The first bismuth(III)-catalyzed guanylation of thioureas

This work describes the first catalytic bismuth-promoted synthesis of polysubstituted guanidines in good yields through the guanylation reaction of N-benzoyl or N-phenylthioureas with primary and secondary amines, but now employing equimolar amounts of each organic reagent. Both bismuth iodine and bismuth nitrate were efficient as inorganic thiophiles at only 5 mol % in relation to substrates, being the first example of inorganic thiophiles acting in guanylation at catalytic levels.     

Anharmonic effects in large-amplitude vibrations of metal clusters

Two types of extreme collective motion, large-amplitude many-phonon vibration of the ionic core and rotation of the cluster with high angular momenta, are considered. The interplay between vibration and collective motion towards fission is discussed. A new mechanism of formation and rupture of the neck is proposed which is based on the Franck-Condon principle, and accounts for the interplay between vibration and fission. Under rotation, the change of the shape of the cluster and a phase transition from axially symmetric to triaxial ellipsoid are predicted. For studying the effects, vibrational motion can be induced by laser radiation. Rotational motion may arise in collisions of clusters. Received 26 April 2001 and Received in final form 15 October 2001     

On the stability of bcc Co in Co/Fe superlattices an NMR and XRD study

While RHEED observations show that 10 to 11 As is the stability limit for an open bcc Co layer when grown on an Fe substrate, our XRD and NMR studies have shown that, in MBE grown Co/Fe superlattices, cobalt can be stabilised in a bcc structure up to a critical Co thickness of 21 Ås. In order to understand this apparent discrepancy, NMR experiments have been carried out in Co_x/Fe_y multilayers with thickness varying in the range 5 Å < x < 42 Å and 24 Å < y < 60 Å, grown on GaAs (1 1 0) as well as on MgO (1 0 0) substrates. The analysis of the chemical short range order by NMR concludes that the larger bcc Co thickness observed in superlattices results from the formation of a rather homogeneous CoFe_20% bcc alloy which contains the supplementary 10–11 As of Co and which coexists with pure Co grains. The concentration of about 20% Fe in the alloyed part of the Co layer happens to be close to the stability limit for a bcc structure in the equilibrium phase diagram of bulk CoFe alloys. However, while a mixture of bcc and fcc phases is observed in bulk alloys, the bcc structure is preserved in all phases under the MBE growth conditions and below the critical thickness. Above the critical thickness amixture of bcc Co, bcc CoFe and hcp Co is observed.     

Production of cellulase in solid-state fermentation withTrichoderma reesei MCG 80 on wheat straw

Applied Biochemistry and Biotechnology - It is an accepted fact that ethanol production from lignocellulosic materials is not economical as yet because of the high cost of cellulase production. To...     

Synthesis of non-agglomerated Ba<Subscript>0.77</Subscript>Ca<Subscript>0.23</Subscript>TiO<Subscript>3</Subscript> nanopowders by a modified polymeric precursor method

In this work, we have studied the influence of the pH on the synthesis and structural properties of the Ba_0.77Ca_0.23TiO₃ nanopowders synthesized by a modified polymeric precursor method, in order to achieve non-agglomerated powders. Synthesis, morphology, thermal reactions, crystallite and average particle size of the synthesized powders were investigated through thermal analysis (DTA/TG), X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) and Infrared spectroscopy. In summary, Ba_0.77Ca_0.23TiO₃ nanopowders were synthesized for the first time at a relative low temperature (500 °C). It was also found that the alkalinity and acidity of the solution presented a great influence on the powder properties. The best results were obtained from solutions with pH = 8.5 and 11 whose nanopowders presented weakly agglomerate, with homogeneous particle size and a narrow size distribution (30–40 nm). This behavior could be explained based on the FT-IR results in which it was possible to see the increased of the chelation in higher pHs.     

Thermal studies of pre-formulates of metronidazole obtained by spray drying technique

Compatibility studies between active drugs and excipients are substantial in the pharmaceutical technology. The objective of the present work was to develop pre-formulated mixtures of metronidazole (MT) obtained by spray drying (SPDR) and their thermoanalytical characterization. Dynamic and isothermal TG, conventional DSC and DSC coupled to a photovisual system were used. DSC experiments with both techniques confirmed the homogeneity of the conventional and pre-formulated mixtures. The TG data made possible the comparison the thermal stability of the different mixtures. Similar thermal stabilities were found of the conventional and pre-formulated mixtures, with slower particles sizes of MT.     

Modification de la position 8 des purines nucleosides et de l'adenosine monophosphate cyclique-3′,5′. Reactions de couplage catalytique des organo-magnesiens avec les bromo-8 purines ribosides et bromo-8 adenosine monophosphate cyclique-3′,5′ silyles en presence de dichloro-bis-triphenylphosphine palladium

The palladium catalysed condensation of Grignard reagents with silyl derivatives of 8-bromopurine nucleosides and 8-bromoadenosine-3′,5′ cyclic monophosphate is a convenient method for the preparation of free 8-alkylpurine nucleosides and 8-alkyladenosine-3′,5′ cyclic monophosphate.     

Fragmentation pathways of organoarsenical compounds by electrospray ion trap multiple mass spectrometry (MS6)

With its detection limit well below 30 pg microl(-1) LC-MS-MS has become a sensitive and thus popular analytical technique for organoarsenical compounds. Collision induced dissociation (CID) is a valuable tool for speciation and facilitates a positive identification of the species detected. However, it is not straightforward to understand the fragmentation pathways of organoarsenical compounds when only CID-MS-MS data is available. In the present paper we have investigated multiple mass spectrometry (MSn, n=1, 2, 3, 4, 5, 6) with electrospray CID fragmentation for a number of organoarsenical compounds likely to occur in the environment. The investigated compounds were tetramethylarsonium, trimethylarsinoxide, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, arsenocholine, and dimethylarsinoylethanol. By CID of (protonated) organoarsenical cations mostly even-electron fragments are produced after neutral loss processes such as elimination of H2, H2O, CH4, C2H2, C2H4, C2H6, HCHO, CH3OH, C2H5OH, C2H4O, and CH2CO. However, abundant odd-electron fragments are also formed after elimination of radical species. Evidence for reduction of As(V) to As(III) as a driving force in the odd-electron ion formation is obtained.     

Properties of block and graft copolymers of polybutadiene with small complexed poly(4-vinylpyridine) segments

Various diblocks, triblocks and a graft copolymer of butadiene with 4-vinylpyridine short blocks have been prepared. They were complexed with ZnCl₂ to give ionomer-like materials. For all copolymers, the T_g of the elastomeric block (?84°C to ?91°C) was unchanged by complexation. For all diblocks and triblocks with short blocks (DP _n ～ 3) the storage modulus was only slightly increased by comparison with uncomplexed materials. For the graft copolymer even with short blocks the material is less sensitive to temperature after complexation. For triblocks, when the DP _n of the vinylpyridine blocks was high enough (15 units), complexes were associated in multiplets of large size and the elastomeric properties were retained up to 200°C.     

Analysis of primary aliphatic short-chain monoamines by LC in water samples

Several derivatization procedures with o-phthaldialdehyde-N-acetylcysteine (OPA-NAC) were compared for a rapid analysis of primary aliphatic short-chain monoamines in water samples by HPLC using a LiChorospher analytical separation column (100RP₁₈ mm i.d., 5 μm). Both the solution and the solid-support assisted off-line derivatization on C₁₈ SPE cartridges were inadequate options because of beginning degradation processes of the instable isoindol derivatives during their transfer to the analytical column. This problem was precluded with the on-column or solid-support assisted on-line derivatization. In the last mentioned procedure, the derivatization took place in a Hypersil C₁₈ precolumn ( mm i.d., 30 μm) connected with an additional preconcentration step resulting in better detection limits (0.002-0.040 μg ml⁻¹ requiring only 150 μl of water sample) than in the on-column procedure (0.08-0.16 μg ml⁻¹). The improved sample handling, the better control of parameters affecting reaction rates, the fully automation of this method with only 10 min analysis time for each sample are further advantageous. The potential of the solid-support assisted on-line derivatization was outlined and applied to water samples from several sources. Recovery values near 100% were obtained.