J.M.F. Nogueira

Characterization of the aroma profile of Madeira wine by sorptive extraction techniques

The characterization of the aroma profile of 33 samples of Madeira wine from five monovarieties (Sercial, Verdelho, Boal, Malvasia and Tinta Negra Mole) having different type and categories is presented, using solid phase microextraction and stir bar sorptive extraction techniques (SPME and SBSE) followed by capillary gas chromatography and mass spectrometry detection (GC-MS). Headspace SPME/GC-MS provided effectiveness to identify the major constituents of the aroma profile of Madeira wine, where no remarkable differences occur among the samples studied. The volatile compounds are mainly constituted by ethyl octanoate (11.3-256.9μgL-1), ethyl decanoate (21.5-210.5μgL-1), ethyl decenoate (0.1-112.8μgL-1), diethyl succinate (0.9-65.6μgL-1), ethyl dodecanoate (1.2-6.5μgL-1), ethyl nonanoate (0.6-5.2μgL-1), ethyl hexanoate (0.2-3.7μgL-1) and isoamyl octanoate (0-2.2μgL-1). C13 norisoprenoids such as vitispirane (0.9-7.0μgL-1) and 1,1,6-trimethyl 1,2-dihydro naphthalene (0.7-12.5μgL-1), as well as phenyl ethanol (0-8.1μgL-1), were also found in Madeira wine samples. The powerful capabilities of SBSE followed thermal desorption and GC-MS analysis allowed higher ability for profiling traces and ultra traces of compounds in Madeira wine samples, including esters (80.7-89.7%), carboxylic acids (1.6-4.2%), alcohols (3.5-8.2%), aldehydes (0.9-3.7%), pyrans (0.2-1.7%), lactones (<3%), monoterpenes (0.1-1.4%), sesquiterpenes (0.1-0.8%) and C13 norisoprenoids (1.7-6.5%), which some of them play a remarkable impact on the aroma complexity. C13 norisoprenoids in particular, seem to play an important role on Madeira wine bouquet since presenting very low sensorial threshold limits. Excellent correlation between Madeira wine ageing and the abundance of cis-oak lactone was attained showing to be an important chemical descriptor to characterize reserves and Vintages as well as a contributor to wine flavour. The differentiation between reserves, dry/medium dry and sweet/medium sweet young wines could be well established by means of chemometric analysis, using particular aroma compounds such as diethyl succinate, cis-oak lactone and ethyl octanoate as discriminating variables.

Waste-derived activated carbons for removal of ibuprofen from solution: Role of surface chemistry and pore structure

The removal of a widespread used drug (i.e., ibuprofen) from water was investigated using high valuable carbon adsorbents obtained from chemical and physical activation of a bioresource (cork) and a municipal waste (plastic). The waste-derived carbons outperformed the adsorption capacity of commercial carbonaceous adsorbents due to their adequate features for the removal of the targeted compound. Regarding the adsorption mechanism, the results obtained point out that ibuprofen retention is favored in activated carbons with basic surface properties. On the other hand, the textural features also play an important role; the presence of a transport pores network (i.e., mesopores) is crucial to ensure the accessibility to the inner porosity, and the microporosity must be large enough to accommodate the ibuprofen molecule. Specifically, adsorbents with a large fraction of ultramicropores (pore widths <0.7 nm) are not adequate to effectively remove ibuprofen.

Advances in stir bar sorptive extraction for the determination of acidic pharmaceuticals in environmental water matrices: Comparison between polyurethane and polydimethylsiloxane polymeric phases

Stir bar sorptive extraction with polyurethane (PU) and polydimethylsiloxane (PDMS) polymeric phases followed by high-performance liquid chromatography with diode array detection [SBSE(PU or PDMS)/HPLC-DAD] was studied for the determination of six acidic pharmaceuticals [o-acetylsalicylic acid (ACA), ibuprofen (IBU), diclofenac sodium (DIC), naproxen (NAP), mefenamic acid (MEF) and gemfibrozil (GEM)], selected as non-steroidal acidic anti-inflammatory drugs and lipid regulators model compounds in environmental water matrices. The main parameters affecting the efficiency of the proposed methodology are fully discussed. Assays performed on 25 mL of water samples spiked at the 10 microg L(-1) level under optimized experimental conditions, yielded recoveries ranging from 45.3+/-9.0% (ACA) to 90.6+/-7.2% (IBU) by SBSE(PU) and 9.8+/-1.6% (NAP) to 73.4+/-5.0% (GEM) by SBSE(PDMS), where the former polymeric phase presented a better affinity to extract these target analytes from water matrices at the trace level. The methodology showed also excellent linear dynamic ranges for the six acidic pharmaceuticals studied, with correlation coefficients higher than 0.9976, limits of detection and quantification between 0.40-1.7 microg L(-1) and 1.5-5.8 microg L(-1), respectively, and suitable precision (RSD <15%). Moreover, the developed methodology was applied for the determination of these target analytes in several environmental matrices, including river, sea and wastewater samples, having achieved good performance and moderate matrix effects. In short, the PU foams demonstrated to be an excellent alternative for the enrichment of the more polar metabolites from water matrices by SBSE, overcoming the limitations of the conventional PDMS phase.

Plant extracts with anti-inflammatory properties-A new approach for characterization of their bioactive compounds and establishment of structure-antioxidant activity relationships

Geranium robertianum L. (Geraniacea) and Uncaria tomentosa (Willd.) DC. (Rubiaceae) plant extracts, frequently used in traditional medicine for treatment of inflammatory and cancer diseases, were studied to identify potential bioactive compounds that may justify their therapeutic use and their underlying mechanisms of action. Since some of the pharmacological properties of these plant extracts may be linked to their antioxidant potential, the antioxidant activity, in relation to free radical scavenging, was measured by the ABTS/HRP and DPPH() assays, presenting U. tomentosa the higher activity. The antioxidant activity was also evaluated by scavenging of HOCl, the major strong oxidant produced by neutrophils and a potent pro-inflammatory agent. U. tomentosa was found to be a better protector against HOCl, which may justify its effectiveness against inflammatory diseases. SPE/LC-DAD was used for separation/purification purposes and ESI-MS/MS for identification/characterization of the major non-volatile components, mainly flavonoids and phenolic acids. The ESI-MS/MS methodology proposed can be used as a model procedure for identification/characterization of unknowns without the prerequisite for standard compounds analysis. The ESI-MS/MS data obtained were consistent with the antioxidant activity results and structure-activity relationships for the compounds identified were discussed.

Novel sorption-based methodologies for static microextraction analysis: A review on SBSE and related techniques.

Stir bar sorptive extraction (SBSE) became a well-established analytical technique in the last years, for which hundreds of applications in almost all types of scientific fields can be found in the literature. In spite of the great enrichment capacity and outstanding performance to operate at the ultra-trace level, this remarkable static sorption-based method is already not quite effective for some complex systems, in particular to monitor the large group of polar organic compounds. This review aims to cover the state-of-the-art in SBSE, as well as supplying a discussion of the analytical potential of the novel adsorptive microextraction techniques, as complementary enrichment approaches, by explaining the main principles and providing technical know-how for the beginners.

Chemical composition and bioactivity of different oregano (Origanum vulgare) extracts and essential oil

BACKGROUND There is a growing interest in industry to replace synthetic chemicals by natural products with bioactive properties. Aromatic plants are excellent sources of bioactive compounds that can be extracted using several processes. As far as oregano is concerned, studies are lacking addressing the effect of extraction processes in bioactivity of extracts. This study aimed to characterise the in vitro antioxidant and antibacterial properties of oregano (Origanum vulgare) essential oil and extracts (in hot and cold water, and ethanol), and the chemical composition of its essential oil. RESULTS The major components of oregano essential oil were carvacrol, β-fenchyl alcohol, thymol, and γ-terpinene. Hot water extract had the strongest antioxidant properties and the highest phenolic content. All extracts were ineffective in inhibiting the growth of the seven tested bacteria. In contrast, the essential oil inhibited the growth of all bacteria, causing greater reductions on both Listeria strains (L. monocytogenes and L. innocua). CONCLUSION O. vulgare extracts and essential oil from Portuguese origin are strong candidates to replace synthetic chemicals used by the industry.

New approach on trace analysis of triclosan in personal care products, biological and environmental matrices

Stir bar sorptive extraction and liquid desorption followed by high performance liquid chromatography with diode array detection (SBSE-LD-LC-DAD) is proposed for the determination of triclosan in personal care products, biological and environmental matrices, which is included in the priority lists, set by several international regulatory organizations. Instrumental conditions and experimental parameters that affecting SBSE-LD efficiency are fully discussed. Throughout systematic assays on 25 mL water samples spiked at the 10.0 microg L(-1) level, it had been established that stir bars coated with 126 microL of polydimethylsiloxane, an equilibrium time of 1h (1000 rpm) and acetonitrile under sonification (60 min) as back-extraction solvent, allowed the best analytical performance to determine triclosan in water matrices. From the data obtained, good recovery and remarkable repeatability were attained, providing experimental average yields (78.5+/-2.2%), although slightly lower than the theoretical equilibrium (99.7%) described by the octanol-water partition coefficients (K(PDMS/W)0.9992) from 0.4 to 108.0 microg L(-1). The application of the present method to determine triclosan in real matrices such as commercial toothpaste, saliva and urban wastewater samples, allowed appropriate selectivity, high sensitivity and accuracy using the standard addition methodology. The proposed method showed to be feasible and sensitive with a low-sample volume requirement to monitor triclosan in personal care products, biological and environmental matrices at the trace level, in compliance with international regulatory directives.

Quantification approach for assessment of sparkling wine volatiles from different soils, ripening stages, and varieties by stir bar sorptive extraction with liquid desorption.

Stir bar sorptive extraction with liquid desorption followed by large volume injection coupled to gas chromatography-quadrupole mass spectrometry (SBSE-LD/LVI-GC-qMS) was applied for the quantification of varietal and fermentative volatiles in sparkling wines. The analytical data were performed by using suitable standards of monoterpene hydrocarbons (alpha-pinene), monoterpenols (linalool), sesquiterpenoids (E,E-farnesol, Z-nerolidol, and guaiazulene), C(13) norisoprenoids (beta-ionone), aliphatic and aromatic alcohols (hexanol and 2-phenylethanol), and esters (hexyl acetate and ethyl decanoate) as model compounds. The wine volatiles were quantified using the structurally related standards. The methodology showed good linearity over the concentration range tested, with correlation coefficients ranging from 0.950 to 0.997, and a reproducibility of 9-18%. The SBSE-LD/LVI-GC-qMS methodology allowed, in a single run, the quantification of 71 wine volatiles that can be quantified accurately at levels lower than their respective olfactory thresholds. This methodology was used for assessment of sparkling wine volatiles from different soils, ripening stages, and varieties. The variety and soil influenced significantly the volatile composition of sparkling wines; lower effect was observed for the ripening stage of grapes picked up one week before or after the maturity state.

Adsorptive micro-extraction techniques—Novel analytical tools for trace levels of polar solutes in aqueous media

A novel enrichment technique, adsorptive μ-extraction (AμE), is proposed for trace analysis of polar solutes in aqueous media. The preparation, stability tests and development of the analytical devices using two geometrical configurations, i.e. bar adsorptive μ-extraction (BAμE) and multi-spheres adsorptive μ-extraction (MSAμE) is fully discussed. From the several sorbent materials tested, activated carbons and polystyrene divinylbenzene phases demonstrated the best stability, robustness and to be the most suitable for analytical purposes. The application of both BAμE and MSAμE devices proved remarkable performance for the determination of trace levels of polar solutes and metabolites (e.g. pesticides, disinfection by-products, drugs of abuse and pharmaceuticals) in water matrices and biological fluids. By comparing AμE techniques with stir bar sorptive extraction based on polydimethylsiloxane phase, great effectiveness is attained overcoming the limitations of the latter enrichment approach regarding the more polar solutes. Furthermore, convenient sensitivity and selectivity is reached through AμE techniques, since the great advantage of this new analytical technology is the possibility to choose the most suitable sorbent to each particular type of application. The enrichment techniques proposed are cost-effective, easy to prepare and work-up, demonstrating robustness and to be a remarkable analytical tool for trace analysis of priority solutes in areas of recognized importance such as environment, forensic and other related life sciences.

Considerations on ultra trace analysis of carbamates in water samples

A new routine method for the ultra trace analysis of carbamates in water samples is presented, using solid-phase extraction followed by high-performance liquid chromatography coupled to atmospheric pressure electrospray ionisation mass spectrometry (SPE-LC-ESI-MS). Instrumental conditions of LC-ESI-MS in the selected ion monitoring (SIM) mode, showed excellent linear response for the six N-methyl carbamates studied (aldicarb, carbaryl, carbofuran, methomyl, oxamyl and pirimicarb) in the range from 1 to 50 microg/l and a precision having a relative standard deviation below 7.8% was achieved. Instrumental limits of detection of 0.10 microg/l were found for these carbamates, with the exception of methomyl for which 0.50 microg/l was measured. The SPE assays were shown to be easy, fast, very sensitive, requiring a low volume (50 ml) of water sample. For laboratory-spiked water samples having 0.03 and 0.30 microg/l of individual N-methyl carbamates, higher selectivities were achieved in cartridges having octadecylsilica, polystyrene-divinylbenzene and N-vinylpyrrolidane-divinylbenzene as solid phases, for which reasonable average recoveries were obtained. Ten replicates using octadecylsilica SPE cartridges, showed average recoveries between 73.7 and 92.6% with a relative standard deviation lower than 14.7%. The present methodology evidences good robustness, accuracy and precision for monitoring of N-methyl carbamates in water samples, and is shown to be a suitable alternative to replace the currently dedicated analytical systems. The limits of detection for the analysis of N-methyl carbamates in water samples reached in the present methodology (0.5 to 3 ng/l), clearly cover the maximum concentration admissible for pesticides, established by the European Union directive on water quality.