Activity of quassinoids as antifeedants against aphids

A series of quassinoids was tested for antifeedant activity against the aphidMyzus persicae (Hemiptera, Aphididae). Isobrucein B, brucein B and C, glaucarubinone, and quassin decreased feeding at concentrations down to 0.05% and isobrucein A was effective at 0.01%. Only quassin showed no phytotoxic effects and is therefore the most promising compound for further development.     

A holistic approach to protein structure alignment

A method of protein structure comparison developed previouslyis extended to incorporate other aspects of protein structurein addition to the inter-atomic vectors on which it was originallybased. Each additional aspect, which included hydrogen bonding,solvent exposure, torsional angles and sequence, was introducedseparately and evaluated for its ability to improve alignmentquality. The components were then combined, suitably weighted,to produce a more holistic comparison method. The method wastested on a group of remotely related ß/ type proteinsthat share a common feature in their overall chain fold. Theresults indicated that while the original inter-atomic vectorcomponent was sufficient to give the correct alignment of mostpairs of topologically equivalent proteins, the inclusion ofhydrogen bonds, torsion angles and a measure of solvent exposureled to improvements in the more difficult comparisons. Considerationof amino acid properties, including hydrophobicity, had no beneficialeffect. The failure of the latter component was not unexpectedconsidering the almost total lack of sequence similarity amongthe proteins considered.     

Factorial design of experiment (DOE) for parametric exergetic investigation of a steam methane reforming process for hydrogen production

Hydrogen is expected to play a significant role in future energy systems. The efficient production of hydrogen at a minimum cost and in an environmentally acceptable manner is crucial for the development of a hydrogen-including economy. The exergy analysis is a powerful tool to quantify sustainable development potential. An important aspect of sustainable development is minimizing irreversibility. The purpose of this study is to perform the exergy analysis of a steam methane reforming (SMR) process for hydrogen production. As a first step, an exergy analysis of an existing process is shown to be an efficient tool to critically examine the process energy use and to test for possible savings in primary energy consumption. The results of this investigation prove that the exergetic efficiency of the SMR process is 65.47%, and the majority of destroyed exergy is localized in the reformer with a 65.81% contribution to the whole process destroyed exergy. Next, an exergetic parametric study of the SMR has been carried out with a factorial design of experiment (DOE) method. The influence of the reformer operating temperature and pressure and of the steam to carbon ratio (S/C) on the process exergetic efficiency has been studied. A second-order polynomial mathematical model has been obtained through correlating the exergetic efficiencies with the reformer operating parameters. The results of this study show that the rational choice of these parameters can improve the process exergetic performance.     

Induction time studies of calcium carbonate in ethylene glycol and water

Induction time for precipitation of calcium carbonate precipitated in mono ethylene glycol and water has been studied by conductivity measurements at ethylene glycol concentrations of 0–90 wt% and temperatures from 25 to 80 °C. The supersaturation ratios, S, were in the range of 3–10. The effect of the solvent was separated from the effect of the supersaturation and temperature. Increasing the concentration of ethylene glycol prolongs the induction times for precipitation of CaCO₃ considerably although the supersaturation actually increases, especially at lower temperatures. It was shown that this effect cannot be explained by the change in the interfacial tension. Induction time studies in seeded and unseeded experiments were performed in order to separate changes in the nucleation rate from the impact of the growth time in the varying solvent compositions. The results show that crystal growth is retarded, causing the increased induction time in ethylene glycol containing solutions, and hence that the nucleation rate is actually promoted by ethylene glycol. The nucleation rates determined by measured particle numbers and induction times from unseeded experiments were underestimated for the same reason, thereby illustrating the complexity of nucleation rate investigations in mixed solvents.     

A Mutant D‐Fructose‐6‐Phosphate Aldolase (Ala129Ser) with Improved Affinity towards Dihydroxyacetone for the Synthesis of Polyhydroxylated Compounds

A mutant of D ‐fructose‐6‐phosphate aldolase (FSA) of Escherichia coli, FSA A129S, with improved catalytic efficiency towards dihydroxyacetone (DHA), the donor substrate in aldol addition reactions, was explored for synthetic applications. The k_cat/K_M value for DHA was 17‐fold higher with FSA A129S than that with FSA wild type (FSA wt). On the other hand, for hydroxyacetone as donor substrate FSA A129S was found to be 3.5‐fold less efficient than FSA wt. Furthermore, FSA A129S also accepted glycolaldehyde (GA) as donor substrate with 3.3‐fold lower affinity than FSA wt. This differential selectivity of both FSA wt and FSA A129S for GA makes them complementary biocatalysts allowing a control over donor and acceptor roles, which is particularly useful in carboligation multi‐step cascade synthesis of polyhydroxylated complex compounds. Production of the mutant protein was also improved for its convenient use in synthesis. Several carbohydrates and nitrocyclitols were efficiently prepared, demonstrating the versatile potential of FSA A129S as biocatalyst in organic synthesis.     

Reactive Element Effects in High-Temperature Alloys Disentangled

Reactive elements—REs—are decisive for the longevity of high-temperature alloys. This work joins several previous efforts to disentangle various RE effects in order to explain apparently contradicting experimental observations in alumina forming alloys. At 800–1000 °C, “messy” aluminum oxy-hydroxy-hydride transients initially formed due to oxidation by H₂O which in turn undergo secondary oxidation by O₂. The formation of the transient oxide becomes supported by dispersed RE oxide particles acting as water equivalents. At higher temperatures, electron conductivity in impurity states owing to oxygen vacancies in grain boundaries (GBs) becomes increasingly relevant. These channels are subsequently closed by REs pinning the said vacancies. The universality of the emerging understanding is supported by a comparative first-principles study by means of density functional theory addressing RE(III): Sc₂O₃, Y₂O₃, and La₂O₃, and RE(IV): TiO₂, ZrO₂, and HfO_2, that upon reaction with water, co-decorate a generic GB model by hydroxide and RE ions. At 100% RE coverage, the GB model becomes relevant at both temperature regimes. Based on reaction enthalpy ΔH_r considerations, “messy” aluminum oxy-hydroxy-hydride transients are accessed in both classes. Larger variations in ΔH_r are found for RE(III)-decorated alumina GBs as compared to RE(IV). For RE(III), correlation with GB width is found, increasing with increased ionic radius. Similarly, upon varying RE(IV), minor changes in stability correlate with minor structural variations. GB decorations by Ce(III) and Ce(IV) further consolidate the emerging understanding. The findings are used to discuss experimental observations that include impact of co-doping by RE(III) and RE(IV).

     

A Review on the Effects of Supercritical Carbon Dioxide on Enzyme Activity

Different types of enzymes such as lipases, several phosphatases, dehydrogenases, oxidases, amylases and others are well suited for the reactions in SC-CO₂. The stability and the activity of enzymes exposed to carbon dioxide under high pressure depend on enzyme species, water content in the solution and on the pressure and temperature of the reaction system. The three-dimensional structure of enzymes may be significantly altered under extreme conditions, causing their denaturation and consequent loss of activity. If the conditions are less adverse, the protein structure may be largely retained. Minor structural changes may induce an alternative active protein state with altered enzyme activity, specificity and stability.     

Copper Transfer from Cu–Aβ to Human Serum Albumin Inhibits Aggregation,Radical Production and Reduces Aβ Toxicity

Amyloid‐β peptides (Aβ) and the protein human serum albumin (HSA) interact in vivo. They are both localised in the blood plasma and in the cerebrospinal fluid. Among other functions, HSA is involved in the transport of the essential metal copper. Complexes between Aβ and copper ions have been proposed to be an aberrant interaction implicated in the development of Alzheimer's disease, where Cu is involved in Aβ aggregation and production of reactive oxygen species (ROS). In the present work, we studied copper‐exchange reaction between Aβ and HSA or the tetrapeptide DAHK (N‐terminal Cu‐binding domain of HSA) and the consequence of this exchange on Aβ‐induced ROS production and cell toxicity. The following results were obtained: 1) HSA and DAHK removed Cu^II from Aβ rapidly and stoichiometrically, 2) HSA and DAHK were able to decrease Cu‐induced aggregation of Aβ, 3) HSA and DAHK suppressed the catalytic HO^. production in vitro and ROS production in neuroblastoma cells generated by Cu–Aβ and ascorbate, 4) HSA and DAHK were able to rescue these cells from the toxicity of Cu–Aβ with ascorbate, 5) DAHK was more potent in ROS suppression and restoration of neuroblastoma cell viability than HSA, in correlation with an easier reduction of Cu^II–HSA than Cu–DAHK by ascorbate, in vitro. Our data suggest that HSA is able to decrease aberrant Cu^II–Aβ interaction. The repercussion of the competition between HSA and Aβ to bind Cu in the blood and brain and its relation to Alzheimer's disease are discussed.     

Chain extension reaction in solid‐state polymerization of recycled PET: The influence of 2,2′‐bis‐2‐oxazoline and pyromellitic anhydride

Conventional and chain extended‐modified solid‐state polymerization (SSP) of postconsumer poly(ethylene terephthalate) (PET) from beverage bottles was investigated. SSP was carried out at several temperatures, reaction times, and 2,2′‐bis‐2‐oxazoline (OXZ) or pyromellitic anhydride (ANP) concentrations. The OXZ was added by impregnation with chloroform or acetone solution. Higher molecular weights were reached when the reaction was carried out with OXZ, resulting in bimodal distribution. The molecular weights of the flakes reacted at 230°C for 4 h were 85,000, 95,000, and 100,000 for samples impregnated with 0, 0.5, and 1.25 wt % OXZ solution, respectively. In the case of reactions with ANP, branched chains were obtained. The thermal and thermal‐mechanical‐dynamic properties of these high‐molecular‐weight recycled PET were determined. For OXZ‐reacted samples, the reduction of crystallinity was observed as the reaction time was increased, becoming evident the destruction of the crystalline phase. The chain extended samples did not show changes in thermal relaxations or thermal degradation behavior. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010