Among stimulant drugs, cocaine deserves attention due to its high rates of seizures worldwide. This work presents the synthesis and characterization of hybrid molecularly imprinted polymers (MIPs) for use in preparing biological samples using a homemade microextraction in a packed sorbent device to extract cocaine. The MIPs synthesized using caffeine and cocaine as templates have been compared. Caffeine was used due to its low value and be easier to obtain than cocaine. Additionally, restricted access molecularly imprinted polymers (RAMIPs) were also produced for comparison purposes. The polymeric materials were characterized using scanning electron microscopy, textural analysis, Fourier transform infrared spectroscopy, and cross polarization/ magic angle spinning 13C nuclear magnetic resonance. The method optimization was performed using linear ion trap mass spectrometer to evaluate the effects of sample pH, type of eluent, washing solvent, adsorption cycles, and eluent volume. In the optimized method, RAMIPs indicated better cocaine extraction compared to MIPs. The quantitative study demonstrated that the developed method was able to accurately quantify cocaine in urine samples with values close to actual concentrations. drugs worldwide (MIPs Additionally (RAMIPs purposes microscopy analysis spectroscopy polarization C resonance pH solvent cycles volume concentrations

This study searched for a new pre-formulation based on the natural compound from the class of the avermectins, named abamectin (ABA), in order to improve its action against Aedes aegypti larvae by complexation with β-cyclodextrin (βCD). Concerning the low aqueous solubility of ABA, even in the presence of βCD, it was also invoked the strategy of working with hydrophobic nanoprecipitates (HNPs). For these purposes, molecular and supramolecular characterizations of 1:1 ABA/βCD complex and evaluation of its toxicity against A. aegypti larvae were performed. In the physical-chemistry characterizations, changes in the infrared spectra and thermal profiles in relation to precursors confirmed the occurrence of interactions between ABA and βCD in solid state. Nuclear magnetic resonance (NMR) data suggest the inclusion of ABA in βCD via benzofuran ring. Isothermal titration calorimetry (ITC) experiments allowed to verify the formation of complex with a 1:1 stoichiometry, which was entropy driven. The dynamic light scattering and zeta potential data from inclusion compounds demonstrated changes in the size of the ABA/βCD HNP if compared with the ABA HNP. Finally, the results for biological assays demonstrate that the strategy to prepare the inclusion compound led to an increase in the larvicidal activity in relation to free ABA.

Um método rápido por cromatografia líquida foi desenvolvido para a determinação simultânea de omeprazol (OMZ), 5-hidroxiomeprazol (5-HOMZ) e omeprazol sulfona (OMZ SUL) em meio de cultura líquido, para aplicação em estudos de biotransformação empregando fungos fitopatogênicos e endofíticos. A separação foi realizada empregando uma coluna monolítica Chromolith Fast gradient RP 18 com a fase móvel constituída por ácido trifluoroacético (TFA) 0,15% (v/v) em água (solvente A) e TFA 0,15% (v/v) em acetonitrila (solvente B). Foi empregado um gradiente linear de 5 a 90% de B em 1 minuto, vazão de 1,0 mL min-1, temperatura de 30 ºC e detecção em 220 nm. A extração líquido-líquido foi empregada na preparação das amostras, com recuperações na faixa de 62,3-76,6% para todos os analitos. O método foi linear na faixa de 0,2-10,0 µg mL-1 (r ≥ 0,995). Os valores de precisão e exatidão intra- e inter-dias (coeficiente de variação e erro relativo) foram inferiores a 15% para todos os analitos. O método validado foi utilizado para avaliar a biotransformação do OMZ em seus principais metabólitos humanos pelos fungos selecionados. Em geral, os fungos fitopatogênicos foram mais eficientes para biotransformar o OMZ. A reação de sulfonação foi mais prevalente em todos os fungos estudados

A fast liquid chromatography method was developed and validated for the simultaneous determination of omeprazole (OMZ), 5-hydroxyomeprazole (5-HOMZ) and omeprazole sulphone (OMZ SUL) in liquid culture medium for application in biotransformation studies employing phytopathogenic and endophytic fungi. The separation was achieved using a monolithic Chromolith Fast gradient RP 18 endcapped column, using a mobile phase consisting of 0.15% (v/v) trifluoroacetid acid (TFA) in water (solvent A) and 0.15% (v/v) TFA in acetonitrile (solvent B), under linear gradient of 5 to 90% of B in 1 min, flow rate of 1.0 mL min-1, temperature at 30 ºC and detection at 220 nm. Sample preparation was performed by liquid-liquid extraction, with recoveries in the range of 62.3 to 76.6% for all analytes. The method was linear in the range of 0.2 to 10.0 µg mL-1 (r ≥ 0.995). The values for intra- and inter-day precision (% coefficient of variation) and accuracy (% relative error) were < 15% for all analytes. The validated method was used to evaluate OMZ biotransformation to their mammalian metabolites by selected fungi. In general, the phytopathogenic fungi studied were more efficient to biotransform OMZ. The sulfonation reaction was more prevalent for all studied fungi.

O tirosol é provavelmente uma molécula sinalizadora em fungos endofíticos. A análise do tirosol em cultura líquida Czapek de fungo endofítico foi realizada através de cromatografia líquida de alta eficiência acoplada a detector por arranjo de diodos. As análises foram obtidas em sistema de fase móvel utilizando gradiente, modo linear, iniciando em acetonitrila/água (1:9 v/v) e terminando em acetonitrila 100% em 30 minutos com vazão de 1 mL min-1. Coluna analítica ZORBAX® ODS (250 × 4,6 mm, 5 μm) à 25 ºC foi utilizada. Extração líquido-líquido de 0,5 mL do meio (pH 7,0) com acetato de etila e injeção de 20 μL após concentração do solvente sob ar comprimido originou bons resultados. Os parâmetros validados foram: linearidade 0,0125-5,0 μg mL-1 (r = 0,9967), limite de quantificação 0,0125 μg mL-1 obtidos pela média das análises; %CV (precisão) e %E (exatidão) com valores abaixo de 15% e recuperação de cerca de 80%. Além disso, o método desenvolvido apresentou valores de validação satisfatórios demonstrando eficiência na análise do tirosol em meio líquido Czapek.

Tyrosol is a possible quorum sensing molecule in endophytic fungi. High-performance liquid chromatography (HPLC) coupled with diode array detector (DAD) was used for the analysis of tyrosol in liquid Czapek fungal cultures. The optimized conditions were gradient mobile phase, in linear mode, consisting initially of acetonitrile/water (1:9 v/v) and increasing up to acetonitrile (100%) in 30 minutes at a flow rate of 1 mL min-1. The column used was a ZORBAX® ODS (250 × 4.6 mm, 5 μm) at 25 ºC. Liquid-liquid extraction of 0.5 mL medium (pH 7.0) with ethyl acetate and injection of 20 μL after solvent evaporation under air flow gave good results. Some validation parameters obtained were: linearity 0.0125-5.0 μg mL-1 medium (r = 0.9967), quantification limit of 0.0125 μg mL-1 medium, %CV (precision) and %E (accuracy) bellow 15% and recovery around 80%. Therefore, the developed method presented satisfactory validation parameters and it was efficient for the analysis of tyrosol in Czapek medium.