Preparation and Properties of Nickel and Iron Oxides obtained by Calcination of Layered Double Hydroxides

A constant pH precipitation method has been applied to obtain solids with Ni/Fe molar ratios of 2/1, 3/2, 1/1, 2/3, and 1/2. In all cases, a phase with the hydrotalcite‐like structure is obtained, containing Ni^II and Fe^III in the brucite‐like layers and carbonate in the interlayer, and, for samples with a Ni/Fe molar ratio lower than 2/1, amorphous hydrated iron oxides, undetected by X‐ray diffraction, are also formed. The solids have been characterized by element chemical analysis, powder X‐ray diffraction, differential thermal analysis, thermogravimetric and differential thermogravimetric analysis, FT‐IR spectroscopy, temperature‐programmed reduction and assessment of specific surface area by nitrogen adsorption at ?196 °C. In all cases reduction leads to zero‐valent state for the metals, reduced nickel particles probably favouring reduction of Fe^III species; the specific surface area increases with the iron content, probably due to the amorphous nature of the hydrated iron oxides formed. Calcination at 1200 °C in air leads to well crystallized solids, formed by NiFe₂O₄ spinel and, additionally, rocksalt‐type NiO for Ni/Fe ratios larger than 1/2. In this way, solids with tailored compositions of these two phases can be prepared.     

Combined Dynamic Model for the Kinetics of Electron Transfer from Cytochrome to a Bacteriochlorophill Dimer in Reaction Centers of Rps. Sulfoviridis

The electron transfer from the heme of cytochrome c to the bacteriochlorophill dimer in reaction centers of photosynthetic purple bacteria Rps. sulfoviridis is studied by laser flash photolysis at 40–296 K in conditions where one, two, or three cytochrome hemes are chemically reduced. In the model used for the electron transfer kinetics, the protein relaxation is described with a temperature-independent oscillatory coordinate and a temperature-dependent diffusion coordinate, with the protein dielectric relaxation times widely distributed along the diffusion coordinate. It is found that all the protein complexes can be divided into proteins with fast (k _et = 10⁷ to 10^–4 s^–1) and slow (k _et 100 s^–1) electron transfer. These populations presumably differ by the protonation state of the functional group. The contribution of the oscillatory and diffusion coordinates alters, which severely affects k _et. Parameters V _ab, G, , ₀, and for these reactions are determined.     

Directed evolution of the dioxygenase complex for the synthesis of furanone flavor compounds

Herein we report a new preparation of 4-hydroxy-2,5-dimethyl-2,3-dihydrofuran-3-one, the flavor compound strawberry furanone, based on a ‘green’ approach with a minimum number of steps. The first step is an enzymatic dioxygenation of p-xylene to form cyclohexadiene-cis-diol, followed by ring opening via ozonolysis, and ring closure to form the furanone. In efforts to improve the efficiency of the enzymatic step, a directed evolution approach was taken to increase the substrate specificity and selectivity of the toluene dioxygenase enzyme system.     

Optimization of acid hydrolysis of sugarcane bagasse and investigations on its fermentability for the production of xylitol by Candida guilliermondii

The dilute-acid hydrolysis of sugarcane bagasse was optimized using a statistical experimental design resulting in hydrolysates containing 57.25 g/L of xylose, which were fermented with a high inoculum concentration (10 g/L of the yeast Candida guilliermondii IM/UFRJ 50088). The addition of urea reduced the time of conversion (t _C) to 75 h (without nitrogen source addition t _C>127 h), and, consequently, improving the rates of xylitol bioproduction. Fermentator experiments, using the optimized conditions, resulted in enhanced conversion rates, reducing t _C to 30 h. The stability of the yeast in the hydrolysate was also verified in a 480-h cultivation.     

Antifungal activity of crown ethers

Some crown ethers were found to show significant antifungal activity against some wood-decay fungi, phytopathogenic fungi and eumycetes,Trichophytons for dermatomycosis. Their toxicity was evaluated by the paper disc method as well as by determining the values of ED₅₀, i.e., the concentration which inhibits the mycelium growth by 50%. The fungi examined areTyromyces palustris, Picnoporous coccineus, Coriolous versicolor, Pyricularia filamentosa, Fusarium sp., Trichophyton rubrum, Trichophyton sp., etc. Among the 26 crown ethers tested, 3,5-di-t-butyl-benzo-15-crown-5 showed relatively high activity, the highest ED₅₀ value of which being 8 M or 3 ppm. Other alkylbenzocrown ethers, dicyclohexyl crown ethers and Kryptofix 22DD also showed considerable activity. On the other hand, unsubstituted crown ethers, benzocrown ethers with a polar substituent, Kryptofix 222B and Kryptofix 221 were inactive.     

Fracture mechanisms in rigid core-shell particle modified high performance epoxies

The fracture mechanisms of a high performance epoxy system modified with two types of preformed rigid core-shell particles (RCSP) were investigated. The use of the preformed RCSP anables the control of the dispersion of the toughener phase in the epoxy, which, in turn, allows the mechanical properties of the modified epoxy to be optimized. The toughening effect via the RCSP modification is found to be as good as that via the core-shell rubber modification. The moduli andT _g of these RCSP-modified epoxies are virtually unaltered via the RCSP modification, when compared with the neat epoxy resin equivalent. The toughening mechanisms in these toughened systems appear to be predominantly crack deflection, crack bifurcation, and microcracking. Approaches for effective toughening of high performance polymers via rigid polymers are discussed.     

AlPO4?ZrO2 catalysts, II. Synthesis, textural properties and crystal structure of systems obtained in ethylene oxide

The effects of surface dehydration on textural properties, crystallinity and the structure of AlPO₄–ZrO₂ (weight ratio AlPO₄/ZrO₂=3) systems precipitated with ethylene oxide have been studied by N₂ adsorption and XRD measurements. The increase in calcination temperature in the range 773–1273 K decreases the textural parameters as a consequence of AlPO₄ crystallization to the tridymite form.

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, AlPO₄–ZrO₂ ( AlPO₄/ZrO₂=3), , N₂ - . 773 1273 , AlPO₄ .

     

Asymmetric Induction in the Synthesis of 3,4,5-Trisubstituted Ferrocenyl-4,5-dihydropyrazoles

The asymmetric induction in the synthesis of 3,4,5-trisubstituted 4,5-dihydropyrazoles with ferrocenyl substituents, starting from the E and Z isomers of ,-unsaturated ketones was studied. A high diastereoselectivity was revealed at the 1,2 chiral center chiral center induction, which is independent of the configuration of the starting chalcones.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

Separation of proteins with a molecular mass difference of 2 kDa utilizing preparative double-inverted gradient polyacrylamide gel electrophoresis under nonreducing conditions: application to the isolation of 24 kDa human growth hormone

A method for separating proteins with a molecular mass difference of 2 kDa using SDS-PAGE under nonreducing conditions is presented. A sample mixture containing several human growth hormone (hGH) isoforms was initially separated on a weak anion-exchange column. Fractions rich in 24 kDa hGH as determined by analytical SDS-PAGE were pooled and further separated by cation-exchange chromatography. The fractions pooled from the cation-exchange chromatography contained two hGH isoforms with a 2 kDa molecular mass difference according to SDS-PAGE analysis, 22 and 24 kDa hGH. The 22 and 24 kDa hGH were separated using continuous-elution preparative double-inverted gradient PAGE (PDG-PAGE) under nonreducing conditions. The preparative electrophoresis gel was composed of three stacked tubular polyacrylamide matrices, a 4% stacking gel, a 13-18% linear gradient gel, and a 15-10% linear inverted gradient gel. Fractions containing purified 24 kDa hGH were pooled and Western blot analysis displayed immunoreactivity to antihGH antibodies. PDG-PAGE provides researchers with an electrophoretic technique to preparatively purify proteins under nonreducing conditions with molecular mass differences of 2 kDa.