A one-parameter family of hamiltonian structures for the KP hierarchy and a continuous deformation of the nonlinear WKP algebra

The KP hierarchy is hamiltonian relative to a one-parameter family of Poisson structures obtained from a generalized Adler map in the space of formal pseudodifferential symbols with noninteger powers. The resulting W-algebra is a one-parameter deformation of W_KP admitting a central extension for generic values of the parameter, reducing naturally to W _n for special values of the parameter, and contracting to the centrally extended W₁₊, W and further truncations. In the classical limit, all algebras in the one-parameter family are equivalent and isomorphic tow _KP. The reduction induced by setting the spin-one field to zero yields a one-parameter deformation of which contracts to a new nonlinear algebra of the W-type.Address after October 1993: Queen Mary and Westfield College, UK     

Beiträge zur Chemie der Pyrrolo[3,2-c]azepine und der Pyrrolo [3,2-b]azepine

Some chemical transformations in the series of the pyrrolo [3,2-b]azepines and the pyrrolo[3,2-c]azepines are reported: alkylation at the pyrrolo nitrogen and/or the azepino nitrogen, reduction of the lactam group by means of LiAlH₄, preparation of lactim ethers and amidines, substitution in position 2 by MANNICH reaction, bromination and condensation with oxalyl chloride or chloral hydrate, and the cyclocondensation with dimethylmalonyl chloride. The structures of the 2-substitution products have been evaluated by NMR.-spectroscopy.     

Reactions of thiosemicarbazones derived from beta-keto amides and beta-keto esters with Zn(II) and Cd(II) acetates: influence of metal, substitution, reagent ratio and temperature on metal-induced cyclization

Zinc(II) and cadmium(II) acetates were reacted in methanol under various experimental conditions with thiosemicarbazones derived from beta-keto amides or beta-keto esters (HTSC). Some of these reactions afforded thiosemicarbazonate complexes [M(TSC)2] with IR and NMR spectra compatible with N,S-coordination, but most gave complexes [ML2], where HL is a substituted 2,5-dihydro-5-oxo-1H-pyrazole-1-carbothioamide resulting from cyclization of the HTSC. Some of these pyrazolonates and two of the HL ligands were studied by X-ray diffractometry, and their structures are discussed. Surprisingly, the reactions of zinc(II) acetate with HTSC in 1:1 mol ratio usually gave a third, previously unreported type of complex with a dideprotonated ligand, [Zn(L-H)], which was also formed when [ZnL2] and Zn(OAc)2 interacted at room temperature in 1:1 mol ratio. These L-H complexes are highly insoluble in all common solvents, which hinders their characterization but suggests that they are polymeric in nature.     

Flow-through optical fiber sensor for automatic sulfide determination in waters by multisyringe flow injection analysis using solid-phase reflectometry

A software-controlled flow-through optical fiber diffuse reflectance sensor capitalized on the implementation of disk-based solid-phase pre-concentration schemes in a multisyringe flow injection analysis (MSFIA) set-up is proposed for the trace determination of sulfide in environmental waters and wastewaters. The fully automated flowing methodology is based on Fischer's coupling reaction of sulfide with N,N-dimethyl-p-phenylenediamine (DMPD) in the presence of Fe(iii) as oxidizing reagent in a 0.5 M HCl medium. The on-line generated methylene blue dye is subsequently delivered downstream to a dedicated optode cell furnished with an octadecyl-chemically modified (C(18)) disk, while continuously recording the diffuse reflectance spectrum of the pre-concentrated compound. A double regeneration protocol is finally executed to warrant minimum background noise and negligible baseline. Under the optimized chemical and hydrodynamic conditions, the optosensing MSFIA method features coefficients of variation better than 0.7%(n= 10) at 50 microg l(-1) concentration, a linear working range of 20-200 microg l(-1) sulfide, a 3sigma(blank) detection limit of 2.9 microg l(-1) sulfide and an injection throughput of 8 h(-1) for a pre-concentration sample volume of 2.9 ml. The interfacing of the robust and versatile multisyringe flow injection-based optode with a plug-in spectrophotometer furnished with a light emitting diode assures the miniaturization of the overall flow analyzer, which is, thus, readily adaptable to real-time monitoring schemes. The potential of the multisyringe flow method was assessed via the determination of sulfide traces in water samples of different complexity (namely, freshwater, seawater and wastewater).     

Development and validation of a liquid chromatography-ultraviolet absorbance detection assay using derivatisation for the novel marine anticancer agent ES-285 x HCl [(2S,3R)-2-amino-3-octadecanol hydrochloride] and its pharmaceutical dosage form

ES-285 x HCl [(2S,3R)-2-amino-3-octadecanol hydrochloride] is a novel investigational anticancer agent, which has shown in vitro and in vivo cytotoxic activity against various tumor cell lines with selectivity for certain solid tumors. The pharmaceutical development of ES-285 x HCl warranted the availability of an assay for the quantification and purity determination of ES-285 x HCl active pharmaceutical ingredient (API) and its pharmaceutical dosage form. A liquid chromatographic method (LC) comprising of derivatisation of ES-285 x HCl with phenylisothiocyanate and UV-detection was developed. The method was found to be linear, precise and accurate. The assay also proved selectivity as determined by analysing ES-285 x HCl in combination with 15 analogues and in combination with hydroxypropyl-beta-cyclodextrin, the excipient used in the lyophilised pharmaceutical dosage form. Stress testing showed that the degradation products were separated from the parent compound, confirming its stability indicating capacity. The method was found robust as determined with design of experiments (DoE), which made it possible to predict system suitability responses in worst case experimental conditions and to define criteria for system suitability testing.     

Synthesis of different chiral amino gamma-butyrolactones and amino gamma-butenolides

Different transformations of chiral epoxy esters 1 afford two different amino gamma-butyrolactones 2 and 6, and amino gamma-butenolides 8, by different nucleophilic opening-closing processes. [reaction: see text]     

Solid-state supramolecular organization, established directly from powder diffraction data, and photoluminescence efficiency of rigid-core oligothiophene-S,S-dioxides

The "rigid-core" material 3,5-dimethyl-2,3'-bis(3-methylthiophene)-dithieno[3,2-b:',3'-d]thiophene-4,4-dioxide (DTTOMe4) has the highest photoluminescence ever reported for thiophene-based molecules in the solid state. We report the structure of this material, determined directly from powder X-ray diffraction data using the Genetic Algorithm method for structure solution, followed by Rietveld refinement, and the structural properties are discussed in relation to the structures of the corresponding subsystems DTTO and DTTOMe. While the crystal structures of the latter compounds contain cofacial dimers, the crystal structure of DTTOMe4 comprises layers of molecules aligned in an antiparallel fashion. Intermediate neglect of differential overlap with single configuration interaction (INDO/SCI) calculations on the intermolecular interactions in the three crystal structures show that the different solid-state photoluminescence efficiencies of DTTOMe4, DTTOMe, and DTTO cannot be correlated with the different types of dipole-dipole alignment in the solid state. Instead, photoluminescence efficiencies correlate well with the rate of formation of nonradiatively decaying charge-transfer pairs upon photoexcitation. Because of larger intermolecular distances in DTTOMe4, the photoluminescence is less effectively quenched by charge-transfer processes than in DTTOMe and DTTO.