An existence theorem for neutral variational problems of Bolza

This note proves an existence theorem for a generalized Bolza-type problem that has time delays in both the state and velocity variables. The assumptions are stated in terms of a modification of the classical Hamiltonian, and extend ideas of Rockafellar to the delay case.     

Magneto-volume effects in Fe–Cu solid solutions

The magnetic properties of Fe–Cu metastable solid solutions have been investigated by means of neutron diffraction and magnetisation measurements. These compounds exhibit ferromagnetic order with Curie temperatures above room temperature for concentrations beyond 40 at% in Fe. The magnetic moment at 5 K can reach values over 2 μ_B, while the high field susceptibility is similar to that found in FCC–FeNi Invar alloys. These features together with the low values for the linear coefficient for thermal expansion in the ferromagnetic region suggest that magneto-volume anomalies, including Invar behaviour, play a major role in the magnetic properties of this system when the crystal structure is face centred cubic. Such behaviour could be explained using theoretical total-band energy calculations.     

Production,purification, and characterization of a low-molecular-mass xylanase from Aspergillus sp. and its application in baking

An extracellular xylanase produced by a Mexican Aspergillus strain was purified and characterized. Aspergillus sp. FP-470 was able to grow and produce extracellular xylanases on birchwood xylan, oat spelt xylan, wheat straw, and corncob, with higher production observed on corncob. The strain also produced enzymes with cellulase, amylase, and pectinase activities on this substrate. A 22-kDa endoxylanase was purified 30-fold. Optimum temperature and pH were 60 degrees C and 5.5, respectively, and isoelectric point was 9.0. The enzyme has good stability from pH 5.0 to 10.0, retaining >80% of its original activity within this range. Half-lives of 150 min at 50 degrees C and 6.5 min at 60 degrees C were found. K(m) and activation energy values were 3.8 mg/mL and 26 kJ/mol, respectively, using birchwood xylan as substrate. The enzyme showed a higher affinity for 4-O-methyl-D-glucuronoxylan with a K(m) of 1.9 mg/mL. The enzyme displayed no activity toward other polysaccharides, including cellulose. Baking trials were conducted using the crude filtrate and purified enzyme. Addition of both preparations improved bread volume. However, addition of purified endoxylanase caused a 30% increase in volume over the crude extract.     

Determination of fluoride in complex liquid matrices by electrothermal atomic absorption spectrometry with in-furnace oxygen-assisted ashing

A new chemical method is reported for the determination of total fluoride in complex liquids and suspensions, such as fruit juices, urine, serum and blood. It is based on the formation of the A1F radical in a graphite furnace afterin situ oxygen-assisted ashing of the untreated sample. The absorbance of this radical is measured at 227.45 nm. The method is relatively easy to use and provides a low detection limit (14 ng/ml) and reasonable reproducibility (5–10%).     

Cycloaddition reaction of 2-azadienes derived from beta-amino acids with electron-rich and electron-deficient alkenes and carbonyl compounds. Synthesis of pyridine and 1,3-oxazine derivatives

Functionalized keto-enamines 6 were obtained by nucleophilic addition of enol ethers to the imine moiety of 2-azadienes derived from dehydroaspartic esters 4. Reactions of 2-azadiene 4c containing three electron-withdrawing substituents (CO(2)R) with enol ethers 5 in the presence of lithium perchlorate led to the formation of tetrahydropyridine derivatives 7 in a regio- and stereoselective fashion. 2H-[1,3]-oxazines 10 and pyridine derivatives 12 and 13 were obtained by heterocycloaddition reactions of electron-poor azadienes 4d-g containing two electron-withdrawing substituents (4-O(2)N-C(6)H(4), CO(2)R) in positions 1 and 4 with carbonyl derivatives (ethyl glyoxalate 9a and diethyl ketomalonate 9b) and the electron-deficient olefin tetracyanoethylene 11.     

Monitoring of the metal displacement from the recombinant mouse liver metallothionein Zn(7)-complex by capillary zone electrophoresis with electrospray MS detection

A solution of a Zn-complex of recombinant mouse MT-1 isoform (Zn(7)-MT-1) was prepared and titrated with Cd(2+) ions. A method based on the coupling of capillary zone electrophoresis (CZE) with electrospray MS detection was developed for the analysis of the stoichiometry of the species formed during the titration. The method offered the possibility of the on-line removal of up to 100 mM Tris or phosphate buffer solutions that would otherwise suppress the electrospray signal. By allowing the determination of the metal stoichiometry of the complex species present in solution the method was shown to be complementary to circular dichroism and UV-VIS spectrophotometry conventionally used for similar studies. The titration of the Zn(7)-MT complex with Cd(II) showed the sequential displacement of the Zn by Cd. The unusually high stability of the Cd(6)Zn(1)-MT species was observed which suggests a structural role of the remaining Zn(II) ion.     

Water-soluble chiral monosulfonamide-cyclohexane-1,2-diamine-RhCp complex and its application in the asymmetric transfer hydrogenation (ATH) of ketones

Monosulfonamide ligands with heteroatom/heterocyclic systems were derived from trans-(1R,2R)-cyclohexane-1,2-diamine and complexed with [Ru(benzene)Cl₂]₂, [Cp^∗RhCl₂]₂ in situ and used in the ATH of aromatic ketones with aqueous sodium formate as the hydrogen source. The chiral secondary alcohols were obtained with >93% enantioselectivity and >89% yield. Reduction in water was faster than in isopropanol/KOH. Addition of surfactants showed little or no effects.     

Asymmetric synthesis of 2H-azirines derived from phosphine oxides using solid-supported amines. Ring opening of azirines with carboxylic acids

A simple and efficient asymmetric synthesis of 2H-azirine-2-phosphine oxides 3 is described. The key step is a solid-phase bound achiral or chiral amine-mediated Neber reaction of beta-ketoxime tosylates derived from phosphine oxides 1. Reaction of 2H-azirines 3 and 11 with carboxylic acids 4 gives phosphorylated ketamides 5 and 12. Ring closure of ketamides 5 and 12 with triphenylphosphine and hexachloroethane in the presence of triethylamine leads to the formation of phosphorylated oxazoles 8 and 13.     

Synthesis of pyrazine-phosphonates and -phosphine oxides from 2H-azirines or oximes

[reaction: see text] Tetrasubstituted pyrazines containing two phosphonate groups 2 in positions 2 and 5 and trisubstituted pyrazines containing a phosphonate 5 or a phosphine oxide group 7 in position 2 are obtained by thermal treatment of 2H-azirine-2-phosphonates 1 and -phosphine oxides 6. These pyrazines can also be prepared from beta-ketoxime tosylates 9 and 10 or from oxime derived from phosphine oxide 11.