Fluorimetric determination of diacetyl and 2,3-pentanedione with isoniazide and a zirconium salt

Diacetyl and 2,3-pentanedione react with isoniazide in acidified solutions to give the corresponding hydrazones which, by reacting with a zirconium (IV) salt, form fluorescent complexes. Both reactions have been studied separately. Variables such as pH, heating time, and excess of reactives are discussed. The method may be used for the determination of these compounds in foods.     

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     

Correlations between Van der Waals' volume and retention index general equation applicable to different homologous series

Summary Correlations between retention index (R_I) and Van der Waals' volume (V_W) in homologous series of n-alcohols, n-aldehydes and esters are studied on the stationary phases Carbowax 1540 and squalane. Influence of functional groups is quantified and a method for obtaining one general equation, valid for an indeterminate number of homologous series, is proposed.     

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.     

A simple and very sensitive spectrophotometric method for the direct determination of copper ions

A sensitive spectrophotometric method for the direct determination of copper in aqueous samples without a preconcentration step has been developed. It is based on the formation of a yellow complex with the chromogenic reagent di-2-pyridyl ketone benzoylhydrazone (dPKBH) in an alkaline medium. The complex stoichiometry was 1:2 (Cu:dPKBH) and presents maximum absorbance at 370 nm. The influence of chemical variables affecting the behaviour of the system such as pH, concentration of dPKBH, buffer solution and ethanol, order of addition of the reagents and stability of the complex, were evaluated. The molar absorptivity (epsilon) was 3.92x10(4) L mol(-1) cm(-1), and Beer's law was obeyed up to 3 mg L(-1) of copper. The relative standard deviation was 0.46% (n=11) for a sample containing 1 mg L(-1) Cu(II). The limit of detection was 2.5 micro g L(-1) and was therefore more sensitive than the direct methods reported previously. Finally, the method was successfully validated by analysing several real samples with different matrices, such as tap water, natural water or copper alloys, with an average relative error of 2.46%.     

Epoxides,cyclic sulfites,and sulfate from natural pentacyclic triterpenoids: theoretical calculations and chemical transformations

Several triterpenic derivatives, with the A-ring functionalized, were semisynthesized from oleanolic and maslinic acids. The reactivities of sulfites, sulfate, and epoxides in these triterpene compounds were investigated under different reaction conditions. Moreover, contracted A-ring triterpenes (five-membered rings) were obtained, by different treatments of the sulfate 7. From the epoxide 8, deoxygenated and halohydrin derivatives were semisynthesized with several nucleophiles. Ozonolysis and Beckmann reactions were used to yield 4-aza compounds, from five-membered ring olanediene triterpenes. The X-ray structure of sulfate 7 is given and compared with density functional theory geometries. Theoretical (13)C and (1)H chemical shifts (gauge-invariant atomic orbital method at the B3LYP/6-31G*//B3LYP/6-31G* level) and (3)J(H,H) coupling constants were calculated for compounds 5-9 and 34-36, identifying the (R)- or (S)-sulfur and alpha- or beta-epoxide configurations together with 4-aza or 3-aza structures.