poly(methyl methacrylate) (PMMA)/multiwalled carbon nanotube (MWCNT) nanocomposite particles with 1, 2 and 4 wt% of MWCNTs were prepared by mechanical grinding of PMMA and MWCNT powders in a mortar at room temperature. Both scanning electron microscopy and Raman scattering characterizations revealed that these nanocomposite particles consist of a PMMA core and a MWCNT shell. The PMMA/MWCNT nanocomposite particles were used to fabricate the corresponding nanocomposites in the form of a hollow cylinder with various diameters and heights under 700 W microwave irradiation within 1 min. A mechanism for the fast microwave assisted forming process is proposed. These experimental results may lead to a new technology for forming hollow polymeric articles that is different from the conventional injection and blowing process.

Effects of ethanol on the surface and bulk properties of a microwave-processed PMMA denture base resin.

PURPOSE: This study evaluated the effect of different concentrations of ethanol on hardness, roughness, flexural strength, and color stability of a denture base material using a microwave-processed acrylic resin as a model system. MATERIALS AND METHODS: Sixty circular (14 x 4 mm) and 60 rectangular microwave-polymerized acrylic resin specimens (65 x 10 x 3 mm(3)) were employed in this study. The sample was divided into six groups according to the ethanol concentrations used in the immersion solution, as follows: 0% (water), 4.5%, 10%, 19%, 42%, and 100%. The specimens remained immersed for 30 days at 37 degrees C. The hardness test was performed by a hardness tester equipped with a Vickers diamond penetrator, and a surface roughness tester was used to measure the surface roughness of the specimens. Flexural strength testing was carried out on a universal testing machine. Color alterations (DeltaE) were measured by a portable spectrophotometer after 12 and 30 days. Variables were analyzed by ANOVA/Tukey's test (alpha= 0.05). RESULTS: For the range of ethanol-water solutions for immersion (water only, 4.5%, 10%, 19.5%, 42%, and 100%), the following results were obtained for hardness (13.9 +/- 2.0, 12.1 +/- 0.7, 12.9 +/- 0.9, 11.2 +/- 1.5, 5.7 +/- 0.3, 2.7 +/- 0.5 VHN), roughness (0.13 +/- 0.01, 0.15 +/- 0.07, 0.13 +/- 0.05, 0.13 +/- 0.02, 0.23 +/- 0.05, 0.41 +/- 0.19 mum), flexural strength (90 +/- 12, 103 +/- 18, 107 +/- 16, 90 +/- 25, 86 +/- 22, 8 +/- 2 MPa), and color (0.8 +/- 0.6, 0.8 +/- 0.3, 0.7 +/- 0.4, 0.9 +/- 0.3, 1.3 +/- 0.3, 3.9 +/- 1.5 DeltaE) after 30 days. CONCLUSIONS: The findings of this study showed that the ethanol concentrations of tested drinks affect the physical properties of the investigated acrylic resin. An obvious plasticizing effect was found, which could lead to a lower in vivo durability associated with alcohol consumption.

Suitability of Filofocon A and PMMA for experimental models in excimer laser ablation refractive surgery.

Experimental corneal models in plastic (in PMMA, and more recently in Filofocon A, a contact lens material) have been proposed recently to overcome some of the limitations of the theoretical approaches aiming at improving the predictability of corneal reshaping by laser ablation. These models have also been proposed for accurate assessment of corneal laser ablation patterns. In this study Filofocon A and PMMA optical and ablation properties were studied using an experimental excimer laser set-up. The effective absorption coefficient and the ablation thresholds of these materials were obtained as a function of the number of pulses. Both materials follow a Beer-Lambert law in the range of fluences used in refractive surgery, and the number of incubation pulses is less than 4 (PMMA) and 2 (Filofocon A) above 140 mJ/cm2. We found that above 40 pulses for Filofocon A and 70 pulses for PMMA, ablation threshold and effective absorption coefficients can be considered constant (F th = 90 mJ/cm2 and alpha eff = 36000 cm(-1), for Filofocon A, and F th = 67 mJ/cm2 and alpha eff = 52000 cm(-1) for PMMA, respectively). The absence of ablation artifacts (central islands), a lower number of incubation pulses, a lower pulse-number dependence of the ablation threshold, and a good correspondence between alpha eff and the absorption coefficient alpha estimated from spectroscopic measurements make Filofocon A a more appropriate material than PMMA for experimental models in refractive surgery and for calibration of clinical lasers.

Thermal stability of acrylic bone cement powder under shelf storage conditions: an isothermal microcalorimetric study.

Heat-conduction isothermal microcalorimetry was used to measure the exothermic heat flow rate (Q) from the powder of a widely used commercially-available acrylic bone cement, Palacos R, when it interacted with ambient laboratory air, as a function of time, t, in the calorimeter, for up to 200 h. Four variants of the powder were used, these being unsterilized, sterilized using ethylene oxide gas, gamma-irradiated, in ambient air, with a minimum dosage of 2.5 Mrad, and gamma-irradiated, in ambient air, with a minimum dosage of 4.5 Mrad. In each case, the powder variant was tested after being stored on the shelf, under ambient conditions, for 2 days, 3 weeks and 9 months immediately following sterilization. Best-fit correlations between Q and t for each powder variant were determined. Then, this relationship was integrated over the period 14 h< or =t< or =200 h to give an estimate of the "effective" heat flow, Q(eff). For powder variants tested 2 days after being sterilized, the difference in their thermal stabilities (Qeff ranged from 0.19+/-0.01 to 0.62+/-0.03 microJ/g, respectively) was significant in the case of some pairs and not for others. However, for powders tested either 3 weeks or 9 months following sterilization, there was no significant difference between the means of Qeff (they ranged from 0.18+/-0.01 to 0.31+/-0.07 microJ/g) for any pair. These results suggest that an acrylic bone cement in which the powder is EtO-sterilized may be mixed with the liquid monomer for use in cemented arthroplasties after any length of time of shelf storage of the powder, under ambient conditions, whereas, for powders that are gamma-irradiated and then stored under the same conditions, at least 3 weeks should elapse before they are used in these procedures.

Secondary radiation measurements for particle therapy applications: charged particles produced by 4He and 12C ion beams in a PMMA target at large angle.

Proton and carbon ion beams are used in the clinical practice for external radiotherapy treatments achieving, for selected indications, promising and superior clinical results with respect to x-ray based radiotherapy. Other ions, like [Formula: see text] have recently been considered as projectiles in particle therapy centres and might represent a good compromise between the linear energy transfer and the radiobiological effectiveness of [Formula: see text] ion and proton beams, allowing improved tumour control probability and minimising normal tissue complication probability. All the currently used p, [Formula: see text] and [Formula: see text] ion beams allow achieving sharp dose gradients on the boundary of the target volume, however the accurate dose delivery is sensitive to the patient positioning and to anatomical variations with respect to photon therapy. This requires beam range and/or dose release measurement during patient irradiation and therefore the development of dedicated monitoring techniques. All the proposed methods make use of the secondary radiation created by the beam interaction with the patient and, in particular, in the case of [Formula: see text] ion beams are also able to exploit the significant charged radiation component. Measurements performed to characterise the charged secondary radiation created by [Formula: see text] and [Formula: see text] particle therapy beams are reported. Charged secondary yields, energy spectra and emission profiles produced in a poly-methyl methacrylate (PMMA) target by [Formula: see text] and [Formula: see text] beams of different therapeutic energies were measured at 60° and 90° with respect to the primary beam direction. The secondary yield of protons produced along the primary beam path in a PMMA target was obtained. The energy spectra of charged secondaries were obtained from time-of-flight information, whereas the emission profiles were reconstructed exploiting tracking detector information. The obtained measurements are in agreement with results reported in the literature and suggests the feasibility of range monitoring based on charged secondary particle detection: the implications for particle therapy monitoring applications are also discussed.