Synthesis of poly(alkenoic acid) with L-leucine residue and methacrylate photopolymerizable groups useful in formulating dental restorative materials

To develop resin-modified glass ionomer materials, we synthesized methacrylate-functionalized acrylic copolymer (PAlk-LeuM) derived from acrylic acid, itaconic acid and N-acryloyl-L-leucine using (N-methacryloyloxyethylcarbamoyl-N′-4-hydroxybutyl) urea as the modifying agent. The spectroscopic (proton/carbon nuclear magnetic resonance, Fourier transform infrared spectroscopy) characteristics, and the gel permeation chromatography/Brookfield viscosity measurements were analysed and compared with those of the non-modified copolymer (PAlk-Leu). The photocurable copolymer (PAlk-LeuM, ~14?mol% methacrylate groups) and its precursor (PAlk-Leu) were incorporated in dental ionomer compositions besides diglycidyl methacrylate of bisphenol A (Bis-GMA) or an analogue of Bis-GMA (Bis-GMA-1), triethylene glycol dimethacrylate and 2-hydroxyethyl methacrylate. The kinetic data obtained by photo-differential scanning calorimetry showed that both the degree of conversion (60.50–75.62%) and the polymerization rate (0.07–0.14?s^?1) depend mainly on the amount of copolymer (40–50 wt.%), and conversions over 70% were attained in the formulations with 40 wt.% PAlk-LeuM. To formulate light-curable cements, each organic composition was mixed with filler (90 wt.% fluoroaluminosilicate/10 wt.% hydroxyapatite) into a 2.7:1 ratio (powder/liquid ratio). The light-cured specimens exhibited flexural strength (FS), compressive strength (CS) and diametral tensile strength (DTS) varying between 28.08 and 64.79?MPa (FS), 103.68–147.13?MPa (CS) and 16.89–31.87?MPa (DTS). The best values for FS, CS and DTS were found for the materials with the lowest amount of PAlk-LeuM. Other properties such as the surface hardness, water sorption/water solubility, surface morphology and fluorescence caused by adding the fluorescein monomer were also evaluated.     

Dermal cells distribution on laser‐structured ormosils

Several dermal substitutes for skin grafting are now commercially available, although their performance still needs improvement. Most artificial dermises have a lower take rate than autologous grafts and require more time for sufficient vascular ingrowth to overlay the skin graft. Herein we characterize new two‐dimensional scaffolds for tissue‐engineering applications, which were fabricated by two‐photon polymerization (2PP) of ormosils hybrid materials. For the 2PP experiments, a Ti:sapphire laser was used to induce the photopolymerization. In this study we showed that the polymeric structures with controlled architectures produced via 2PP could be used as scaffolds for the in vitro culture and proliferation of human dermal fibroblasts. Fluorescence microscopy revealed that the fibroblasts' orientation was guided by the scaffold geometry, consisting of ormosils lines or grids. This 'dermal equivalent' was investigated for its ability to accommodate epidermal cells. To evaluate this interaction, two experimental approaches were hence used: (a) fibroblast–melanocyte co‐cultures; and (b) fibroblast–keratinocyte organotypic cultures. During their growth on ormosil scaffolds, productive interaction of fibroblasts with both epidermal cell types was found. Moreover, this pseudo‐dermis was shown to support the growth of keratinocytes for up to 8 days after their seeding. Copyright © 2011 John Wiley & Sons, Ltd.     

Polyurethanes based on dihydroxamic acids. Synthesis, chemical characterization, and biological activity

A series of segmented polyurethanes based on polyethylene oxide/polycaprolactone diol, isophorone diisocyanate, and dihydroxamic acids were synthesized and characterized. Biocompatibility and antitumoral activity were in vivo tested on Wistar male rats and Wistar rats affected with Walker 256 carcinosarcoma, respectively. The effect of dihydroxamic acid structure on the biological properties was determined. A better antitumoral response of the polyurethanes containing aliphatic dihydroxamic segment compared with those which resulted using terephthaloyl dihydroxamic acid was evidenced. With increasing polymer chain polyethylene oxide content the antitumoral activity was also enhanced. Some attempts on the in vitro biodegradation of above polyurethanes were also performed.     

Synthesis and characterization of novel polyurethane cationomers with dipeptide sequences and alkylammonium groups

A synthetic approach to polyurethane cationomers containing S-pyroglutamyl-S-glutamic acid dipeptide (S-PyGlu-S-Glu) and alkylammonium groups is presented. Two segmented polycations, based on polycaprolactone diol, isophorone diisocyanate and dipeptide together with N-methyldiethanolamine, subsequently quaternized with dodecylbromide, were synthesized and characterized by IR spectroscopy, GPC, DSC and reduced viscosity measurements. Such polycations exhibited excellent film forming properties and their soft elastomeric nature provides adequate physical properties. Optical rotation varying from +10 (monomer) to -15 (polycation) could be associated with a configuration pertubation through the asymmetric carbon atoms of glutamic residues. Susceptibility of the cationic surface to heparinization and then to blood-polymer interaction suggested an anticoagulant activity of the heparinized polymeric films.     

A comparison of MTA, Super-EBA, composite and amalgam as root-end filling materials using a bacterial microleakage model

AIM: The aim of this study was to compare traditional and newly developed root-end filling materials for resistance to bacterial microleakage. METHODOLOGY: Sixty extracted single-rooted teeth were randomly divided into five groups for root-end filling with mineral trioxide aggregate, Super-EBA, TPH composite resin with ProBond dentine bonding agent, Dispersalloy amalgam with and without ProBond, and positive and negative control groups. Root canals were instrumented using the step-back technique and simulated root-end resections performed. Root-end filling materials were placed in 3 mm ultrasonic retropreparations. Nail varnish was applied to all external root surfaces to the level of the resected root ends to prevent lateral microleakage. Samples were sterilized in an ethylene oxide sterilizer for 12 h. Using a newly designed model system, the apical 3-4 mm of the roots were immersed in BHI culture medium with phenol red indicator within culture chambers. The coronal access of each specimen was inoculated every 48 h with a suspension of Streptococcus salivarius. Culture media were observed every 24 h for colour change indicating bacterial contamination. Media demonstrating colour change were plated for S. salivarius. Samples were observed for 12 weeks. RESULTS: At 4 weeks 10% of specimens from each experimental group had evidence of leakage. At 8 weeks 20% of specimens filled with amalgam without dentine bonding agent, Super-EBA and MTA had evidence of leakage. At 12 weeks minor differences between materials were noted. CONCLUSIONS: Under the conditions of the study, despite some variations, there were no statistically significant differences in rate of microleakage among the five groups tested at either 4, 8 or 12 weeks.     

Influence of Deposition Method on the Structural and Optical Properties of Ge2Sb2Te5

Ge2Sb2Te5 (GST-225) is a chalcogenide material with applications in nonvolatile memories. However, chalcogenide material properties are dependent on the deposition technique. GST-225 thin films were prepared using three deposition methods: magnetron sputtering (MS), pulsed laser deposition (PLD) and a deposition technique that combines MS and PLD, namely MSPLD. In the MSPLD technique, the same bulk target is used for sputtering but also for PLD at the same time. The structural and optical properties of the as-deposited and annealed thin films were characterized by Rutherford backscattering spectrometry, X-ray reflectometry, X-ray diffraction, Raman spectroscopy and spectroscopic ellipsometry. MS has the advantage of easily leading to fully amorphous films and to a single crystalline phase after annealing. MS also produces the highest optical contrast between the as-deposited and annealed films. PLD leads to the best stoichiometric transfer, whereas the annealed MSPLD films have the highest mass density. All the as-deposited films obtained with the three methods have a similar optical bandgap of approximately 0.7 eV, which decreases after annealing, mostly in the case of the MS sample. This study reveals that the properties of GST-225 are significantly influenced by the deposition technique, and the proper method should be selected when targeting a specific application. In particular, for electrical and optical phase change memories, MS is the best suited deposition method.     

New Chalcogenide Glass-Ceramics Based on Ge-Zn-Se for IR Applications

The consumer market requests infrared (IR) optical components, made of relatively abundant and environmentally friendly materials, to be integrated or attached to smartphones. For this purpose, three new chalcogenides samples, namely Ge_23.3Zn_30.0Se_46.7 (d_GZSe-1), Ge_26.7Zn_20.0Se_53.3 (d_GZSe-2) and Ba_4.0Ge_12.0Zn_17.0Se_59.0I_8.0 (d_GZSe-3) were obtained by mechanical alloying and processed by spark plasma sintering into dense bulk disks. Obtaining a completely amorphous and homogeneous material proved to be difficult. d_GZSe-2 and d_GZSe-3 are glass-ceramics with the amount of the amorphous phase being 19.7 and 51.4 wt. %, while d_GZSe-1 is fully polycrystalline. Doping with barium and iodine preserves the amorphous phase formed by milling and lowers the sintering temperature from 350 °C to 200 °C. The main crystalline phase in all of the prepared samples is cubic ZnSe or cubic Zn_0.5Ge_0.25Se, while in d_GZSe-3 the amorphous phase contains GeSe4 clusters. The color of the first two sintered samples is black (the band gap values are 0.42 and 0.79 eV), while d_GZSe-3 is red (E_g is 1.37 eV) and is transparent in IR domain. These results are promising for future research in IR materials and thin films.