Annealing effect reversal by water sorption-desorption and heating above the glass transition temperature-comparison of properties.

Our objective is to compare the physical properties of materials obtained from two different methods of annealing reversal, that is, water sorption-desorption (WSD) and heating above glass transition temperature (HAT). Trehalose was annealed by storing at 100 °C for 120 h. The annealing effect was reversed either by WSD or HAT, and the resulting materials were characterized by differential scanning calorimetry (DSC), water sorption studies, and positron annihilation spectroscopy (PAS). While the products obtained by the two methods of annealing reversal appeared to be identical by conventional characterization methods, they exhibited pronounced differences in their water sorption behavior. Positron annihilation spectroscopy (PAS), by measuring the fractional free volume changes in the processed samples, provided a mechanistic explanation for the differences in the observed behavior.

Decoupling free-carriers contributions from oxygen-vacancy and cation-substitution in extrinsic conducting oxides.

The intrinsic oxygen-vacancies and the extrinsic dopants are two major fundamental free-carrier sources for the extrinsic conducting oxides, such as Sn-doped In(2)O(3). Yet, the individual contributions of the above two free-carrier sources to the total carrier concentrations have never been unraveled. A carrier-concentration separation model is derived in this work, which can define the individual contributions to the total carrier concentration from the intrinsic oxygen-vacancies and the extrinsic dopants, separately. The individual contributions obtained from the present carrier-concentration separation model are verified by the two-state trapping model, photoluminescence, and positron annihilation lifetime (PAL) spectroscopy. In addition, the oxygen-vacancy formation energy of the Sn:In(2)O(3) thin film is determined to be 0.25 eV by PAL spectroscopy.

Correlation between free-volume properties and pervaporative flux of polyurethane-zeolite composites on organic solvent mixtures.

Micron-sized zeolite particles were incorporated into a polyurethane (PU) matrix to prepare ethylbenzene-selective membranes. The resulting composite membranes were used in the pervaporation (PV) of ethylbenzene/styrene (EB/ST) mixtures. The sorption, diffusion, and PV permeation behaviors as a result of zeolite addition were elucidated. Zeolite is less chemically compatible with organic solvents than PU and the PU-zeolite composites, which exhibited suppressed solvent solubilities compared with pristine PU. However, these membranes favor EB transport by diffusion selectivity. The diffusivity and permeation flux increases in parallel with the enlarged radius of the free-volume hole size (R(4) increasing from 3.46 to 3.64 Å using positron annihilation lifetime spectroscopy analysis) by increasing the zeolite content from 0 to 23%. The enlarged free volume at a zeolite loading of 23% promoted pure solvent diffusivities by 10% higher than that of the unfilled film. During the PV operation on the EB/ST mixture, a significant diffusion-coupling was observed, and the permeant diffusion coefficients from the binary mixture exceeded the pure solvent diffusivity. The permeation flux was greatly improved (up to 0.72 kg/m(2)·h) by zeolite addition without any detrimental effect on the separation efficiency.

Subsurface characterization of carbon nanotubes in polymer composites via quantitative electric force microscopy.

Subsurface characterization of carbon nanotubes (CNTs) dispersed in free-standing polymer composite films was achieved via quantitative electric force microscopy (EFM). The effects of relative humidity, EFM probe geometry, tip-sample distance and bias voltage on the EFM contrast were studied. Non-parabolic voltage dependence of the EFM signal of subsurface CNTs in polymer composites was observed and a new mechanism was proposed taking consideration of capacitive coupling as well as coulombic coupling. We anticipate that this quantitative EFM technique will be a useful tool for non-destructive subsurface characterization of high dielectric constant nanostructures in low dielectric constant matrices.

Positron annihilation spectroscopy for surface and interface studies in nanoscale polymeric films.

Positron annihilation spectroscopy (PAS), coupled with a variable mono-energetic positron beam, has been used to investigate surface and interfacial properties in thin polymeric films. Free-volume properties have been measured from ortho-Positronium (o-Ps) lifetime and the S parameter of Doppler broadening of energy spectra from annihilation radiation as a function of the depth and of the temperature in thin polymeric films. Depth profiles of glass transition temperature and nanoscale layered structures in polystyrene (PS) thin films on the Si substrate are presented.

Depth profile of free volume in a mixture and copolymers of poly(N-vinyl-pyrrolidone) and poly(ethylene glycol) studied by positron annihilation spectroscopy.

Effect of hydrogen bonding on the depth profile of the free-volume in a mixture (weight ratio of 65:35) of poly(N-vinyl-pyrrolidone) (PVP) and poly(ethylene glycol) (PEG) and the copolymers of vinyl pyrrolidone with poly(ethylene glycol) diacrylate (PVP-PEGDA) and monomethacrylate (PVP-PEGMMA) was studied using positron annihilation spectroscopy. Doppler broadening energy spectra of annihilation radiation and positron annihilation lifetime were measured as a function of positron incident energy (0-30 keV). Significant variations of the free-volume depth profile in terms of the S parameter, ortho-positronium lifetime, intensity, and lifetime distribution are observed as a result of the hydrogen-bonding replacement of covalent bonds. The polymer mixture with hydrogen bonding through two sides of PEG short chains has a larger free volume and a wider distribution than the comb-structured PVP-PEGMMA and the network structured PVP-PEGDA. A longer ortho-positronium lifetime is observed near the surface than in the bulk. This is interpreted in terms of surface effect, free volume, and hydrogen bonding for drug delivery applications of polymeric materials.

Amplified potentiometric determination of pK(00), pK(0), pK(l), and pK(2) of hydrogen sulfides with Ag(2)S ISE.

The chemical capacitor theory has been applied to accurately determine dissociation constants of H(2)S with the Ag(2)S ion-selective electrode (ISE). The theory's principle is based on the measurement of the change in electrode charge density as a result of protonated or unprotonated sulfide adsorbed on the electrode surface. This charge density is related to the potential. Connection of each individual capacitor in series amplifies the potential according to the equation, E(total)=E(1)+E(2)+E(3)+cdots, three dots, centeredE(n). As the charges of individual capacitors are concentrated to one capacitor area, the charge density rises, and the potential increases. The pK(00), pK(0), pK(1), and pK(2) are reported as 1.8, 2.12, 7.05, and 12.0, respectively. The pK(00) and pK(0) are reported here for the first time. The pK(1) agrees well with the literature values; however, the pK(2) differs from those reported recently under extreme conditions. Reasons for disproving the unreasonably high pK(2)>>17-19 values are given based on calculations. Mainly, when pK(2)>>17-19, the experimental results do not fit the equilibrium equations, pH=(pK(1)+pK(2))/2, pK(1)=(pK(0)+pK(2))/2, and pH=pK(2)+log(HS(-))/(S(2-)).

Traumatic spinal cord injuries in the rural region of Taiwan: an epidemiological study in Hualien county, 1986-1990.

In order to survey the epidemiological characteristics of traumatic spinal cord injuries (SCI) in Hualien county, a retrospective study was conducted from January 1986 to December 1990 in four local general hospitals. During this period, 135 traumatic SCI patients were identified and 99 of them were residents of Hualien county. The estimated annual incidence of traumatic SCI in Hualien county was 56.1 per million population. As a result of injury 36 patients were tetraparetic, 33 tetraplegic, 12 paraparetic and 18 paraplegic. The male/female ratio was 4:1. The mean age of onset for male patients was 44 years, and that for female patients was 46 years. The major causes of SCI were traffic accident (61.6%) followed by accidental falls (23.3%). The average duration of hospitalisation ranged from 62 days in paraparetics to 132 days in tetraplegics. Ten patients died of respiratory failure or sepsis, and the mortality rate was 10.1%. Our data revealed that traumatic SCI was prevalent in Hualien county in comparison with epidemiological studies elsewhere. The special population composition of Hualien county and the preponderance of the motorcycle as a transportation vehicle in this area might result in its unique epidemiological characteristics.

Z-DNA structure of a modified DNA hexamer at 1.4-A resolution: aminohexyl-5'-d(pCpGp[br5C]pGpCpG).

Oligonucleotides with modification at the 5'-end have been used for various biochemical applications. As a first step to better assess the effects of those modifications on DNA conformation, we determined at 1.4-A resolution the left-handed Z-DNA structure of a DNA hexamer, aminohexyl-5'-d(pCpGp[br5C]pGpCpG), by X-ray diffraction analysis. This hexamer was crystallized in the monoclinic C2 (a = 51.13 A, b = 18.44 A, c = 34.67 A, and beta = 120.9 degrees) space group. Its structure has been refined by the restrained least-squares refinement to a final R factor of 0.164 using 3727 [> 2.0 sigma (F)] observed reflections. The overall conformation of the double helix resembles that of the canonical Z-DNA. The terminal 5'-phosphate groups of the dC residues adopt conformations (beta approximately 180 degrees and gamma approximately 60 degrees) similar to phosphodiester's conformation of the internal dC residues. Two types of interhelical stackings are observed, one of which may serve as a model for a single-strand nick in the backbone of DNA double helix. A barium ion is found to bridge two side-by-side Z-DNA helices by coordinating to the O6 and N7 atoms of two guanines simultaneously. This "cross-linking" ability of barium ion may be a useful property in promoting the reversible aggregation of nucleic acids.

Positron Annihilation Spectroscopy for Chemical Analysis.

The prediction and discovery of the existence of positron (e+)1-4 and positronium atom (Ps)5,6 led rapidly to the development of a new spectroscopic technique for the study of the structure and composition of matter. The technique quickly expanded across interdisciplinary from physics to chemistry, metallurgy, biochemistry and recently to superconductors. As an early non-destructive and in situ testing tool, positron annihilation spectroscopy (PAS) has been utilized extensively to measure crystal defects.7-9.