Detailed mapping of biaxial orientation in polyethylene terephthalate bottles using polarised attenuated total reflection FTIR spectroscopy

Polarised attenuated total reflection FTIR spectroscopy has been used for detailed orientation mapping of 2l polyethylene terephthalate bottles subjected to different preform heating times. The results for the bottle with the standard preform heating time reveal significant surface orientation variations along the bottle hoop and length directions, with the inner bottle surface also showing consistently greater chain orientation in the hoop direction than found for the outer surface. Decreasing the preform heating time has less effect on the chain orientation than increasing the heating time, with the latter causing reduced chain orientation in the final bottle. The absorbance of the 1340 cm⁻¹ band provides a quick and reliable indication of these chain orientation trends. In contrast, the extent of benzene ring orientation parallel to the bottle surface showed little variation and remained consistently high at the majority of the surface bottle positions probed.     

The Complex and Critical Role of Glycine 12 (G12) in Beta-Connexins of Human Skin

Glycine is an amino acid with unique properties because its side chain is composed of a single hydrogen atom. It confers conformational flexibility to proteins and conserved glycines are often indicative of protein domains involving tight turns or bends. All six beta-type connexins expressed in human epidermis (Cx26, Cx30, Cx30.3, Cx31, Cx31.1 and Cx32) contain a glycine at position 12 (G12). G12 is located about halfway through the cytoplasmic amino terminus and substitutions alter connexin function in a variety of ways, in some cases altering protein interactions and leading to cell death. There is also evidence that alteration of G12 changes the structure of the amino terminus in connexin- and amino acid- specific ways. This review integrates structural, functional and physiological information about the role of G12 in connexins, focusing on beta-connexins expressed in human epidermis. The importance of G12 substitutions in these beta-connexins is revealed in two hereditary skin disorders, keratitis ichthyosis and erythrokeratodermia variabilis, both of which result from missense mutations affecting G12.     

Usher Syndrome in the Inner Ear: Etiologies and Advances in Gene Therapy

Hearing loss is the most common sensory disorder with ~466 million people worldwide affected, representing about 5% of the population. A substantial portion of hearing loss is genetic. Hearing loss can either be non-syndromic, if hearing loss is the only clinical manifestation, or syndromic, if the hearing loss is accompanied by a collage of other clinical manifestations. Usher syndrome is a syndromic form of genetic hearing loss that is accompanied by impaired vision associated with retinitis pigmentosa and, in many cases, vestibular dysfunction. It is the most common cause of deaf-blindness. Currently cochlear implantation or hearing aids are the only treatments for Usher-related hearing loss. However, gene therapy has shown promise in treating Usher-related retinitis pigmentosa. Here we review how the etiologies of Usher-related hearing loss make it a good candidate for gene therapy and discuss how various forms of gene therapy could be applied to Usher-related hearing loss.     

Microstructure and morphology of amine-cured epoxy coatings before and after outdoor exposures—An AFM study

Atomic force microscopy (AFM) has been used to study the morphology and microstructure of an amine-cured epoxy before and after outdoor exposure. Measurements were made from samples prepared in an essentially CO₂-free, H₂O-free glove box and from samples prepared in ambient conditions. For those prepared in a CO₂-free glove box, AFM imaging was conducted on (1) an unexposed air/coating surface, (2) an unexposed coating bulk, (3) an unexposed coating/substrate interface, and (4) a field exposed air/coating surface. For samples prepared in ambient conditions, only the unexposed air/coating surface was investigated. The same regions of the exposed samples were scanned periodically by the AFM to monitor changes in the surface morphology of the coating as UV exposure progressed. Small angle neutron scattering and Fourier transform infrared spectroscopy (FTIR) studies were performed to verify the microstructure and to follow chemical changes during outdoor exposure, respectively. The results have shown that amine blushing, which occurs only under ambient conditions, had a significant effect on the surface morphology and microstructure of the epoxy. The surface morphology of the samples prepared under CO₂-free, dry conditions was generally smooth and homogeneous. However, the interface and the bulk samples clearly revealed a two-phase structure consisting of bright nodular domains and dark interstitial regions, indicating an inhomogeneous microstructure. Such heterogeneous structure of the bulk was in good agreement with results obtained by small angle neutron scattering of unexposed samples and by AFM phase imaging of the degraded sample surface. The relationship between submicrometer physical changes and molecular chemical degradation is discussed. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.     

Multivehicle coverage control for a nonstationary spatiotemporal field

This paper presents a multivehicle sampling algorithm to generate trajectories for nonuniform coverage of a nonstationary spatiotemporal field characterized by spatial and temporal decorrelation scales that vary in space and time, respectively. The sampling algorithm described in this paper uses a nonlinear coordinate transformation that renders the field locally stationary so that existing multivehicle control algorithms can be used to provide uniform coverage. When transformed back to the original coordinates, the sampling trajectories are concentrated in regions of short spatial and temporal decorrelation scales. For fields with coupled spatial statistics, i.e., the spatial decorrelation scales are functions of both spatial dimensions, the coordinate transformation is implemented numerically, whereas for decoupled spatial statistics, the transformation is expressed analytically. We show that the analytical transformation results in vehicle motion that preserves the vehicle sampling speed (which is a measure of vehicle speed scaled by the ratio of the spatial and temporal decorrelation scales), in the original domain; the sampling speed determines the minimum number of vehicles needed to cover a spatiotemporal domain. Theoretical results are illustrated by numerical simulations.     

Growth Mechanisms for SiC–AlN Solid Solution Crystals Prepared by Combustion Synthesis

AlN–SiC solid solution particles with a variety of morphologies including faceted polyhedrons with or without ledges; hexagonal platelets; hexagonal columns with a hexagonal plate or a pyramidal cap; and interpenetrating cones, have been found in the combustion products of a mixture of Al, Si, and carbon black under a nitrogen pressure of 10 MPa. Combustion temperature (the growth temperature of crystals) is the most important factor controlling the morphology of crystals formed in the combustion product. When temperatures are close to the melting point of the solid solutions, a small driving force for nucleation and long distances of surface migration make nucleation on the basal plane difficult, and thus the solid solution particles tend to grow as platelets. Supersaturation is the second key factor influencing crystal growth. At relatively low temperatures, a low supersaturation at the large pores renders nucleation difficult and the solid solution particles tend to grow as platelets. At relatively low temperatures and high supersaturation, a relatively high driving force for nucleation and short mean distances of surface migration promote the growth of AlN–SiC solid solutions as polyhedrons. The formation of the ledges on the polyhedral particles is attributed to the differences in the evaporation rates and the deposition rates between Al and Si. At relatively low temperatures and an intermediate supersaturation, the solid solution particles grow as prismatic columns. The formation of the prismatic columns with a hexagonal plate, or a pyramidal cap, is attributed to a sudden change of temperature during combustion. A possible growth mechanism for the AlN–SiC solid solution cones is proposed.     

Bond strengths of toluenes, anilines, and phenols: to hammett or not

The Hammett equation correlates the effects of Y on many different chemical properties of YC(6)H(4)ZX families of compounds. One of the most surprising is that the Z-X bond dissociation enthalpy (BDE), a homolytic property, can be correlated for some 4-YC(6)H(4)ZX families with electrophilic substituent constants, sigma(p)(+)(Y), which were largely derived from the rates of the heterolytic S(N)1 solvolyses of para-substituted cumyl chlorides. Although there is no Hammett correlation of the C-X BDEs in 4-YC(6)H(4)CH(2)X (X = H, halide, OPh) families, there are good correlations of N-X BDEs with sigma(p)(+)(Y) in 4-YC(6)H(4)NHX (X = H, CH(3), OH, F) and excellent correlations of O-X BDEs with sigma(p)(+)(Y) in 4-YC(6)H(4)OX (X = H, CH(3), CH(2)Ph) families. The reasons for this varied behavior are discussed.     

Chemical nature of a supercritical-gas extract of coal at 350 °C

A novel supercritical-gas (toluene) extract, comprising 17.0% of a low-rank coal, was separated by a combination of solvent fractionation and both silica-gel and gel-permeation chromatography. The average structure of the soluble fractions, together amounting to 85% of the extract, was investigated by a variety of spectroscopic methods, including high-resolution ¹H nuclear magnetic resonance, proton-decoupled pulse Fourier transform ¹³C magnetic resonance, infrared and low-ionizing-voltage mass spectrometry. Analyses were also made by gas chromatography. The results for the low-oxygen fractions are consistent with a generally open-chain polynuclear aromatic average structure with about 33% of the available sites carrying alkyl substituents. The most common of these is methyl, but there are also substantial numbers of longer-chain alkyls, some branched, and naphthenic groups. The fractions rich in oxygen also have similar structure but for the presence of phenolic hydroxyl groups, and, as is demonstrated for the first time by ¹³C n.m.r., ether oxygen links. Aliphatic constituents are mainly straight-chain alkanes with some branched-chain and isoprenoid hydrocarbons. These conclusions are discussed in terms of the thermal history of the extract and are compared with other contemporary views on the low-molecular-weight constituents of coal.     

Determination of non-spherical particle size distribution from chord length measurements. Part 2: Experimental validation

In this paper, the theory on the translation of a measured chord length distribution (CLD) into its particle size distribution (PSD), which was developed in the first part of this study [Li and Wilkinson, 2005. Determination of non-spherical particle size distribution from chord length measurements. Part 1: theoretical analysis. Chemical Engineering Science 60, 3251-3265], has been validated using experimental results. CLDs were measured using the Lasentec focused beam reflectance measurement (FBRM) with three different materials, spherical ceramic beads and non-spherical plasma aluminium and zinc dust particles. Meanwhile, the particle shape and PSD of each material were also investigated by image analysis (IA). Comparison of the retrieved PSDs with the measured PSDs by IA shows that the PSD can be retrieved from a measured CLD successfully using the proposed iterative nonnegative least squares (NNLS) method based on the PSD-CLD model.     

Partitioning of polymers into pores with surface interactions at dilute solution limit

The partitioning of a single polymer chain into a slit in a good solvent with different surface interactions is examined through Monte Carlo simulations from subcritical regime to adsorptive regime. The chain conformation in the subcritical regime is not perturbed by the surface interactions significantly. In the adsorptive regime, the conformation of the chain is strongly perturbed by the surface interactions. The confinement free energy in the two regimes maybe written in a uniform formula, βΔμ_conf∼c₁N(a/D)^xε_w+c₂N(a/D)^1/ν with x∼2.0 or larger in the subcritical regime and ∼1.0 in the adsorptive regime, where ν is the Flory exponent, D is the slit width, N is the chain length, a is the monomer size, and ε_w is the surface interaction energy between the polymer beads and the slit. This formula is valid for a long chain in the narrow slit in the subcritical regime or when the adsorption layer h>D in the adsorptive regime. A critical behavior occurs when ε_w is at the critical adsorption point and x=1/ν, then Δμ_conf will have little dependence on N or D. Higher order terms that are neglected in the above equation, however, may be present that could lead to a weak dependence of K on N and D even in the critical adsorption point.