Fifty-two samples of street cocaine seized in the state of Rio de Janeiro, from May 2016 to April 2017, were evaluated according to their purity, presence of inorganic and sugar diluents and concentration of pharmacologically active adulterants. Cocaine contents, as well as the adulterants caffeine, lidocaine and phenacetin, were evaluated by gas chromatography coupled with mass spectrometry. The samples were screened by Raman spectroscopy for the presence of inorganic diluents and carbohydrates. The main diluents were calcium carbonate and sodium bicarbonate, which were found in 93% and 71% of the cocaine hydrochloride samples, respectively. Caffeine was found in 91% of the cocaine hydrochloride samples, while phenacetin was found in all freebase cocaine samples. Freebase cocaine samples were majorly composed of pharmacological active compounds (adulterants), unlike cocaine hydrochloride samples, which were majorly composed of inorganic compounds (diluents). It could be observed, by Raman Spectroscopy associated to multivariate analysis, similarities on cocaine hydrochloride composition according to certain criminal gangs. The percentage of pharmacological active compounds varied significantly on the analyzed samples, showing that these adulterants are indiscriminately added to street cocaine, what may increase consumers’ health risks.

<p>GC-FID, GC-MS and NMR spectral data were used to analyze the composition of the essential oils extracted from young and mature leaves of <italic>E. uniflora</italic> L. grown in Seropédica - RJ. Thirty and twenty-five compounds were identified, corresponding to approximately 98.19% and 93.77% of the total amount of oils, respectively. The major components of the young leaves were (3<italic>Z</italic>,7<italic>E</italic>)-3,7-dimethyl-10-(propan-2-ylidene)cyclodeca-3,7-dienone (germacrone, 34.59%), 4,5,6,7-tetrahydro-3,6-dimethyl-5-(prop-1-en-2-yl)-6-vinylbenzofuran (curzerene, 26.56%) and (1<italic>Z</italic>,5<italic>E</italic>)-1,5-dimethyl-8-(propan-2-ylidene)cyclodeca-1,5-diene (germacrene B, 12.72%), and of the mature leaves were curzerene (35.75%), germacrene B (19.22%) and β-(<italic>E</italic>,1<italic>R</italic>,9<italic>S</italic>)-4,11,11-trimethyl-8-methylenebicyclo[7.2.0]undec-4-ene (caryophyllene, 12.55%). The multivariate analysis applied to data from GC-MS allowed discrimination of the differences in the chemical composition of oils based on the age of the leaves. The components germacrone, curzerene e furanodiene (not observed during conventional chromatographic analysis) were isolated from the essential oil of young leaves. These compounds were characterized by GC-MS, and ¹H and ¹³C NMR (1D and 2D).</p>

The effect of the introduction of nitrogen atoms upon the triplet excited state reactivity of 1,4-diaza-9-fluorenone (1) and 1,4-diaza-9-benz[b]fluorenone (2), in acetonitrile, was investigated employing the nanosecond laser flash photolysis technique. The intersystem crossing quantum yield (Φces) for 1 and 2 was determined using 9-fluorenone as a secondary standard (Φces= 0.48, in acetonitrile) and for both diazafluorenones a value of Φces= 0.28 was found. Quenching rate constants ranged from 8.17x10(4) L mol-1 s-1 (2-propanol) to 1.02x10(10) L mol-1 s-1 (DABCO) for 1,4-diaza-9-fluorenone and from 6.95x10(5) L mol-1 s-1 (2-propanol) to 5.94x10(9) L mol-1 s-1 (DABCO) for 1,4-diaza-9-benz[b]fluorenone, depending if the quenching process involves energy, hydrogen or electron transfer. A comparison between quenching rate constants for both diazaflurenones and the parent compound, i.e. 9-fluorenone, a ketone with lowest triple state of ππ* configuration, lead to the conclusion that the reactive triplet excited state for 1,4-diaza-9-fluorenone and 1,4-diaza-9-benz[b]fluorenone has ππ* configuration.

Rate constants for the quenching of 1,3-indandione (1) triplet by olefins and by hydrogen and electron donors were obtained employing the laser flash photolysis technique in benzene solution. These rate constants ranged from 2.5x10(5) Lmol-1s-1 (for 2-propanol) to 5.9x10(9) Lmol-1s-1 (for DABCO). From the quenching rate constants by 1,3-cyclohexadiene, trans- and cis-stilbene a value between 49.3 and 52.4 kcal/mol was estimated for the energy of the triplet state of 1,3-indandione. The npi* character of this triplet state was evidenced by the quenching rate constants obtained when typical hydrogen donors were employed as quenchers. For 2-phenyl-1,3-indandione (2, R=phenyl) a fast Norrish type I reaction is operating which prevents the determination of kinetic and spectroscopic data of its triplet state.

The catalytic decomposition of soybean oil was studied in a fix bed reactor at 673 and 773 K and using amorphous silica-alumina and the zeolites USY, H-Mordenite and H-ZSM-5 as catalysts. Both the selectivity and the catalytic activity were determined by studying the product composition resulting from the chemical reactions. Physicochemical characteristics of the catalysts were obtained by X-ray fluorescence, Fourier Transform infrared spectroscopy, 29Si and 27Al Nuclear Magnetic Ressonance and textural analysis. The zeolites USY and H-ZSM-5, showing higher Brönsted acidity, yielded products with higher concentration in aromatic hydrocarbons, whereas with both H-Mordenite and amorphous silica-alumina the main products were paraffins.