Heuristic analysis of <Emphasis Type="Italic">Eucalyptus globulus</Emphasis> bark depolymerization via acid-liquefaction

A clear, direct and rapid analysis of the preliminary results concerning the acid liquefaction of Eucalyptus globulus’ bark is herein presented. The results led to a methodology for the selective liquefaction of hemicellulose and amorphous cellulose. Liquefaction was conducted at various temperatures, as well as different reaction times. The process results are heuristically explained in view of the experiments of ATR-FTIR, hydroxyl number, and acid value. The procedure method allows reusing the wastes arising from the paper industry. Valuable products and chemical building blocks from lignocellulosic biomass, mostly based on cellulose can be thus accessed.     

Solution Chemistry of Arsenic Anions in the Presence of Metal Cations

The interaction of arsenic(V) and arsenic(III) oxyanions with metal cations was investigated by potentiometry under temperature and ionic strength conditions approaching those prevailing in natural waters. The selection includes the major metal cations and some other ions of high environmental relevance. Ionic pairs [M(As^VO₄)]^?, [M(HAs^VO₄)] and [M(H₂As^IIIO₃)]⁺ formation is suggested for all +2 metal cations, based on the potentiometric results. These ion-pairs between arsenic anions and other metal cations are hardly ever mentioned or taken into account when arsenic speciation in natural waters is considered. These results provide the basis for studying arsenic speciation in natural aquatic systems, on which environmental fate, bioavailability and toxicity of the element depend. Some extrapolations to the conditions of the natural waters are presented as well as some insights into the adsorption process onto hydrous oxides.     

Application of HPLC-NMR coupling using C30 phase in the separation and identification of flavonoids of taxonomic relevance

The on-line separation and identification of two important taxonomic markers for plant species of the Paepalanthus genus, the flavonoids 6-methoxykaempferol-3-O-β-D-glucopyranoside and 6-methoxykaempferol-3-O-β-D-6″(p-coumaroyl)glucopyranoside, has been performed with an HPLC-NMR coupling using C₃₀ phase. 1D spectra have been recorded in the stopped-flow mode for the two predominant chromatographic peaks. This is the first application of HPLC-NMR coupling using C₃₀ phase to a taxonomic problem. The technique drastically reduces the required amount of sampling for structure determination. Received: 20 March 2000 / Revised: 14 June 2000 / /Accepted: 23 June 2000     

Liberation of excess energy and retransformation of mechanically activated cadmium sulphide

On heating vibro-milled CdS containing the strained high-pressure rock salt phase, the excess energy was gradually liberated accompanied by the retransformation into more stable phases and the restoration of their crystallinity. Profiles of DSC curves, inter-relationships between thermal and crystallographical properties, the stability of each phase and the mechanism of the mechanochemical activation are discussed. A direct retransformation of the strained high-pressure phase was found to accompany the liberation of the excess energy.     

On the High Viscosity of Aqueous Solution of Lysozyme Induced by Some Organic Solvents

A remarkably high viscosity has been induced in protein aqueous solutions by the addition of certain structurally related organic solvents. The effect has been observed for lysozyme aqueous solutions containing tetramethylurea (TMU), dimethylsulfoxide (DMSO), dimethylformamide, and hexamethylphosphortriamide. The effect has also been induced in ferrocytochrome c aqueous solutions by TMU. Critical concentrations for both the protein and organic solvent were verified for the onset of the viscosity increase. A common feature of the solvents which were able to induce the effect is a dipolar moiety (C=O, S → O and P → O) and a nonpolar region represented by the methyl groups. The resulting fluids show an extremely restricted flow and a typical non-Newtonian, pseudoplastic behavior. Use was made of¹H nuclear magnetic resonance (NMR) and Raman spectroscopy to characterize protein structural modifications and of¹³C NMR to investigate changes in relaxation times and chemical shifts in the solvent/water solutions. A systematic rheological characterization of the systems was undertaken for some of the solvents, and unusual patterns of viscous effects were identified for the solvent/water systems both with and without protein. The process was found to be at least partially reversible, as concluded from the recovered original solution rheological characteristics and the original protein¹H NMR spectrum, after eliminating the organic solvent by ultrafiltration. The whole process was characterized as consisting of two mutually independent stages. The first involves an extensive conformational transition of the polypeptide backbone, from a predominantly α-helical to increased random coiled and β-sheet structures, with the occurrence of nonorthodox protein secondary structures at regions above the solvent critical point. The second stage consists of short-lived interchain contacts leading to an entanglement of the macromolecular system as a whole. A microphase reversion in the organic solvent/water mixture, supported by¹³C NMR and rheological results, is proposed as the driving force causing the observed behavior.     

An Efficient and Simple Entry to N-Substituted beta-Enamino Acid Derivatives from 2-Alkyl-2-oxazolines and 2-Alkyl-2-thiazolines

Reaction of azaenolates of 2-alkyl-oxa(thia)zolines 6 with imidoyl chlorides 7 as electrophiles to furnish masked N-substituted beta-enamino acid derivatives 1-2 in 70-90% yield is described. Alternative routes are discussed. Compounds 1-2 generally appear in one tautomeric form, imino or enamino, depending on the nature of the imidoyl chloride. The configuration of the enamino moiety (Z) and the conformation (s-cis) of compounds 1-2 obtained were established by an NMR study and unequivocally set by nuclear Overhauser effect difference experiments. An X-ray structure of compound 1e is also reported, showing a strong intramolecular NH.N hydrogen bond. Ab initio calculations (HF/3-21G and HF/3-21+G) have been carried out on several representative examples (1e, 1p, and 1l) in an attempt to support and provide the correct geometry of these derivatives. Structural considerations among the possible isomers of compounds 1 are discussed. From these studies it was concluded that the theoretical calculations agree with the experimental results. In addition, a very simple one-pot procedure for the preparation of masked N-substituted alpha-alkylated beta-enamino acid derivatives 2 from 6, 7, and different alkyl halides (R(3)Y) is described.     

Production and Characterization of β-Glucanase Secreted by the Yeast Kluyveromyces marxianus

An extracellular β-glucanase secreted by Kluyveromyces marxianus was identified for the first time. The optimal conditions for the production of this enzyme were evaluated by response surface methodology. The optimal conditions to produce β-glucanase were a glucose concentration of 4 % (w/v), a pH of 5.5, and an incubation temperature of 35 °C. Response surface methodology was also used to determine the pH and temperature required for the optimal enzymatic activity. The highest enzyme activity was obtained at a pH of 5.5 and a temperature of 55 °C. Furthermore, the enzyme was partially purified and sequenced, and its specificity for different substrates was evaluated. The results suggest that the enzyme is an endo-β-1,3(4)-glucanase. After optimizing the conditions for β-glucanase production, the culture supernatant was found to be effective in digesting the cell wall of the yeast Saccharomyces cerevisiae, showing the great potential of β-glucanase in the biotechnological production of soluble β-glucan.