Spectroscopic investigation of structure in octarellin (a de novo protein designed to adopt the {alpha}/{beta}-barred packing)

We present here a spectroscopic structural characterizationof octarellin, a recently reported de novo protein modelledon /ß-barrel proteins [K. Go raj, A.Renard and J.A.Martial(1990) Protein Engng, 3, 259–266]. Infrared and Ramanspectra analyses of octarellin‘s secondary structure revealthe expected percentage of -helices (30%) and a higher ß-sheetcontent (40%) than predicted from the design. When the Ramanspectra obtained with octarellin and native triosephosphateisomerase (a natural /ß-barrel) are compared, similarpercentages of secondary structures are found. Thermal denaturationof octarellin monitored by CD confirms that its secondary structuresare quite stable, whereas its native-like tertiary fold is not.Tyrosine residues, predicted to be partially hidden from solvent,are actually exposed as revealed by Raman and UV absorptionspectra. We conclude that the attempted /ß-barrelconformation in octarellin may be loosely packed. The criteriaused to design octarellin are discussed and improvements suggested.     

Decomposition de l'acetylene,de l'ethylene et du benzene sur le carbone aux tres hautes temperatures et sous de basses pressions

At high temperatures (1000–2000°C) and low pressures (10^?5?10^?2 Torr) ethylene, acetylene and benzene decompose helerogeneously on pyrolytic carbon giving mainly hydrogen and deposited carbon, with collision yields of the order of 10^?4. The kinetics of these carbon deposition reactions show some striking similarities with carbon removal reactions by oxygen or oxygenated compounds.The true reaction order of these decomposition reactions is one above 1400°C, but becomes smaller at lower temperatures. This behaviour, common in gas-solid reactions, is generally interpreted as an inhibition due to chemisorption of some intermediate or reaction product. Evidence is also obtained that decomposition of the hydrocarbon molecules only occurs on peculiar sites of the carbon surface, i.e. the decomposition is not a purely thermal process, but involves a specific chemical interaction with the surface.Moreover, the behaviour of the pyrocarbon surface in carbon deposition reactions is similar to that observed in gasification reactions, i.e. the reactivity of the surface accommodates itself to the temperature and pressure conditions, as revealed by the observation of “transitory” and “stationary rates”. Transitory rates show that the surface deactivates with increasing temperatures (Figs. 4 and 5) [from which a maximum in the stationary rate results (Figs. 1–3)] and decreasing pressures (Figs. 7 and 8). The interpretation assumes that reaction sites are continuously created as an effect of carbon atoms deposition, but also deactivated by a thermal healing process.A main difference between carbon deposition reactions from hydrocarbons and carbon gasification reactions concerns the temperature range where reactivity is temperature dependent: in carbon deposition reactions, deactivation of the pyrocarbon surface is still effective up to much higher temperatures (Fig. 12).     

Hydrogenation of brown coal. 2. Iron-based catalysis

Some of the inherent cations of Victorian brown coals have been exchanged for iron by treatment with solutions of iron salts. Coals with various iron contents are obtained by variation of the pH of the solutions used. Hydrogenation of coals treated in this way at 395 °C, and an initial hydrogen pressure of 10 MPa, give product yields similar to those obtained using commercial cobalt molybdate on alumina catalysts, and greater than those obtained using red mud as a catalyst. The increase in yields compared with non-catalysed experiments results mainly from increased production of asphaltenes. The amount and composition of gas (80–90 wt% C0₂, resulting from decarboxylation) remains constant. Despite the similar conversions, the hydrogen consumption and tetralin/naphthalene ratios for iron-catalysed experiments are less than for cobalt—molybdate-catalysed experiments.     

A refined model for the active site within the NO decomposition catalyst, Cu-ZSM-5

Static atomistic simulation techniques have been employed to identify a model for the active site configuration and its location within the NO decomposition catalyst, Cu-ZSM-5. We propose that the active site comprises a copper pair, bridged by OH and forming a six membered ring, specifically, {-O-Cu(II)-OH-Cu(I)-O-Al-}, within the zeolite framework. The six-membered ring arises from the strong association of both of the copper species with a single aluminium in the zeolite framework and consequently the ring is strained, reflected in the low (3.1 Å) intercopper distance in the cluster. Indeed, this Cu-Cu distance compares well with the experimentally determined value of 3.0. In addition, it is expected that the strain in the cluster influences the activity of the cluster, which we suggest may be responsible for its unique activity for NO decomposition.     

New telechelic polymers and sequential copolymers by polyfunctional initiator transfer agents (inifers)

Summary The Kennedy-Smith plot routinely used for the characterization of end-reactive (telechelic) polyisobutylenes has been recast to increase its accuracy and thus to increase its diagnostic value for the compositional analysis of telechelic polymers containing chromophores. A detailed error estimation is given. The plotting method and error limits are shown for representative mono-, di-, and tri-ended telechelic polyisobutylenes.     

Elastomeric alloys of PVC

The performance standards for flexible PVC compounds continue to become more demanding as manufacturers pursue more value-added applications traditionally dominated by rubbers and thermoplastic elastomers. Blending of PVC with other polymers has proven to be a viable approach in developing higher performance flexible PVC-based materials. This paper will review some of the typical approaches to producing PVC-based elastomers, and show how these standard flexible PVC blends compare to a newly developed family of PVC alloys. The advantages of these materials will be discussed, and some examples of commercial materials and their application will also be reviewed.     

ON THE INVERTIBILITY OF PERIODIC MOVING-AVERAGE MODELS

Abstract. A sufficient condition for the invertibility of univariate periodic moving-average models has been given by Cipra and Ghysels and Hall. We show that this condition is not a necessary one, and provide a necessary and sufficient condition for the general m -variate, d -periodical moving-average MA( q ) case.