15 research outputs found
Detection of counterfeit Durateston using Fourier transform infrared spectroscopy and partial least squares : discriminant analysis
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
Brazilian Federal District cocaine chemical profiling : mass balance approach and new adulterant routinely quantified (Aminopyrine)
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
Challenges in the Identification of New Thermolabile Psychoactive Substances: the 25I-NBOH case
The continuous emergence of NPS over the last years poses a series of novel challenges for
forensic analysts. Most of those new compounds are synthesized with minimal chemical
modifications to the structure of already known chemicals in order to avoid regulations. Some
of these new compounds may undergo chemical changes during analysis leading to
misidentification and detrimental legal consequences. GC–MS is one of the most widely used
analytical techniques employed by forensic laboratories all over the world for drug analysis.
Nevertheless, thermolabile NPS, such as 25I-NBOH can generate artefacts in the traditional GCMS
analysis. In this paper, we describe the fragmentation mechanism of the 25I-NBOH into a
major peak corresponding to 2C-I and a minor one corresponding to the associated orthophenolic
benzyl ether (o-PBE), which exact identity is directly linked with the solvent used for
the analysis. Also, a series of method adjustments is displayed, encompassing variation on the
injector temperature, split ratio and flow ratio, although with no success to prevent 25I-NBOH
thermo degradation in the GC injector. Furthermore, differential scanning calorimetry and
thermogravimetric analysis demonstrated that 25I-NBOH´s thermal stability is due to a smaller
temperature window between fusion and decomposition points. Finally, we perform
derivatization experiments and demonstrate how to overcome 25I-NBOH degradation in the
GC/MS analysis
The Performance Evaluation of Hybrid Ziegler-Natta/Metallocene Catalysts in Homo- and Copolymerization of Ethylene
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/gcat.h na polimerização de etileno e da ordem de 7,0 kgPol/gcat.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/gcat.h for ethylene polymerization and 7.0 kgPol/gcat.h for ethylene-1-butene coplymerization
The Performance Evaluation of Hybrid Ziegler-Natta/Metallocene Catalysts in Homo- and Copolymerization of Ethylene
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/gcat.h na polimerização de etileno e da ordem de 7,0 kgPol/gcat.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/gcat.h for ethylene polymerization and 7.0 kgPol/gcat.h for ethylene-1-butene coplymerization
Raman hyperspectral imaging in conjunction with independent component analysis as a forensic tool for explosive analysis: the case of an ATM explosion
In this work, Raman hyperspectral imaging, in conjunction with independent component analysis, was employed as an analytical methodology to detect an ammonium nitrate fuel oil (ANFO) explosive in banknotes after an ATM explosion experiment. The proposed methodology allows for the identification of the ANFO explosive without sample preparation or destroying the sample, at quantities as small as 70 μg cm−2. The explosive was identified following ICA data decomposition by the characteristic nitrate band at 1044 cm−1. The use of Raman hyperspectral imaging and independent component analysis shows great potential for identifying forensic samples by providing chemical and spatial information.174628632CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQCOORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPESFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPSem informação573672/2008-308/57805-
Bis(n-butylcyclopentadienyl)zirconium dichloride ((nBuCp)2ZrCl2) immobilization on magnesium dichloride adducts (MgCl2.nEtOH) and its performance in ethylene homopolymerization
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
Bis(n-butylcyclopentadienyl)zirconium dichloride ((nBuCp)2ZrCl2) immobilization on magnesium dichloride adducts (MgCl2.nEtOH) and its performance in ethylene homopolymerization
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
Direct detection of triacetone triperoxide (TATP) in real banknotes from ATM explosion by EASI‐MS
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)In Brazil, automated teller machine (ATM) has become a major target of theft incursions toward explosion. Efficient analysis of explosives residues on suspect banknotes is a serious issue in forensic labs, and guide to the crime solution. Easy ambient sonic-spray ionization mass spectrometry (EASI-MS) is shown to be a simple and selective screening tool to identify peroxide explosives on real banknotes collected from ATM explosion. Analyses were carried out directly on the banknotes surfaces without any sample preparation, identifying triacetone triperoxide (TATP) and diacetone diperoxide (DADP). Homemade EASI source was coupled to ultrahigh-resolution and ultrahigh accuracy FT-ICR MS and revealed the ion of m/z 245 correspondent to sodiated TATP [C9H18O6Na](+) and the ion of m/z 171 related to sodiated DADP [C6H12O4Na](+), ions that is the sodiated DADP and the ions of m/z 173 and 189 related to [C6H14O4Na](+) and [C6H14O4K](+), respectively, which are associated to chemical markers of TATP domestic route synthesis. EASI source coupled to a single quadrupole mass spectrometer provides an intelligent and simple way to identify the explosives TATP, DADP and its domestic synthesis markers.In Brazil, automated teller machine (ATM) has become a major target of theft incursions toward explosion. Efficient analysis of explosives residues on suspect banknotes is a serious issue in forensic labs, and guide to the crime solution. Easy ambient son424370375CAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)23038.006844/2014–4