Identification (GC and GC-MS) of unsaturated acetates in Elasmopalpus lignosellus and their biological activity (GC-EAD and EAG)

Two insect colonies of Elasmopalpus lignosellus were reared in our laboratory, the first being initiated from pupae obtained from a cornfield in the region of Sete Lagoas, Minas Gerais and the second from a cornfield in the region of Goiania, Goiás. From the two colonies, two extracts were prepared from the pheromone glands of virgin E. lignosellus females. The extract obtained from the first colony was designated as extract 1 while the extract obtained from the second colony was designated as extract 2. Extract 1 was analyzed by gas chromatography-mass spectrometry (GC-MS) with (Z)-9-hexadecenyl acetate [(Z)-9-HDA] and (Z)-11-hexadecenyl acetate [(Z)-11-HDA] being identified and confirmed by the formation of DMDS derivatives. In addition, a third acetate, which could be either (E)-8-hexadecenyl acetate [(E)-8-HDA] or (E)-9-hexadecenyl acetate [(E)-9-HDA] was detected by GC-MS. Extract 2 was analyzed by gas chromatography (GC) and gas chromatography-electroannetography (GC-EAD) revealing the presence of (Z)-11-HDA and (Z)-9-TDA. In addition, the same compounds elicited a response with the E. lignosellus male antenna obtained from the second insect colony. Electroantennography (EAG) screening with the male E. lignosellus antenna (obtained from the second insect colony) was conducted with the 23 possible tetradecenyl acetates (TDA) and 22 hexadecenyl acetates (HDA) as standards. Out of the 23 TDA isomers evaluated, only (Z)-9-TDA elicited a response and out of the 22 HDA [(Z) and (E) isomers gamma2 to delta13] evaluated only (Z)-11-HDA elicited a response. The acetate compositions of two extracts obtained from insects originating from the two states (Minas Gerais and Goiás) of Brazil were different from one another as well as from that obtained from insects in Tifton, GA, USA. The bioactivity data (GC-EAD) of the extract 2 differed from those reported for the Tifton, GA, USA population. These data suggest polymorphism in relation to the insect populations found in Brazil and in the USA. The possibility of the existence of an E. lignosellus sub-species cannot be ruled out.     

Diorganotin(IV) derivatives of substituted benzohydroxamic acids with high antitumor activity

A series of diorganotin(IV) and dichlorotin(IV) derivatives of 4-X-benzohydroxamic acids, [HL(1) (X = Cl) or HL(2) (X = OCH(3))] formulated as [R(2)SnL(2)] (R = Me, Et, nBu, Ph or Cl; L = L(1) or L(2)), along with their corresponding mixed-ligand complexes [R(2)Sn(L(1))(L(2))] have been prepared and characterized by FT-IR, (1)H, (13)C, and (119)Sn NMR spectroscopy, mass spectrometry, elemental analysis, and melting points. In addition, single-crystal X-ray diffraction analyses were carried out for [Me(2)SnL(2)] (L = L(1) or L(2)), which show coordination structures intermediate between distorted octahedra and bicapped tetrahedra. The hydroxamate ligands are asymmetrically coordinated by the oxygen atoms, the carbonyl oxygen atom is further away from the metal center than the other oxygen atom. The complexes are stable monomeric species; most of them are soluble not only in chlorohydrocarbon solvents, but also in alcohols and hydroalcoholic solutions. In polar solvents, the mixed-ligand complexes gradually decompose into the corresponding single-ligand complex couples. The complexes exhibit in vitro antitumor activities (against a series of human tumor cell lines) which, in some cases, are identical to, or even higher than, that of cisplatin. For the dialkyltin complexes, the activity increases with the length of the carbon chain of the alkyl ligand and is higher in the case of the chloro-substituted benzohydroxamato ligand. The [nBu(2)Sn(L(1))(2)] complex displays a high in vivo activity against H22 liver and BGC-823 gastric tumors, and has a relatively low toxicity.     

Preliminary characterization of anhydrous ethanol used in Brazil as automotive fuel

This work reports preliminary studies on the characterisation of anhydrous ethanol (AEA) used as an automotive fuel mixed with gasoline in Porto Alegre (South Brazil). Pre-concentration of the impurities contained in 1000 ml of AEA was carried on through solid-phase extraction using XAD4 resin. The main compounds in the extract were identified by means of spectral data from the library of the equipment. The concentrate was then fractionated using a preparative liquid chromatographic column filled with activated silica gel and the elution procedure was carried out with, n-hexane, n-hexane-benzene (1:1, v/v) and dichloromethane. Prior to analysis by GC-MS, each fraction was reduced to 1 ml with a gentle stream of nitrogen. Saturated linear hydrocarbons and aromatic hydrocarbons eluted in the first fraction and oxygenated compounds such as aldehydes. ketones and alcohols, eluted in the second one. were the main compounds detected in the sample.     

Determination of moxifloxacin in tablets and human urine by square-wave adsorptive voltammetry

This work presents an electroanalytical methodology developed for square-wave voltammetry based in the electrochemical reduction in hanging mercury drop electrode (HMDE), which is simple, fast, reliable and sensitive for determination of moxifloxacin (MOXI) in tablets and spiked urine human samples. The support electrolyte that provided a more defined and intense peak current for MOXI determination was the phosphate buffer 0.04 mol l^{− 1} pH 8.0. In the best-optimized conditions the drug presented an only peak of reduction at − 1.38 V vs. Ag/AgCl, using an E_acc. of − 0.30 V. An LOD of 0.44 and 3.20 ng ml^{− 1} and an LOQ of 1.46 and 10.60 ng ml^{− 1} were found for the pure standard of moxifloxacin and in the presence of matrix, respectively. A good recovery was obtained for assay spiked urine samples and a good quantification of MOXI was achieved in a commercial formulation. The methodology proposed was more sensitive than the spectrofluorimetric and spectrophotometric method with precision and accuracy equivalent.     

Interdiffusion studies in Bi-based layered systems with nanosecond laser pulses

Interdiffusion processes are induced by nanosecond laser pulses from an excimer laser. The Bi-based systems studied are formed by a Bi layer and a Sb or Ge layer. Configurations with Bi at the surface layer or at the innermost layer are both studied. Real-time reflectivity measurements are performed during the irradiation to determine the process kinetics and times and Rutherford backscattering spectrometry is used to obtain the concentration depth profiles. It will be shown that there is an interfacially initiated diffusion process in the Bi-Sb system and that the diffusion coefficients of this system within the liquid phase are in the 10^–5–10^–6 cm²/s range. The Bi-Ge system shows instead little mixing, the diffusion coefficients of the system within the liquid phase being at least two orders of magnitude lower. The differences observed when Bi is the surface layer or the innermost one are related to the different thermal responses of the system.     

On the cube problem of Las Vergnas

We prove a conjecture of Las Vergnas in dimensions d7: The matroid of the d-dimensional cube C ^d has a unique reorientation class. This extends a result of Las Vergnas, Roudneff and Salaün in dimension 4. Moreover, we determine the automorphism group G ^d of the matroid of the d-cube C ^d for arbitrary dimension d, and we discuss its relation to the Coxeter group of C ^d . We introduce matroid facets of the matroid of the d-cube in order to evaluate the order of G ^d . These matroid facets turn out to be arbitrary pairs of parallel subfacets of the cube. We show that the Euclidean automorphism group W ^d is a proper subgroup of the group G ^d of all matroid symmetries of the d-cube by describing genuine matroid symmetries for each Euclidean facet. A main theorem asserts that any one of these matroid symmetries together with the Euclidean Coxeter symmetries generate the full automorphism group G ^d . For the proof of Las Vergnas' conjecture we use essentially these symmetry results together with the fact that the reorientation class of an oriented matroid is determined by the labeled lower rank contractions of the oriented matroid. We also describe the Folkman-Lawrence representation of the vertex figure of the d-cube and a contraction of it. Finally, we apply our method of proof to show a result of Las Vergnas, Roudneff, and Salaün that the matroid of the 24-cell has a unique reorientation class, too.