Destabilizing interactions between the partners of a bifunctional fusion protein

Hybrid MalE–GVP is a bifunctional protein in vitro sinceit binds maltose as protein MalE of Escherichia coli and sinceit is dimeric and specifically binds single-stranded DNA asprotein GVP of phage M13. The oxidation rate of a unique cysteineresidue was used to compare the stabilities of GVP in its freeand hybrid forms, under conditions where MalE was either foldedor unfolded by a denaturing agent. The results showed that boththe covalent link and tertiary non-covalent interactions betweenMalE and GVP destabilized GVP in MalE–GVP. To test whetherGVP had identical structures in its free and hybrid forms, mutationswere used as local conformational probes. The effects of thesemutations on the capabilities of MalE–GVP to dimerizeand to bind single-stranded DNA were assayed in vitro. Theywere compatible with the effects of the same mutations on theglobal activity of free GVP in vivo and with the effects thatcould be predicted from the known data on free GVP, in particularits crystal structure. Thus, one partner of a hybrid proteincan be destabilized by the other partner while maintaining itsstructural and functional characteristics.     

Combination of non-thermal plasma and heterogeneous catalysis for oxidation of volatile organic compounds: Part 2. Ozone decomposition and deactivation of γ-Al2O3

The role of ozone was studied for two different configurations combining non-thermal plasma (NTP) and heterogeneous catalysis, namely the use of a gas phase plasma with subsequent exposure of the effluent to a catalyst in a packed-bed reactor (post-plasma treatment) and the placement of the catalyst directly in the discharge zone (in-plasma catalysis). Non-porous and porous alumina and silica were deployed as model catalysts. The oxidation of immobilised hydrocarbons, toluene as a volatile organic compound and CO as an inorganic pollutant were studied in both operational modes.

While conversion and selectivity of hydrocarbon oxidation in the case of catalytic post-plasma treatment can be fully explained by the catalytic decomposition of O₃ on γ-Al₂O₃, the conversion processes for in-plasma catalysis are more complex and significant oxidation was also measured for the other three materials (-Al₂O₃, quartz and silica gel). It became obvious that additional synergetic effects can be utilised in the case of in-plasma catalysis due to short-lived species formed in the NTP.

The capability of porous alumina for ozone decomposition was found to be correlated with its activity for oxidation of carbon-containing agents. It could be clearly shown that the reaction product CO₂ poisons the catalytic sites at the γ-Al₂O₃ surface. The catalytic activity for O₃ decomposition can be partially re-established by NTP treatment. However, for practical purposes the additional reaction pathways provided by in-plasma catalytic processes are essential for satisfactory conversion and selectivity.     

Copolyester studies. I. Preparation and characterization of tetramethylene terephthalate–tetramethylene sebacate copolymers

Tetramethylene terephthalate–tetramethylene sebacate copolymers containing up to 20 mol % sebacate have been prepared and characterized. Molecular weights and distributions have been evaluated using viscometry and gel-permeation chromatography. Compositions have been established by NMR spectroscopy. Thermal properties have been studied by differential scanning calorimetry and dynamic mechanical methods. Melting and glass-transition temperatures and moduli are discussed in terms of the structural differences, particularly the effect of composition on chain flexibility. Density and thermal methods of crystallinity determination are critically discussed for these systems.     

The behaviour of PbO2 in concentrated sulphuric acid

Linear sweep experiments on Pb in H₂SO₄ at concentrations in excess of 5 mol dm^–3 have been conducted using computer controlled techniques. Measurements have indicated that the maximum charge in the PbO₂ reduction peak occurs at 5 mol dm^–3, the available capacity decreasing with the concentration of H₂SO₄.     

Iron(II)‐based catalysts for ethene oligomerization

The synthesis of iron(II) complexes with various tridentate di(imino)pyridine ligands and their potential as ethene oligomerization catalysts are described. The ligands are characterized by ¹H‐ and ¹³C‐NMR spectroscopy and the complexes only by mass spectrometry due to their paramagnetism. After activation either with methylalumoxane (MAO) or with a heterogeneous cocatalyst consisting of partially hydrolyzed trimethylaluminum and silica gel, the prepared complexes proved to be good catalysts for the oligomerization of ethene. 1‐Octene, 1‐hexene, and 1‐decene were the major products, formed in very high isomeric purity (99.9 %). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 476–482, 2003     

PHASE-SPACE DIFFUSION EQUATIONS FOR SINGLE BROWNIAN PARTICLE MOTION NEAR SURFACES

In numerous physical processes involving the motion of micron and submicron sized particles near surfaces, such as the filtration of hydrosols and aerosols, the particle motion is the net result of the combined effects of fluid convection, external forces, particle inertia, Brownian particle motion, and particle-surface fluid dynamic interactions. The most general method of describing particle motion under the combined action of these effects is through the so-called Fokker-Planck equation. In the absence of particle-surface fluid dynamic interactions, the Fokker-Planck equation is well-known, and it has been applied in a general way to problems involving the adsorption or deposition of Brownian particles onto surfaces through a solution technique known as the Brownian dynamics simulation method.

In this study, the Fokker-Planck equation for Brownian particle motion near surfaces is generalized to include particle-surface fluid dynamic interactions. The Fokker-Planck equation is shown to follow from the Liouville equation for the Brownian particle and n-fluid molecules present in the system, thus, establishing a firm theoretical foundation for the Fokker-Planck equation and the various other phase-space diffusion equations that follow from it.

Based on diagonalization of the Fokker-Planck equation, its short-time behavior is also derived here which enables a generalization of the Brownian dynamics method for the study of particle motion near surfaces including fluid dynamic interactions. Additionally, a perturbation solution of the Fokker-Planck equation under the conditions of small, but finite particle Stokes number is also derived. These solutions are shown to agree with previously given representations of the Smoluchowski or convective-diffusion equation for Brownian particle motion near surfaces, as well as with inertial corrections to the Smoluchowski equation available in the literature. This latter equation is also generalized here to include particle-surface fluid dynamic interactions.     

Chemical analysis of volatiles emitted by Pinus svlvestris after induction by insect oviposition

Gas chromatography – mass spectrometry analyses of the headspace volatiles of Scots pine (Pinus sylvestris) induced by egg deposition of the sawfly Diprion pini were conducted. The odor blend of systemically oviposition-induced pine twigs, attractive for the eulophid egg parasitoid Chrysonotomyia ruforum, was compared to volatiles released by damaged pine twigs (control) that are not attractive for the parasitoid. The mechanical damage inflicted to the control twigs mimicked the damage by a sawfly female prior to egg deposition. The odor blend released by oviposition-induced pine twigs consisted of numerous mono- and sesquiterpenes, which all were also present in the headspace of the artificially damaged control twigs. A quantitative comparison of the volatiles from oviposition-induced twigs and controls revealed that only the amounts of (E)--farnesene were significantly higher in the volatile blend of the oviposition-induced twigs. Volatiles from pine twigs treated with jasmonic acid (JA) also attract the egg parasitoid. No qualitative differences were detected when comparing the composition of the headspace of JA-treated pine twigs with the volatile blend of untreated control twigs. JA-treated pine twigs released significantly higher amounts of (E)--farnesene. However, the JA treatment induced a significant increase of the amount of further terpenoid components. The release of terpenoids by pine after wounding, egg deposition, and JA treatment is discussed with special respect to (E)--farnesene.     

An electrochemical impedance spectroscopy and scanning electron microscopy study of the influence of positive plate compression on the electrochemical behaviour of lead-acid batteries

This study has developed an electrochemical impedance spectroscopy (EIS) method for the in situ investigation of the influence of positive plate compression on the electrochemical behaviour of lead-acid batteries during charge/discharge cycling. The EIS data for a fully charged and fully discharged battery are internally consistent with the expected kinetics of a battery in the opposite states of charge, and demonstrate that EIS measurements may be recorded with a high level of reproducibility. Furthermore, this study has necessitated the development of a special cell incorporating horizontally orientated battery plates that can be subjected to elevated pressure through the stacking of lead bricks on top of the cell, as well as a physically robust reference electrode system that can withstand the application of pressure. For this purpose, a platinum-wire pseudo-reference electrode has been developed, and has been shown to exhibit sufficient electrode stability over the period of an EIS recording, enabling the measurement of reproducible and meaningful EIS data. Additionally, the influence of positive plate compression on the behaviour of the lead-acid battery has been investigated by using scanning electron microscopy (SEM). Clearly, the experimental data show that plate compression enhances significantly the kinetics and concomitant performance of the lead-acid battery, and this is related to the enhanced reactivity of the active material, as rationalized by using the agglomeration-of-spheres (AOS) model.     

A predicted three-dimensional structure of human cytochrome P450: implications for substrate specificity

A three-dimensional structure for human cytochrome P450IA1 waspredicted based on the crystal coordinates of cytochrome P450camfrom Pseudomonas putida. As there was only 15% residue identitybetween the two enzymes, additional information was used toestablish an accurate sequence alignment that is a prerequisitefor model building. Twelve representative eukaryotic sequenceswere aligned and a net prediction of secondary structure wasmatched against the known -helices and ß-sheets ofP450cam. The cam secondary structure provided a fixed main-chainframework onto which loops of appropriate length from the humanP450IA1 structure were added. The model-built structure of thehuman cytochrome conformed to the requirements for the segregationof polar and nonpolar residues between the core and the surface.The first 44 residues of human cytochrome P450 could not bebuilt into the model and sequence analysis suggested that residues1–26 formed a single membrane-spanning segment. Examinationof the sequences of cytochrome P450s from distinct gene familiessuggested specific residues that could account for the differencesin substrate specificity. A major substrate for P450IA1, 3-methyl-cholanthrene,was fitted into the proposed active site and this planar aromaticmolecule could be accommodated into the available cavity. Residuesthat are likely to interact with the haem were identified. Thesequence similarity between 59 eukaryotic enzymes was representedas a dendrogram that in general clustered according to genefamily. Until a crystallographic structure is available, thismodel-building study identifies potential residues in cytochromeP450s important in the function of these enzymes and these residuesare candidates for site-directed mutagenesis.     

Adsorption of Cationic Dyes by Acrylic Films II—Kinetics of Dyeing

Concentration distributions of basic dyes in a film of acrylic polymer have been determined using a microdensitometric technique. The diffusion coefficients calculated from them are dependent on concentration. An explanation of the dependence is offered based on the ionic transfer of hydrogen (or sodium) ions for dye. From the concentration dependence an average diffusion coefficient was calculated and found to agree with that calculated from rates of dyeing. Rates of dyeing of a binary mixture have demonstrated the competitive effect predicted by the diffusion equation derived for the individual dyes.