Preparation of USY zeolite VOx supported catalysts from V(AcAc)3 and NH4VO3. Catalytic properties for the dehydrogenation of n-butane in oxygen-free atmosphere

The preparation of different samples of vanadia supported on ultrastable zeolite (VO(x)/USY) is discussed. The samples were prepared in order to obtain highly dispersed V-species, avoiding the formation of crystalline vanadia and the destruction of the zeolite framework. Two methods were employed for preparing VO(x)/USY samples: an organic route using V(AcAc)3 and an inorganic route using NH4VO3. The characterization of the samples was performed with XRD, TPR, NH3-TPD, and N2 isotherms. From these results it is concluded that when VO(x) is supported on the surface of USY from acidic aqueous solution of ammonium metavanadate, the destruction of the zeolite framework is accomplished. For higher pH values in the impregnating solution, undesired V2O5 is formed on the USY surface. On the other hand, VO(x)/USY prepared from the organic precursor shows no destruction of the USY structure. In addition, highly dispersed VO(x) are formed, though for relatively high V loadings (6%) an obstruction of the zeolite windows takes place. The samples are tested as catalysts for gas phase dehydrogenation of n-butane to olefins. The catalysts prepared from NH4VO3 are almost inactive for the reaction. On the other hand, both samples prepared from V(AcAc)3 present initial conversion levels in the 8-12% range. However, the selectivity depends on the V loading, the catalysts with 6% loading being the most selective (75%). The catalytic patterns of the samples (activity and selectivity) are in agreement with the physicochemical features of the VO(x)/USY surface.     

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.     

AlPO-Catalysed asymmetric Diels-Alder reactions of cyclopentadiene with chiral acrylates

Reactions of cyclopentadiene with several chiral acrylates are studied and compared with the same reactions catalysed by Zn(II)-exchanged K10 montmorillonite. In general, amorphous AlPO₄ is a more efficient catalyst than the clay. In particular, the reaction of cyclopentadiene with (−)-8-phenylmenthyl acrylate leads to 74% diastereomeric excess (d.e.) in methylene chloride at low temperatures. This result constitutes the highest asymmetric induction described to date for a solid-catalysed asymmetric Diels-Alder reaction. When the reactions are carried out in the absence of a solvent a noticeable decrease in selectivity is observed, probably due to an extensive competition of the non-catalysed reaction.     

Polarization of the Electrical Double Layer. Time Evolution after Application of an Electric Field

Electrophoresis is one of the electrokinetic phenomena most widely investigated, both from a fundamental point of view and as a research tool in academia and industry. However, the dependence between electrophoretic mobility and zeta potential is, in a general case, far from simple, because of the many physical processes involved. In this work, we first describe qualitatively and (in some cases) quantitatively the time behavior of the dipole moment induced in the electrical double layer by an applied electric field. Further, a simple relationship is deduced between the dipole moment and the electrophoretic mobility. Through the analysis of the time dependence of the former, it is possible to resolve the different contributions to the stationary values of the mobility. Three characteristic relaxation times are distinguished in the time evolution of the dipole moment: tau(H) (the time needed for hydrodynamic flows to be established), tau(MW) (time for ionic electromigration to develop), and tau(VD) (after this time, diffusion flows are established in the system, and the double layer polarization is complete). This means that different mechanisms are operating on the double layer for different times after the application of the field, and that computing the mobility at such different times is equivalent to calculating the steady-state electrophoretic mobility under different approximations. A comparison is shown between estimated and computed mobility values as functions of time and of zeta potential, confirming the validity of the asymptotic calculations. Copyright 2000 Academic Press.     

Derivative spectrophotometric resolution of mixtures of the food colourants Tartrazine, Amaranth and Curcumin in a micellar medium

A study of the absorption spectra of the food colourants Tartrazine (E-102), Amaranth (E-123) and Curcumin (E-100) in various organic solvents and pH media, have been carried out. In addition, the spectral behaviour in aqueous micellar systems of anionic, cationic and non-ionic surfactants, as well as beta-cyclodextrin, was investigated. Analytical methods are proposed for the determination of the three dyes in mixtures without any prior separation step, by the application of the derivative technique to the normal absorption spectra, based on the use of cetyltrimethylammonium bromide (CTAB) in 0.1 M NaOH, over the concentration range 2-50 mug ml(-1). The methods are applied for determining the three dyes in commercial food products.     

Synthesis and acid-base properties of (1H-benzimidazol-2-yl-methyl)phosphonate (Bimp2-). Evidence for intramolecular hydrogen-bond formation in aqueous solution between (N-1)H and the phosphonate group

The synthesis of (1H-benzimidazol-2-yl-methyl)phosphonic acid, H2(Bimp)+/-, is described: 2-chloromethylbenzimidazole was reacted with ethylchloroformate to give 1-carboethoxy-2-chloromethylbenzimidazole which was treated with trimethyl phosphite and after hydrolysis with aqueous HBr H2(Bimp)+/- was obtained. In H2(Bimp)+/- one proton is at the N-3 site and the other at the phosphonate group; both acidity constants were determined in aqueous solution by potentiometric pH titrations (25 degrees C; I = 0.1 M, NaNO3) and this furnished the pKa values of 5.37 +/- 0.02 and 7.41 +/- 0.02, respectively. The acidity constant for the release of the primary proton from the P(O)(OH)2 group of H3(Bimp)+ was estimated: pKa = 1.5 +/- 0.2. Moreover, Bimp2- can be further deprotonated at its neutral (N-1/N-3)H site to give the benzimidazolate residue, but this reaction occurs only in strongly alkaline solution (KOH); application of the H_ scale developed by G. Yagil (J. Phys. Chem., 1967, 71, 1034) together with UV spectrophotometric measurements gave pKa = 14.65 +/- 0.12. Comparisons with acidity constants taken from the literature show that this latter pKa value is far too large and this allows the conclusion that an intramolecular hydrogen bond is formed between the (N-1/N-3)H site and the phosphonate group of Bimp2-; the formation degree of this hydrogen-bonded isomer is estimated to be 98 +/- 2%. The general relevance of this and the other results are shortly discussed and the species distribution for the Bimp system in dependence on pH is provided.     

Design and synthesis of 2-alkylbenzimidazole derivatives as novel non-peptide angiotensin Ⅱ AT1 receptor antagonists

A series of 2-alkylbenzimidazole derivatives 9a-n have been designed and synthesized as a novel class of non-peptide angiotensin Ⅱ AT1 receptor antagonists. The synthesized compounds were evaluated for their antagonism of angiotensin Ⅱ, induced contraction in the rabbit thoracic aortic ring and the results showed that compounds 9a, 9g and 9j exhibited potent antagonistic activity of AT1 receptor.     

On the Synthesis of Some 2-Arylhydrazono-3-oxothieno[2,3-<Emphasis Type="Italic">b</Emphasis>]pyridines by Reaction of Nitrilimines with 2-Mercaptonicotinic Acid

Summary. Nitrilimines prepared from N-arylhydrazono chlorides reacted with 2-mercaptonicotinic acid yielding the corresponding addition products, 2-[(2-oxo-1-arylhydrazonopropan-1-yl)mercapto] nicotinic acids, which were treated with 1,1-carbonyldiimidazole in THF affording by cyclocondensation the corresponding hitherto unknown 2-arylhydrazono-3-oxothieno[2,3-b]pyridines.     

Quantitative analysis of six pesticides in fruits by capillary electrophoresis-electrospray-mass spectrometry

A method to identify and quantify six pesticide residues - dinoseb, pirimicarb, procymidone, pyrifenox, pyrimethanil, and thiabendazole - in peaches and nectarines using capillary electrophoresis-electrospray ionization-quadrupole ion trap-tandem mass spectrometry (CE-ESI-MS/MS) is described. Separation was carried out using a buffer of 0.3 M ammonium acetate at pH 4 with 10% methanol. Pesticide residues present in peach and nectarine samples were preconcentrated by solid-phase extraction using C(18), eluted with CH(2)Cl(2), concentrated to dryness, and redissolved in buffer to obtain lower detection limits. The recoveries of the analytes ranged from 58 to 99% and the relative standard deviations were 9 to 19%. Under optimized CE-MS/MS conditions the minimum detectable levels for the six pesticides in spiked peach samples were between 0.01 mg/kg for pirimicarb and 0.05 mg/kg for procymidone with pressure injection of 50 mbar for 5 s (5 nL) at a signal-to-noise ratio of 3, which constitutes a severalfold increase in sensitivity compared to CE-MS, using a single quadrupole, and to conventional CE-UV. The potential of the method was demonstrated by analyzing different samples taken from regional agricultural cooperatives. The pesticides most often detected were thiabendazole and procymidone.