Analytical13C NMR: A rapid,nondestructive method for determining the cis,trans composition of catalytically treated unsaturated lipid mixtures

High resolution natural abundance 13C Fourier transform nuclear magnetic resonance (NMR) has been found to be an effective tool for the rapid and direct determination of the cis/trans composition in partially hydrogenated and isomerized unsaturated lipids. With the eis and trans allylic carbon resonances as representative probes for double bond stereo-chemistry. Evaluation of the cis/trans composition of complex, positionally isomerized mixtures can be made without the necessity of carrying out detailed analyses of multishift olefinic carbon resonances. Migration of double bonds in monoenes and polyenes and formation of conjugated unsaturation in cata-lytically treated fats are discussed and assessed as possible sources of error in the evaluation of cis/trans isomer ratios. Carbon spin lattice relaxation times T₁ were measured for both cis and trans allylic reson-ances in isomeric mixtures of varying composition to assure quantitative intensity relationships. 13C NMR compositional analysis of complex mixtures is demonstrated.     

Effect of carbon deposition on porosity and reactivity of a lignite char

Carbon deposition from the cracking of methane into the pores of a lignite char occurs at a significant rate at temperatures between 815 and 855 °C. The maximum amount of carbon deposited is much less than the amount of open pore volume within the char which is potentially available to accommodate carbon. Removal of the inorganic impurities from the char by acid washing significantly reduces the extent of carbon deposition. Carbon deposition reduces surface area and open pore volume of the char and accessibility of methane into the pore structure. Deposition of carbon has a large and lasting adverse effect on the subsequent reactivity of the char to air. This has been attributed both to a decrease in active surface area, and deactivation of catalytic inorganic impurities due to coating with carbon. Deposited carbon is much less reactive to air than the lignite char. Results indicate that in order to maximize subsequent char reactivity to oxidizing gases, carbon deposition from volatiles during the conversion of coal to char should be kept to a minimum.     

Thermal behaviour of mineral fractions separated from selected American coals

The thermal behaviour of four samples of mineral matter, whose quantitative mineralogical compositions had previously been determined, was investigated using thermogravimetric and derivative thermogravimetric analysis methods. The mineral fractions were initially separated from the coal substance by a low-temperature ashing technique. The decomposition of the individual mineral species associated with coals is briefly reviewed. A synthetic standard mineral mixture was examined under various combustion atmospheres. X-ray diffraction analysis was utilized to study the high-temperature phases yielded by the mineral fractions. Ash-fusion data were also obtained, and can be understood in relation to the corresponding mineralogical analyses. No evidence was found of solid-state interactions below 1100 °C.     

Synthetic hydrogels: 3. Hydroxyalkyl acrylate and methacrylate copolymers: surface and mechanical properties

The surface and mechanical properties of copolymers of hydroxyalkyl acrylates and methacrylates have been examined by a variety of techniques. This work is complementary to earlier parts of this series which describe the effect of copolymer structure on water binding properties. Water structure has been demonstrated to exert a profound effect upon mechanical properties whether measured in compression or in tension. In particular, water that is characterized by differential scanning calorimetry as ‘freezing’ water is observed to have a marked plasticizing effect upon the gel, whereas ‘non-freezing’ water has little such effect. Similarly, the ‘freezing’ water produces a more marked effect on thermally induced transitions. Two distinct transition points are observed as a result of its presence. One corresponds to the freezing point of water and the other to a glass transition temperature, whose value depends upon the proportion of ‘freezing’ or ‘plasticizing’ water in the gel. Several predictive and direct measurement techniques have been used to study the surface properties of the copolymers in both hydrated and dehydrated states. Taken together they have established a sound understanding of the way in which polar and dispersive components of surface free energy vary as a function of copolymer composition and water content. Use of protein adsorption and fibroblast cell interaction techniques demonstrate that biological phenomena respond to changes at a molecular level which current macroscopic surface energy techniques are unable to discern.     

X-ray photoelectron spectroscopic study of the oxidation and reduction of a cerium(III) oxide/cerium foil substrate

X-ray photoelectron spectroscopy has been used to examine the nature of the oxide overlayers on a passivated cerium metal foil as a function of a variety of oxidation and reduction treatments. Oxidation of a clean uncontaminated cerium(III) oxide surface is facile at room temperature and produces non-stoichiometric ceria (CeO_2–x) at oxygen doses as low as 10 L. At higher doses the overlayer thickens, and after a dose of 160 L the layer depth exceeds the Ce 3d photoelectron attenuation distance of about 20 Å. High pressure treatment of the foil in oxygen (0.5 bar at RT and 473 K) produces CeO₂ in a high degree of crystallographic order such that O 1s photoelectron intensities are increased above that expected from a randomly oriented powder. An attempt to reduce the CeO₂ layer formed by controlled oxidation with CO (633 K, 14 h, 0.6 bar) results in the formation of a carbonated surface layer. Results following attempts to reoxidise this layer are discussed.     

Efficient generation of a reshaped human mAb specific for the {alpha} toxin of Clostridium perfringens

We have used the technique of antibody reshaping to producea humanized antibody specific for the a toxin of Clostridiumperfringens. The starting antibody was from a mouse hybridomafrom which variable (V) region nucleo-tide sequences were determined.The complementarity-determining regions (CDRs) from these Vregions were then inserted into human heavy and light chainV region genes with human constant region gene fragments subsequentlyadded. The insertion of CDRs alone into human frameworks didnot produce a functional reshaped antibody and modificationsto the V region framework were required. With minor frameworkmodifications, the affinity of the original murine mAb was restoredand even exceeded. Where affinity was increased, an alteredbinding profile to overlapping peptides was observed. Computermodelling of the reshaped heavy chain V regions suggested thatamino acids adjacent to CDRs can either contribute to, or distort,CDR loop conformation and must be adjusted to achieve high bindingaffinity.     

The use of environmental, health and safety research in nanotechnology research

Environmental, health, and safety (EHS) concerns are receiving considerable attention in nanoscience and nanotechnology (nano) research and development (R&D). Policymakers and others have urged that research on nano's EHS implications be developed alongside scientific research in the nano domain rather than subsequent to applications. This concurrent perspective suggests the importance of early understanding and measurement of the diffusion of nano EHS research. The paper examines the diffusion of nano EHS publications, defined through a set of search terms, into the broader nano domain using a global nanotechnology R&D database developed at Georgia Tech. The results indicate that nano EHS research is growing rapidly although it is orders of magnitude smaller than the broader nano S&T domain. Nano EHS work is moderately multidisciplinary, but gaps in biomedical nano EHS's connections with environmental nano EHS are apparent. The paper discusses the implications of these results for the continued monitoring and development of the cross-disciplinary utilization of nano EHS research.     

Dressing plasmons in particle-in-cavity architectures

Placing metallic nanoparticles inside cavities, rather than in dimers, greatly improves their plasmonic response. Such particle-in-cavity (PIC) hybrid architectures are shown to produce extremely strong field enhancement at the particle-cavity junctions, arising from the cascaded focusing of large optical cross sections into small gaps. These simply constructed PIC structures produce the strongest field enhancement for coupled nanoparticles, up to 90% stronger than for a dimer. The coupling is found to follow a universal power law with particle-surface separation, both for field enhancements and resonant wavelength shifts. Significantly enhanced Raman signals are experimentally observed for molecules adsorbed in such PIC structures, in quantitive agreement with theoretical calculations. PIC architectures may have important implications in many applications, such as reliable single molecule sensing and light harvesting in plasmonic photovoltaic devices.