Biocompatible Bacterial Cellulose-Poly(2-hydroxyethyl methacrylate) Nanocomposite Films

A series of bacterial cellulose-poly(2-hydroxyethyl methacrylate) nanocomposite films was prepared by in situ radical polymerization of 2-hydroxyethyl methacrylate (HEMA), using variable amounts of poly(ethylene glycol) diacrylate (PEGDA) as crosslinker. Thin films were obtained, and their physical, chemical, thermal, and mechanical properties were evaluated. The films showed improved translucency compared to BC and enhanced thermal stability and mechanical performance when compared to poly(2-hydroxyethyl methacrylate) (PHEMA). Finally, BC/PHEMA nanocomposites proved to be nontoxic to human adipose-derived mesenchymal stem cells (ADSCs) and thus are pointed as potential dry dressings for biomedical applications.

Temperature-and pH-Sensitive Nanohydrogels of Poly(N-Isopropylacrylamide) for Food Packaging Applications: Modelling the Swelling-Collapse Behaviour

Temperature-sensitive poly(N-isopropylacrylamide) (PNIPA) nanohydrogels were synthesized by nanoemulsion polymerization in water-in-oil systems. Several cross-linking degrees and the incorporation of acrylic acid as comonomer at different concentrations were tested to produce nanohydrogels with a wide range of properties. The physicochemical properties of PNIPA nanohydrogels, and their relationship with the swelling-collapse behaviour, were studied to evaluate the suitability of PNIPA nanoparticles as smart delivery systems (for active packaging). The swelling-collapse transition was analyzed by the change in the optical properties of PNIPA nanohydrogels using ultraviolet-visible spectroscopy. The thermodynamic parameters associated with the nanohydrogels collapse were calculated using a mathematical approach based on the van't Hoff analysis, assuming a two-state equilibrium (swollen to collapsed). A mathematical model is proposed to predict both the thermally induced collapse, and the collapse induced by the simultaneous action of two factors (temperature and pH, or temperature and organic solvent concentration). Finally, van't Hoff analysis was compared with differential scanning calorimetry. The results obtained allow us to solve the problem of determining the molecular weight of the structural repeating unit in cross-linked NIPA polymers, which, as we show, can be estimated from the ratio of the molar heat capacity (obtained from the van't Hoff analysis) to the specific heat capacity (obtained from calorimetric measurements).

Experimental Characterization Of Electrical Current Leakage In Poly(Dimethylsiloxane) Microfluidic Devices

Poly(dimethylsiloxane) (PDMS) is usually considered as a dielectric material and the PDMS microchannel wall can be treated as an electrically insulated boundary in an applied electric field. However, in certain layouts of microfluidic networks, electrical leakage through the PDMS microfluidic channel walls may not be negligible, which must be carefully considered in the microfluidic circuit design. In this paper, we report on the experimental characterization of the electrical leakage current through PDMS microfluidic channel walls of different configurations. Our numerical and experimental studies indicate that for tens of microns thick PDMS channel walls, electrical leakage through the PDMS wall could significantly alter the electrical field in the main channel. We further show that we can use the electrical leakage through the PDMS microfluidic channel wall to control the electrolyte flow inside the microfluidic channel and manipulate the particle motion inside the microfluidic channel. More specifically, we can trap individual particles at different locations inside the microfluidic channel by balancing the electroosmotic flow and the electrophoretic migration of the particle.

Micromachining Of Passive Planar Micromixer On Poly (Methyl Methacrylate) Substrate With Excimer Laser Ablation

Excimer laser ablation technique was introduced into this work to fabricate a passive planar micromixer on the PMMA substrate. T-junction shaped and width-changed S-shaped microchannels were both designed in this micromixer to enhance mixing effect. The mixing experiment of distilled water and Rhodamine B with injection flow rate of 500 and 1,500 mu m/s validates the mixing effectivity of this micromixer, and indicates the feasibility of excimer laser ablation in the microfabrication of mu-TAS device.

Mechanisms of femtosecond laser-induced damage in magnesium fluoride

We studied the single-shot damage in magnesium fluoride irradiated by 800 nm femtosecond (fs) laser. The dependence of damage thresholds on the laser pulse durations from 60 to 750 fs was measured. The pump-probe measurements were carried out to investigate the time-resolved electronic excitation processes. A coupled dynamic model was applied to study the microprocesses in the interaction between fs laser and magnesium fluoride. The results indicate that both multiphoton ionization and avalanche ionization play important roles in the femtosecond laser-induced damage in MgF2. (C) 2006 Elsevier Ltd. All rights reserved.

Pulse NMR in solids : chemical shift, lead fluoride and thorium hydride

Part one of this thesis consists of two sections. In the first section the fluorine chemical shift of a single crystal CaF_2 has been measured as a function of external pressure up to 4 kilobar at room temperature using multiple pulse NMR techniques. The pressure dependence of the shift is found to be -1.7 ± 1 ppm/kbar, while a theoretical calculation using an overlap model predicts a shift of -0.46 ppm/kbar. In the second section a separation of the chemical shift tensor into physically meaningful "geometrical" and "chemical" contributions is presented and a comparison of the proposed model calculations with recently reported data on hydroxyl proton chemical shift tensors demonstrates, that for this system, the geometrical portion accounts for the qualitative features of the measured tensors.

Part two of the thesis consists of a study of fluoride ion motion in β-PbF_2 doped with NaF by measurement of the ^(19)F transverse relaxation time (T_2), spin lattice relaxation time (T_1) and the spin lattice relaxation time in the rotating frame (T_(1r)). Measurements over the temperature range of -50°C to 160°C lead to activation energies for T_1, T_(1r) and T_2 of 0.205 ± 0.01, 0.29 + 0.02 and 0.27 ± 0.01 ev/ion, and a T_(1r) minimum at 56°C yields a correlation time of 0.74 μsec. Pressure dependence of T_1 and T_2 yields activation volumes of <0.2 cm^3/g-mole and 1.76 ± 0.05 cm^3/g-mole respectively. These data along with the measured magnetic field independence of T_1 suggest that the measured T_1's are not caused by ^(19)F motion, but by thermally excited carriers.

Part three of the thesis consists of a study of two samples of Th_4H_(15), prepared under different conditions but both having the proper ratio of H/Th (to within 1%). The structure of the Th_4H_(15) as suggested by X-ray measurements is confirmed through a moment analysis of the rigid lattice line shape. T_1 and T_2 measurements above 390 K furnish activation energies of 16.3 ± 1.2 kcal/mole and 18.0 ± 3.0 kcal/mole, respectively. Below 350 K, T_(1r) measurements furnish an activation energy of 10.9 ± 0.7 kcal/mole, indicating most probably more than a single mechanism for proton motion. A time-temperature hysteresis effect of the proton motion was found in one of the two samples and is strongly indicative of a phase change. T_1 at room temperature and below is dominated by relaxation due to conduction electrons with the product T_1T being 180 ± 10 K-sec. Using multiple pulse techniques to greatly reduce homonuclear dipolar broadening, a temperature-dependent line shift was observed, and the chemical shift anisotropy is estimated to be less than 16 ppm.

Miscibility and Hydrogen Bonding in Blends of Poly(4-vinylphenol)/Poly(vinyl methyl ketone)

The miscibility and phase behavior of poly(4-vinylphenol) (PVPh) with poly(vinyl methyl ketone) (PVMK) was investigated by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). It was shown that all blends of PVPh/PVMK are totally miscible. A DSC study showed the apparition of a single glass transition (T-g) over their entire composition range. When the amount of PVPh exceeds 50% in blends, the obtained T(g)s are found to be significantly higher than those observed for each individual component of the mixture, indicating that these blends are capable of forming interpolymer complexes. FTIR analysis revealed the existence of preferential specific interactions via hydrogen bonding between the hydroxyl and carbonyl groups, which intensified when the amount of PVPh was increased in blends. Furthermore, the quantitative FTIR study carried out for PVPh/PVMK blends was also performed for the vinylphenol (VPh) and vinyl methyl ketone (VMK) functional groups. These results were also established by scanning electron microscopy study (SEM).

Poly(lactic acid)-based bio-blends and nanocomposites

172 p.

Tm-doped fibre laser pumped Cr2+: ZnSe poly-crystal laser

Demonstrations of cw lasing in Cr2+:ZnSe poly-crystal are reported. The laser consists of a 1.7-mm-thick Cr2+:ZnSe poly-crystal disc pumped by a Tm-silica double-clad fibre laser at 2050nm. Using a concave high-reflection mirror with a radius of curvature of 500mm as the rear mirror, the laser delivers up to 1030mW of radiation around 2.367 mu m.

Structural role of fluoride in aluminophosphate sol-gel glasses: High-resolution double-resonance NMR studies

The local structure of Na-Al-P-O-F glasses, prepared by a novel sol-gel route, was extensively investigated by advanced solid-state NMR techniques. Al-21{F-19} rotational echo double resonance (REDOR) results indicate that the F incorporated into aluminophosphate glass is preferentially bonded to octahedral Al units and results in a significant increase in the concentration of six-coordinated aluminum. The extent of Al-F and Al-O-P connectivities are quantified consistently by analyzing Al-27{P-31} and Al-21{F-19} REDOR NMR data. Two distinct types of fluorine species were identified and characterized by various F-19{Al-27}, F-19{Na-23}, and F-19{P-31} double resonance experiments, which were able to support peak assignments to bridging (Al-F-Al, -140 ppm) and terminal (Al-F, -170 ppm) units. On the basis of the detailed quantitative dipole-dipole coupling information obtained, a comprehensive structural model for these glasses is presented, detailing the structural speciation as a function of composition.

Investigation of the effect of fluoride ions introduction on structural, OH- content and up-conversion luminescence properties in Er3+-doped heavy metal oxide glasses

Effect of fluoride ions introduction on structural, OH- content and up-conversion luminescence properties in Er3+-doped heavy metal oxide glasses have been investigated. Structure was investigated, indicating that fluoride has an important influence on the phonon density, maximum phonon energy of host glasses. With increasing fluoride content, the up-conversion luminescence intensity and quantum efficiencies increase notably, which could not be explained only by the maximum phonon energy change of host glasses. Our results show that, with the introduction of PbF2, the decrease of phonon density and OH- content contributes more to the enhanced up-conversion emissions than that of maximum phonon energy. (c) 2005 Elsevier B.V. All rights reserved.

Effect of alkali and alkaline earth fluoride introduction on thermal stability and structure of fluorophosphate glasses

The thermal stability and structure of RF-RF2-AIF(3)-Al(PO3)(3) fluorophosphate glasses were investigated. Analyses of infrared absorbance spectra and Raman spectra reveal that with increasing number of alkali and alkaline earth fluoride components, the sum of P-O-P bond and O-P-O bond increases and glass network is strengthened. Consequently, the inhibition to nucleation and crystallization processes is improved, which is proved by the increment of thermal stability factors AT and S determined by differential scanning calorimetry. In addition, it was found that LiF has poor ability to form glass in univalent alkali fluorides and MgF2 has comparative strong ability to form glass in bivalent alkaline earth fluorides. (c) 2006 Published by Elsevier B.V.

UV-blue upconverted emission from Nd3+-doped InF3-based heavy-metal fluoride glasses for blue upconversion fibre laser

We report spectral properties and thermal stability of Nd3+-doped InF3-based heavy-metal fluoride glasses. Fluoroindate glasses in the chemical compositions (in mol%) of (38-x)InF3-16BaF(2)-20ZnF(2)-20SrF(2)-3GdF(3)-1GaF(3-)2NaF-xNdF(3) (x = 0.1, 0.5, 1, 2, 3) have been prepared under a controlled atmosphere in a dry box. Strong UVblue upconversion emission from a green excitation wavelength has been observed and the involved mechanisms have been explained. Near-infrared emission occurs simultaneously upon excitation of the UV-blue upconversion emissions with a cw Ar(+)laser. The upconversion spectra have revealed four dominant emissions at 354, 380, 412 and 449 nm, which belong to the transitions of D-4(3/2) -> I-4(9/2), D-4(3/2) -> I-4(11/2) and P-2(3/2) -> I-4(9/2), D-4(3/2) -> I-4(13/2) and P-2(3/2) -> I-4(11/2), D-4(3/2) -> I-4(15/2) and P-2(3/2) -> I-4(13/2), respectively.

Effects of chloride substitution on the chemical and physical properties and the crystallization behavior in heavy metal fluoride glasses

Effect of the substitutions of chloride for fluoride on the chemical and physical properties and the crystallization behavior in heavy metal fluoride glasses has been investigated. The characteristic temperature of the glass does not changed obviously when the fluoride was taken place by chloride. Compared with samples of being free of ErF3, the doping samples are more inclined to be surface crystallization. Optical basicity in the glass system increases with increasing the negative charge provided by the chloride atoms and the absorption peak red shifted is observed in absorption spectra. XRD measurements show that not a single crystalline phase appears in the heated glass samples, which indicate the substitutions of chloride for fluoride with a variety of crystalline precipitation trends. (c) 2007 Elsevier B.V All rights reserved.

Temperature-and pH-Sensitive Nanohydrogels of Poly(N-Isopropylacrylamide) for Food Packaging Applications: Modelling the Swelling-Collapse Behaviour

Temperature-sensitive poly(N-isopropylacrylamide) (PNIPA) nanohydrogels were synthesized by nanoemulsion polymerization in water-in-oil systems. Several cross-linking degrees and the incorporation of acrylic acid as comonomer at different concentrations were tested to produce nanohydrogels with a wide range of properties. The physicochemical properties of PNIPA nanohydrogels, and their relationship with the swelling-collapse behaviour, were studied to evaluate the suitability of PNIPA nanoparticles as smart delivery systems (for active packaging). The swelling-collapse transition was analyzed by the change in the optical properties of PNIPA nanohydrogels using ultraviolet-visible spectroscopy. The thermodynamic parameters associated with the nanohydrogels collapse were calculated using a mathematical approach based on the van't Hoff analysis, assuming a two-state equilibrium (swollen to collapsed). A mathematical model is proposed to predict both the thermally induced collapse, and the collapse induced by the simultaneous action of two factors (temperature and pH, or temperature and organic solvent concentration). Finally, van't Hoff analysis was compared with differential scanning calorimetry. The results obtained allow us to solve the problem of determining the molecular weight of the structural repeating unit in cross-linked NIPA polymers, which, as we show, can be estimated from the ratio of the molar heat capacity (obtained from the van't Hoff analysis) to the specific heat capacity (obtained from calorimetric measurements).