Micellization and Thermogelation of Poly(ether urethane)s Comprising Poly(ethylene glycol) and Poly(propylene glycol)

A series of multiblock poly(ether urethane)s comprising poly(ethylene glycol) (PEG), and poly(propylene glycol) (PPG) segments were synthesized. Their aqueous solutions exhibited thermogelling behavior at critical gelation concentrations (CGC) ranging from 8 to 12 wt%. The composition and structural information of the copolymers were studied by GPC and ¹H NMR. The critical micellization concentration (CMC) and thermodynamic parameters for micelle formation were determined at different temperatures. The temperature response of the copolymer solutions were studied and found to be associated with the composition of the copolymers.     

Singularities of elliptic mixed boundary problems. Application to boundary stabilization of hyperbolic systems

For elliptic partial differential equations, mixed boundary conditions generate singularities in the solution, mainly when the boundary of the domain is connected. We here consider two classical cases: the Laplace equation and the Lamé system. The knowledge of singularities allows us to construct adapted Rellich relations. These are useful in the problem of boundary stabilization of the wave equation and the elastodynamic system, respectively, when using the multiplier method.     

Cationic Poly([R]‐3‐hydroxybutyrate) Copolymers as Antimicrobial Agents

Poly([R]‐3‐hydroxybutyrate) (PHB), a natural biodegradable polyester, has attracted much attention as a new biomaterial because of its sustainability and good biocompatibility. In this study, it is discovered that PHB can be conveniently functionalized to obtain a number of platform chain architectures that may provide a wide range of functional copolymers. In a transesterification reaction, linear (di‐hydroxylated) and star shaped (tri‐ and tetra‐hydroxylated) PHB oligomers are synthesized, followed by copolymerization with 2‐(dimethylamino)ethyl methacrylate and quaternization with benzyl bromide to afford antimicrobial properties. The antimicrobial activities of the quaternary salts against clinically relevant pathogens on the interactions with outer and cytoplasmic membranes, lethal mechanisms, multipassage resistance, and synergy effect with antibiotics are investigated. Cationic PHB copolymers show effectiveness as antimicrobial agents, with minimum inhibitory concentration values 0.24–0.65 µm (or µmol dm^?3) (or 32–128 µg mL^?1) against Gram‐positive and Gram‐negative bacteria. Modifying the copolymer architectures into star shapes results in enhanced effectiveness to disrupt the membrane integrity. Synergistic effects are attained for all the quaternized PHB derivatives when they are used together with tobramycin. Multipassage resistance does not occur in both the linear and star derivatives against Gram‐negative bacteria after 20 passages.     

Efficient single-frequency fiber lasers with novel photosensitive Er/Yb optical fibers

Boron- and germanium-doped highly photosensitive cladding is used in a novel design to achieve photosensitive Er/Yb-doped fibers, permitting short, strong gratings (length ~1 cm, reflectivity >99%) to be written without hydrogenation. The high absorption at 980 nm in Er/Yb fibers permits efficient pump absorption over a short device length, which is ideal for achieving highly efficient single-frequency fiber lasers. Both single-frequency Bragg-grating reflector and distributed-feedback lasers with slope efficiencies of 25% with respect to launched pump power have been realized in such fibers.     

Structure and phase equilibria of mixtures of the complex salt hexadecyltrimethylammonium polymethacrylate, water and different oils

This work reports on phase diagrams for mixtures of a complex salt formed by a cationic surfactant and an oppositely charged polyelectrolyte, hexadecyltrimethylammonium polymethacrylate, in binary mixtures with water and in ternary mixtures containing water and organic solvents of different polarity ('oils'): decanol, octanol, p-xylene and cyclohexane. The liquid crystalline structures formed were identified by small angle X-ray scattering measurements, which also provided information about changes in the size of the aggregates as a function of the system composition. These results are analysed in comparison with others previously reported [Bernardes et al., J. Phys. Chem. B 110 (2006) 10332-10340] for the analog complex formed with polyacrylate and, in general, reveal that the presence of an extra methylene group in the polymer chain does not produce significant changes in the complex phase diagrams nor in the structure of the liquid crystalline phases formed. Additionally, the obtained results confirm once more the approach used to analyze these kinds of systems formed by polymer and oppositely charged surfactant.     

Adsorption and reaction of 1-epoxy-3-butene on Pt(111): implications for heterogeneous catalysis of unsaturated oxygenates

High-resolution electron energy loss spectroscopy (HREELS), temperature-programmed desorption (TPD), and density functional theory (DFT) calculations were used to study the adsorption and reaction of 1-epoxy-3-butene (EpB) on Pt(111). These investigations were conducted to help elucidate mechanisms for improving olefin hydrogenation selectivity in reactions of unsaturated oxygenates. EpB dosed to Pt(111) at 91 K adsorbs molecularly on the surface through the vinyl group with apparent rehybridization to a di-sigma-bound state. By 233 K, however, EpB undergoes epoxide ring opening to form an aldehyde intermediate, which further decomposes upon heating to yield gas phase products CO, H2, and propylene. Comparison of the HREELS and TPD data to experiments performed with 2-butenal (crotonaldehyde) shows that EpB and 2-butenal decompose through related pathways. However, the EpB-derived aldehyde intermediate clearly has a unique structure, features of which have been elucidated by DFT calculations. In conjunction with previous surface science studies of EpB chemistry, these results can help explain selectivity trends for reactions of EpB on Pt catalysts and bimetallic PtAg catalysts, with indications that the enhanced olefin hydrogenation selectivity of PtAg catalysts likely originates from a bifunctional effect.     

Cell adhesion properties on photochemically functionalized diamond

The biocompatibility of diamond was investigated with a view toward correlating surface chemistry and topography with cellular adhesion and growth. The adhesion properties of normal human dermal fibroblast (NHDF) cells on microcrystalline and ultrananocrystalline diamond (UNCD) surfaces were measured using atomic force microscopy. Cell adhesion forces increased by several times on the hydrogenated diamond surfaces after UV irradiation of the surfaces in air or after functionalization with undecylenic acid. A direct correlation between initial cell adhesion forces and the subsequent cell growth was observed. Cell adhesion forces were observed to be strongest on UV-treated UNCD, and cell growth experiments showed that UNCD was intrinsically more biocompatible than microcrystalline diamond surfaces. The surface carboxylic acid groups on the functionalized diamond surface provide tethering sites for laminin to support the growth of neuron cells. Finally, using capillary injection, a surface gradient of polyethylene glycol could be assembled on top of the diamond surface for the construction of a cell gradient.