Determinação do coeficiente de atividade na diluição infinita em sistemas etanol-água-sal por microextração em fase sólida-gc-fid

A new method using the headspace solid phase microextraction (HS-SPME) technique was used to evaluate the infinite dilute activity coefficient (γ1∞) in an alcohol/water/salt system. The studied systems were ethanol and water with NaCl and NH4Cl at salt concentrations of 5, 10, 15, and 30% m/v and temperatures of 303.15 and 313.15 K. The method was used to investigate the salt effect on vapor/liquid equilibrium in an ethanol/water system, yielding satisfactory results. The study focused on the rich side in ethanol. The data were compared with the literature infinite dilution data determined by other methods such as differential ebulliometry (EBUL), differential static cell equilibrium (STAT), and gas-liquid chromatography with no gas phase correction (GC). In this study, NaCl showed better separation rates than NH4Cl.

Avaliação da eficiência de degradação de hidrocarbonetos aromáticos por bactérias provinientes de estação de tratamento de efluente de refinaria de petróleo

Three bacterial strains were isolated from the activated sludge system of petroleum refinery wastewater, identified by partial sequencing of 16S rDNA, and classified as Acinetobacter genomospecies 3, Bacillus pumilus, and Bacillus flexus. The degradation efficiency of aromatic hydrocarbons was evaluated by gas chromatography with a flame ionization detector. In a mineral medium containing anthracene and phenanthrene and the consortium of microorganisms, the removal efficiency was 96% and 99%, respectively, after 30 days. The good rate of hydrocarbon degradation proves the operational efficiency of the microbial consortium in treating effluents containing these compounds.

Cromatografia gasosa quiral na resolução de enantiômeros envolvidos em flavours de frutas

This work addresses the use of chiral gas chromatography in resolving optically active stereoisomers and racemates found in fruit flavours. It presents the types of chiral selectors applied to terpene-derived metal coordination compounds, polysiloxane-linked α-amino acid and mixed chiral stationary phases, and focuses on derivatized cyclodextrins, the most popular chiral stationary phases presently used in chromatographic analysis. Knowledge about the techniques involved in chiral recognition and enantiomer identification in the fruit flavour field is given along with examples from the latest studies.

Separação e determinação quantitativa dos alcanos lineares e dos cíclicos/ramificados em petróleos brasileiros por aduto de ureia e cromatografia gasosa: um estudo de caso revisitado

A complete analysis of oils and their fractions allows correlations to be defined between their composition and derivatives or related geological materials. This work focused on optimization and implementation of a method for separation and quantification of n-alkanes in Brazilian oil samples by urea adduction and GC-FID techniques. Ten samples with different ºAPI were analyzed in triplicate to quantify individual n-alkanes and cyclic/branched alkane fraction. For individual quantification of n-alkanes, internal standardization with deuterated n-tetracosane was used. The use of urea adduction for the separation and quantification of n-alkanes was highly effective, with recovery values of above 80%.

VOLATILE COMPONENTS FROM GALLS INDUCED BY Baccharopelma dracunculifoliae(Hemiptera: Psyllidae) ON LEAVES OF Baccharis dracunculifolia(Asteraceae)

The volatile components of the galls induced by the insect Baccharopelma dracunculifoliae (Hemiptera: Psyllidae) on leaves of Baccharis dracunculifolia (Asteraceae) were analyzed by gas chromatography-mass spectrometry (GC-MS) and gas chromatographyflame- ionisation detection (GC-FID), and then comparison with volatile oil samples from healthy leaves collected in the vicinity. The galls produced around 3.5% of the total organic volatiles whereas healthy leaves rendered an average yield of 0.6%. The observed higher proportions of germacrene D, bicyclogermacrene, limonene, and β-pinene in the galls suggest that all these compounds are important targets in the search for natural enemies of this Psyllid. Moreover, higher relative percentages of (E)-nerolidol and spathulenol were found in healthy leaves.

CONSTRUÇÃO DE UM REATOR DE PLASMA DESCARGA CORONA PARA ELIMINAÇÃO DE COMPOSTOS ORGÂNICOS VOLÁTEIS

The impacts derived from the emission of volatile organic compounds (VOC) into the atmosphere can have harmful consequences for human health and the environment. In this regard, the present paper proposes the construction of a low-cost cold plasma reactor for the treatment of these compounds. Tests with the prototype were performed to confirm the efficiency for BTEX (benzene, toluene and xylene) samples. Degradation efficiency was confirmed by the gas chromatography method.

ENZYMATIC RESOLUTION OF ANTIDEPRESSANT DRUG PRECURSORS IN AN UNDERGRADUATE LABORATORY

The use of biocatalysts in synthetic chemistry is a conventional methodology for preparing enantiomerically enriched compounds. Despite this fact, the number of experiments in chemical teaching laboratories that demonstrate the potential of enzymes in synthetic organic chemistry is limited. We describe a laboratory experiment in which students synthesized a chiral secondary alcohol that can be used in the preparation of antidepressant drugs. This experiment was conducted by individual students as part of a Drug Synthesis course held at the Pharmacy Faculty, Lisbon University. This laboratory experiment requires six laboratory periods, each lasting four hours. During the first four laboratory periods, students synthesized and characterized a racemic ester using nuclear magnetic resonance spectroscopy and gas chromatography. During the last two laboratory periods, they performed enzymatic hydrolysis resolution of the racemic ester using Candida antarctica lipase B to yield enantiomerically enriched secondary alcohol. Students successfully prepared the racemic ester with a 70%-81% overall yield in three steps. The enzymatic hydrolysis afforded (R)- secondary alcohol with good enantioselectivity (90%-95%) and reasonable yields (10%-19%). In these experiments, students were exposed to theoretical and practical concepts of aromatic acylation, ketone reduction, esterification, and enzymatic hydrolysis.

HS-SPME-GC-MS ANALYSIS OF VOLATILE AND SEMI-VOLATILE COMPOUNDS FROM DRIED LEAVES OF Mikania glomerata Sprengel

This paper reports on the identification of volatile and semi-volatile compounds and a comparison of the chromatographic profiles obtained by Headspace Solid-Phase Microextraction/Gas Chromatography with Mass Spectrometry detection (HS-SPME-GC-MS) of dried leaves of Mikania glomerata Sprengel (Asteraceae), also known as 'guaco.' Three different types of commercial SPME fibers were tested: polydimethylsiloxane (PDMS), polydimethylsiloxane/divinylbenzene (PDMS/DVB) and polyacrylate (PA). Fifty-nine compounds were fully identified by HS-SPME-HRGC-MS, including coumarin, a marker for the quality control of guaco-based phytomedicines; most of the other identified compounds were mono- and sesquiterpenes. PA fibers performed better in the analysis of coumarin, while PDMS-DVB proved to be the best choice for a general and non-selective analysis of volatile and semi-volatile guaco-based compounds. The SPME method is faster and requires a smaller sample than conventional hydrodistillation of essential oils, providing a general overview of the volatile and semi-volatile compounds of M. glomerata.

ANÁLISE COMPARATIVA DO CONTEÚDO EM ESTEROIDES LIVRES DE DIFERENTES ÓLEOS, GORDURAS E BIODIESEIS POR CROMATOGRAFIA GASOSA

In this study, the percentage content of free steroid in oils, fats and biodiesel was analyzed. For this, the saponification reaction on a microscale was used, and this procedure for extraction of unsaponifiable fraction was studied in several experimental steps. After the process of saponification, the unsaponifiable fraction was analyzed by gas chromatography with flame ionization detector, where all steroids present in each oil, fat and biodiesel were identified and their contents determined and compared to their respective biodiesel. A reduction in unsaponifiable fraction of each oil and fat and its biodiesel was noted, as well as a reduction in the content of free steroids. The results showed that, compared to the sedimentation problem of steroids in biodiesel, some raw materials, such as chicken fat and babassu oil may be promising because they have low content and high reduction percentages of steroids when converted to biodiesel.

EVALUATION OF A BUFFERED SOLID PHASE DISPERSION PROCEDURE ADAPTED FOR PESTICIDE ANALYSES IN THE SOIL MATRIX

An evaluation of the pesticides extracted from the soil matrix was conducted using a citrate-buffered solid phase dispersion sample preparation method (QuEChERS). The identification and quantitation of pesticide compounds was performed using gas chromatography-mass spectrometry. Because of the occurrence of the matrix effect in 87% of the analyzed pesticides, the quantification was performed using matrix-matched calibration. The method's quantification limits were between 0.01 and 0.5 mg kg-1. Repeatability and intermediate precision, expressed as a relative standard deviation percentage, were less than 20%. The recoveries in general ranged between 62% and 99%, with a relative standard deviation < 20%. All the responses were linear, with a correlation coefficient (r) ≥0.99.

PYROLIGNEOUS LIQUOR PRODUCED FROM ACACIA MEARNSII DE WILD WOOD UNDER CONTROLLED CONDITIONS AS A RENEWABLE SOURCE OF CHEMICALS

Acacia mearnsii de Wild (black wattle) is one of the most important trees planted in Southern Brazil for tannin extraction and charcoal production. The pyrolysis of the black wattle wood used for obtaining charcoal is performed in brick ovens, with the gas fraction being sent directly into the environment. The present study examines the condensable compounds present in the liquor produced from black wattle wood at different thermal degradation conditions, using gas chromatography coupled with mass spectrometry (GC/MS). Branches of black wattle were thermally degraded at controlled ambient and temperature conditions. Overall, a higher variety of compounds were obtained under atmospheric air pressure than under synthetic air pressure. Most of the tentatively identified compounds, such as carboxylic acids, phenols, aldehydes, and low molecular mass lignin fragments, such as guayacol, syringol, and eugenol, were products of lignin thermoconversion. Substituted aromatic compounds, such as vanillin, ethyl vanillin, and 2-methoxy-4-propeny-phenol, were also identified. At temperatures above 200 ºC, furan, 2-acetylfuran, methyl-2-furoate, and furfural, amongst others, were identified as polysaccharide derivatives from cellulose and hemicellulose depolymerization. This study evidences the need for adequate management of the condensable by-products of charcoal production, both for economic reasons and for controlling their potential environmental impact.

CONSTITUENTS OF ESSENTIAL OIL AND HYDROLATE OF LEAVES OF Campomanesia viatoris LANDRUM

The chemical composition of the essential oil and hydrolates of Campomanesia viatoris Landrum were investigated by gas chromatography/mass spectrometry (GC/MS) and a GC flame ionization detector (GC-FID). The major constituents were tasmanone (70.50, essential oil; 74.73%, hydrolate), flavesone (12.77, essential oil; 12.24%, hydrolate) and agglomerone (6.79, essential oil; 10.84%, hydrolate). Tasmonone was isolated and its structure was characterized by spectrometric analysis, specifically 1D and 2D nuclear magnetic resonance (NMR) and mass spectrometry (MS). These findings supports the quimiotaxonomic relationship with Campomanesia and Eucalyptus genera.

SEASONAL CHEMICAL COMPOSITIONS OF THE ESSENTIAL OILS OF TWOEugenia SPECIES AND THEIR ACARICIDAL PROPERTIES

The leaf essential oils of Eugenia lutescens Cambess andEugenia langsdorffii O. Berg, collected in the rainy (RS) and dry seasons (DS), were extracted by hydrodistillation and then characterized by a gas chromatography-flame ionization detector and a gas chromatography-mass spectrometer. The potential acaricidal activity and oviposition deterrence of these oils were evaluated against Tetranychus urticae . The oil yields were higher in the RS for E. lutescens, while those forE. langsdorffii were higher in the DS. α-Pinene and β-pinene were determined to be the major constituents of the oils fromE. lutescens, while bicyclogermacrene, spathulenol, and β-caryophyllene predominated in E. langsdorffii . Seasonal variations in the oils were primarily related to chemical diversity, and E. lutescens was more affected than was E. langsdorffii . The E. langsdorffii oil collected in the DS was most toxic to the spider mite, while the oils of E. lutescens and E. langsdorffii collected in the RS drastically reduced its egg quantities. This study successfully determined the periods of greater oil production and acaricidal activity.

FASES ESTACIONÁRIAS DE LÍQUIDOS IÔNICOS EM CROMATOGRAFIA GASOSA: FUNDAMENTOS, AVANÇOS RECENTES E PERSPECTIVAS

Since their original discovery in 1914, ionic liquids (IL) have been widely examined and explored in chemistry due to their unique physical and chemical properties. Ionic liquids are collectively known as organic salts and have melting points of 100 °C or under. The molten salts most employed in analytical chemistry, including gas chromatography (GC), consist of an organic cation paired with an organic or inorganic anion. This class of materials exhibits negligible vapor pressure and may have their properties (e.g.thermal stability and selectivity) structurally tuned by imparting different moieties to the cation/anion. Currently, there are an estimated 1018possible combinations of IL. In this context, the prospection of highly selective IL-based stationary phases for gas-liquid chromatography has enabled high peak capacity and efficient separations of many critical pairs in complex samples. In this review, we present and discuss fundamental characteristics of ionic liquids and introduce important solvation models for gas-liquid systems. In addition, recent advances and applications of IL in conventional and multidimensional gas chromatography are outlined.

2-(4-IODO-2,5-DIMETOXIFENIL)-N-[(2-METOXIFENIL)METIL]ETAMINA OU 25I-NBOME: CARACTERIZAÇÃO QUÍMICA DE UMA DESIGNER DRUG

Drug trafficking and the introduction of new drugs onto the illicit market are one of the main challenges of the forensic community. In this study, the chemical profile of a new designer drug, 2-(4-iodine-2,5-dimethoxyphenyl)-n-[(2-methoxyphenyl)methyl]etamine or 25I-NBOMe was explored using thin layer chromatography (TLC), ultraviolet-visible spectrophotometry (UV-Vis), attenuated total reflection with Fourier transform infrared spectroscopy(ATR-FTIR), gas chromatography mass spectrometry (GC-MS) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS). First, the TLC technique was effective for identifying spots related to 25C-, 25B- and 25I-NBOMe compounds, all with the same retention factor, Rf ≈ 0.50. No spot was detected for 2,5-dimethoxy-4-bromoamphetamine, 2,5-Dimethoxy-4-chloroamphetamine or lysergic acid diethylamide compounds. ATR-FTIR preserved the physical-chemical properties of the material, whereas GC-MS and ESI-MS showed better analytical selectivity. ESI(+)FT-ICR MS was used to identify the exact mass (m/z428.1706 for the [M + H]+ ion), molecular formula (M = C18H22INO3), degree of unsaturation (DBE = 8) and the chemical structure (from collision induced dissociation, CID, experiments) of the 25I-NBOMe compound. Furthermore, the ATR-FTIR and CID results suggested the presence of isomers, where a second structure is proposed as an isomer of the 25I-NBOMe molecule.