The quantification of minor alkaloids in seized cocaine can provide information for drug profiling and law enforcement initiatives. This work presents the development and validation of an analytical method to quantitate minor alkaloids in cocaine samples using gas chromatography with flame ionization detector, after derivatization. The method was validated in accordance with the ISO/IEC 17.025:2017 requirements. The calibration was linear (determination coefficient (R2) ≥ 0.998), ranging from 1.0 to 3,500 mg L-1 for all target analytes with suitable selectivity and precision (relative standard deviation lower than 10%). The method showed stability and robustness with respect to analytical parameter variations and presented good accuracy (recovery ranging from 90 to 108%). The method was considered adequate to routine forensic analysis in simultaneous quantification of anhydroecgonine methyl ester, anhydroecgonine, methylecgonine, tropacocaine, norcocaine, N-formylcocaine, trimethoxycocaine, ecgonine, benzoylecgonine, trans- and cis-cinnamoylcocaine. Eleven cocaine samples seized in different Brazilian regions were analyzed and their relative amounts of tropacocaine and trimethoxycocaine with respect to cocaine indicate both the possible varieties of coca leaf used for cocaine production and the likely origin of drug samples (Bolivia/Peru or Colombia). The contents of other minor alkaloids depict aspects of sample history such as purification by oxidation, hydrolysis and dehydration by thermal processes.

Medicines containing anabolic steroids are one of the main targets for counterfeiting worldwide, including Brazil. The aim of this work was to propose a method for discriminating original and counterfeit Durateston® ampoules by Fourier transform infrared spectroscopy (FTIR) followed by chemometric analysis. Ninety-six ampoules of Durateston®, 49 originals and 47 counterfeits, were analyzed by gas chromatography with mass spectrometry (GC-MS) and by FTIR. Principal component analysis was applied to the infrared spectra to detected different clusters, corresponding to original samples and different types of counterfeits. A partial least squares - discriminant analysis method was proposed to discriminate original samples from those counterfeits that were indistinguishable from the originals in the infrared analysis. A training subset comprised of one-third of the available spectra was used to establish a suitable model that correctly discriminated all samples in the test subset, resulting in 0% of false positive or negative results and 100% of efficiency rate, sensitivity and specificity. In addition to the low cost of the infrared technique, the proposed method is fast, reliable and suitable to replace GC-MS methods used in Durateston® ampoule analyses to detect counterfeiting.

This work describes results of chemical profiling by gas chromatography with flame ionization detector (GC-FID) of the main components (purity, oxidation level, and cutting agents) in 642 street cocaine samples seized in five different Brazilian States between 2011 and 2014. The analysis revealed the presence of cocaine with mean content of 49.8%. Freebase samples showed cocaine average content of 66.0%, whereas hydrochloride and not determined (n.d.) present cocaine content of 44.5% and 11.8%, respectively. Cocaine base samples show moderately (16%) to not oxidized (81%) levels, whereas cocaine hydrochloride samples exhibit moderate (37%) to high (22%) oxidation degrees. Approximately 34% of all the analyzed samples did not have any adulterant identified. Base cocaine samples are even less adulterated (42% uncut) with phenacetin being present in 53% (average content of 15%). Caffeine and lidocaine were mostly found in hydrochloride samples, while the n.d. samples show a combination of either phenacetin or a caffeine/lidocaine mixture. A mass balance approach is presented and seizures information can be combined to deliver intelligence and statistical analysis that might contribute to the understanding of street cocaine composition scenario. A total of 269 samples were characterized as crack cocaine showing phenacetin as the main adulterant and presenting an average cocaine content of 68.3%.

From a set of 159 samples seized by Brazilian Federal Police between 2010 to 2013 in the Federal District, the major component chemical profiling routine analyses revealed the presence of cocaine with purity range of 5.5 to 99.9% (mean 69.8%). Most cocaine base samples show moderately and not oxidized levels, whereas cocaine hydrochloride samples exhibit moderate to high oxidation degrees. More than 40% of the analyzed samples did not have any adulterant. Phenacetin was the most abundant adulterant (24% average purity). Aminopyrine, a new adulterant, was identified and quantified only in cocaine base samples, mainly as a trace adulterant but also as a major compound. In most samples adulterated with aminopyrine, phenacetin was also identified as a major adulterant, suggesting a possible association of the two pharmaceuticals in the cutting process. Aminopyrine was not detected in 2010 seizures, but became a common adulterant throughout the years of 2011 to 2013. A mass balance approach analysis also established that adulterants are responsible for only 12% of the mass of all seizures (i.e., 84 kg), whereas 77% (i.e., 553 kg) is due to alkaloids (cocaine and cis/trans-cinnamoylcocaine), contributing to provide forensic intelligence information to police investigators.

A determinação do teor de cocaína em amostras de drogas consiste em uma importante tarefa em órgãos como a Polícia Federal Brasileira (BFP). Nesse sentido, este trabalho propõe apresentar um método baseado em espectros de infravermelho obtidos por refletância total atenuada (ATR) e regressão por mínimos quadrados parciais (PLSR) para quantificar cloridrato de cocaína em amostras de drogas. O método foi desenvolvido e validado com 275 amostras reais de drogas apreendidas pela BFP em todo o Brasil. A determinação foi realizada no intervalo de 35 a 99% (m/m) de cocaína nas amostras. Os resultados indicaram que o método é capaz de analisar diretamente amostras de drogas contendo cocaína na forma de cloridrato sem necessidade de qualquer preparo de amostra com erros médios de aproximadamente 3,00%, precisão de 1,50% (m/m) e concentração mínima detectável de 13% (m/m).

The determination of cocaine in drug samples is an important task for law enforcement agencies such as the Brazilian Federal Police (BFP). In this sense, this paper proposes a method based on infrared spectra obtained by attenuated total reflectance (ATR) and partial least squares regression (PLSR) to quantify cocaine hydrochloride in drug samples. The method was developed and validated with 275 actual samples of drugs seized by the BFP. The determination was performed between 35 to 99% (m/m) of cocaine in the drug samples. Results indicate that the method is able to directly analyze drug samples containing cocaine in its hydrochloride form without any sample preparation with average prediction errors of 3.00% (m/m), 1.50% (m/m) precision and 13% (m/m) of minimum detectable concentration.

A análise de tintas é realizada para verificar a ocorrência de falsificações em documentos. Nesse aspecto, métodos espectroscópicos são atrativos, pois preservam a integridade do documento. Neste trabalho, é proposto um método para a discriminação de tintas de canetas pretas entre tipos, marcas e modelos para a aplicação em documentos. Espectros de reflectância na região visível foram obtidos através do equipamento comparador espectral de vídeo VSC®6000 e da análise discriminante por mínimos quadrados parciais (PLS-DA). O método foi validado com dados independentes e um teste cego. O viés presente nos resultados foi corrigido para a detecção das amostras anômalas. Os modelos PLS-DA apresentaram baixos erros médios quadráticos de previsão (RMSEP) e permitiram a discriminação de todas as tintas de forma rápida, não destrutiva e eficiente. O método se mostrou exato e robusto com respeito a escrita de diferentes indivíduos e capaz de identificar o tipo, a marca e o modelo de caneta em um caso forense.

The analysis of inks is performed to verify the occurrence of forgery in documents. Spectroscopic methods are attractive techniques for use in forensic document analysis as they, in most instances, preserve the integrity of the document. In this work, it is proposed a discrimination method of black pen inks of different types, brands and models for application in cursive handwriting. The visible reflectance spectra was obtained by the video spectral comparator VSC®6000 and discrimination analysis performed by partial least squares (PLS-DA). The method was validated with an independent test set and with a blind test. The bias in the results was corrected for the outlier identification. The PLS-DA models presented low root mean squared error of predictions (RMSEPs) and allowed a fast, non-destructive and an efficient discrimination of all pen inks evaluated. The method has proved to be accurate and robust regarding the handwriting of different individuals and capable of identifying the pen type, brand and pen model in a forensic case.

Foram preparados catalisadores híbridos a partir de um catalisador do tipo Ziegler-Natta heterogêneo (MgCl2.TiCl4) e de um metalocênico (CpTiCl3), afim de se obter catalisadores com diferentes tipos de centros ativos. Foi proposta a formação de um novo centro ativo (CpTi(iBu)Cl2) na face 100 do suporte de MgCl2. Estes catalisadores foram avaliados na síntese de polietileno de alta densidade (PEAD) e de polietileno linear de baixa densidade (PELBD), utilizando-se somente trietilalumínio (TEA) como cocatalisador. Foi verificada a influência da razão molar Al/Ti, temperatura e tempo de polimerização na produtividade dos catalisadores e nas propriedades dos polímeros obtidos. Os catalisadores mistos apresentaram atividade catalítica da ordem de 5,0 kgPol/g cat.h na polimerização de etileno e da ordem de 7,0 kgPol/g cat.h na copolimerização etileno-1-buteno.

Hybrid catalysts formed by a heterogeneous Ziegler-Natta catalyst (MgCl2.TiCl4) and a metallocene (CpTiCl3) were prepared in this work. The formation of a new catalytic species CpTi(iBu)Cl2 on the (100) MgCl2 face has been proposed. These catalyst systems were applied to synthesize high density polyethylene (HDPE) and linear low density polyethylene (LLDPE), using only triethyl aluminium (TEA) as a cocatalyst. The influence of Al/Ti molar ratio, temperature and time of polymerization on the catalyst activity and on the polymer properties were evaluated. The catalyst activities were about 5.0 kgPol/g cat.h for ethylene polymerization and 7.0 kgPol/g cat.h for ethylene-1-butene coplymerization.

Neste trabalho foram preparados catalisadores a partir da imobilização do precursor catalítico (nBuCp)2ZrCl2 em adutos de cloreto de magnésio (MgCl2.nEtOH). Observou-se que o conteúdo residual de etanol do suporte teve influência significativa no teor de metal fixado, o qual variou de 0,5 a 1,5% em peso de Zr/MgCl2, bem como na atividade do catalisador em homopolimerização de etileno. Dentro da faixa de temperatura de 25 a 75°C, o maior rendimento foi obtido com o catalisador preparado a 25°C. Com base nos resultados, foram sugeridas as reações, possíveis de ocorrer, durante a preparação do catalisador. Os polímeros foram avaliados quanto ao seu peso molecular e polidispersão.

This work describes the preparation of catalysts by the immobilization of bis(n-butylcyclopentadienyl)zirconium dichloride, (nBuCp)2ZrCl, on magnesium dichloride adducts, MgCl2.nEtOH. The metal content on the support, which varied from 0,5 to 1,5 wt.-% Zr/MgCl2 and the catalysts activity were dependent on the ethanol content. In the temperature immobilization range between 25 and 75°C, the highest Zr incorporation and polymerization yield were obtained with the catalyst prepared at 25°C. Based on the results obtained in this work, a series of reactions that may occur between the catalyst components during its preparation are proposed. The polyethylenes obtained were characterized by its molecular weight and polydispersivity.