Aroylhydrazone Cu(II) complexes in keto form: structural characterization and catalytic cctivity towards cyclohexane oxidation

The reaction of the Schiff base (3,5-di-tert-butyl-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (H3L) with a copper(II) salt of a base of a strong acid, i.e., nitrate, chloride or sulphate, yielded the mononuclear complexes [Cu(H2L)(NO3)(H2O)] (1), [Cu(H2L)Cl]center dot 2MeOH (2) and the binuclear complex [{Cu(H2L)}(2)(mu-SO4)]center dot 2MeOH (3), respectively, with H2L- in the keto form. Compounds 1-3 were characterized by elemental analysis, Infrared (IR) spectroscopy, Electrospray Ionisation-Mass Spectrometry (ESI-MS) and single crystal X-ray crystallography. All compounds act as efficient catalysts towards the peroxidative oxidation of cyclohexane to cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone, under mild conditions. In the presence of an acid promoter, overall yields (based on the alkane) up to 25% and a turnover number (TON) of 250 (TOF of 42 h(-1)) after 6 h, were achieved.

Exploring redox-driven self-assembly of mixed metal polyoxometalates

How can we control the experimental conditions towards the isolation of specific structures? Why do particular architectures form? These are some challenging questions that synthetic chemists try to answer, specifically within polyoxometalate (POM) chemistry, where there is still much unknown regarding the synthesis of novel molecular structures in a controlled and predictive manner. This work covers a wide range of POM chemistry, exploring the redox self-assembly of polyoxometalate clusters, using both “one-pot”, flow and hydrothermal conditions. For this purpose, different vanadium, molybdenum and tungsten reagents, heteroatoms, inorganic salts and reducing agents have been used. The template effect of lone-pair containing pyramidal heteroatoms has been investigated. Efforts to synthesize new POM clusters displaying pyramidal heteroanions (XO32-, where X= S, Se, Te, P) are reported. The reaction of molybdenum with vanadium in the presence of XO32- heteroatoms is explored, showing how via the cation and experimental control it is possible to direct the self-assembly process and to isolate isostructural compounds. A series of four isostructural (two new, namely {Mo11V7P} and {Mo11V7Te} and two already known, namely {Mo11V7Se} and {Mo11V7S} disordered egg-shaped Polyoxometalates have been reported. The compounds were characterized by X-ray structural analysis, TGA, UV-Vis, FT-IR, Elemental and Flame Atomic Absorption Spectroscopy (FAAS) analysis and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Cyclic Voltammetry measurements have been carried out in all four compounds showing the effect of the ionic density of the heteroatom on the potential. High-Resolution ESI-MS studies have revealed that the structures retain their integrity in solution. Efforts to synthesize new mixed-metal compounds led to isolation, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyoxometalate cluster anion, {H2W4V9O33(C6H13NO3)}, by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster. Control experiments (in the absence of the organic compound) have proven that the tripodal ligand plays crucial role on the formation of the isomer. The six vanadium metal centres, which consist the upper part of the cluster, are bonded to the “capping” TEA tripodal ligand. This metal-ligand bonding directs and stabilises the formation of the final product. The δ-Keggin species was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, NMR and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations and changing colour under light. Non-conventional synthetic approaches are also used for the synthesis of the POM clusters comparing the classical “one-pot” reaction conditions and exploring the synthetic parameters of the synthesis of POM compounds. Reactions under hydrothermal and flow conditions, where single crystals that depend on the solubility of the minerals under hot water and high pressure can be synthesized, resulted in the isolation of two isostructural compounds, namely, {Mo12V3Te5}. The compound isolated from a continuous processing method, crystallizes in a hexagonal crystal system, forming a 2D porous plane net, while the compound isolated using hard experimental conditions (high temperature and pressure) crystallizes in monoclinic system, resulting in a different packing configuration. Utilizing these alternative synthetic approaches, the most kinetically and thermodynamically compounds would possibly be isolated. These compounds were characterised by single-crystal X-ray diffraction, FT-IR and UV-vis spectroscopy. Finally, the redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {M18O54(XO4)2} cluster is further investigated using UV-vis spectroscopy as a function of reaction time, showed that more than six complete oscillations interconverting the capsule species present in solution from {P2M18} to {V2M18} were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution. In an effort to investigate the periodicity of the exchange of the phosphate and vanadate anions, time dependent Uv-vis measurements were performed for a period at a range of 170-550 hours. Different experimental conditions were also applied in order to investigate the role of the reducing agent, as well as the effect of other experimental variables on the oscillatory system.

Antioxidant profile of Stevia rebaudiana Bertoni cultivated in Portugal and submitted to different conservation conditions

The demand for natural sweeteners has been gaining more and more importance due to the great controversy associated with the use of some synthetic sweeteners as cyclamates, aspartame and acesulfame-K. The steviol glycosides (E 960) are a group of natural sweeteners of generalized use; these compounds are obtained from Stevia rebaudiana Bertoni, a sweet plant native from South America (Carocho et al., 2015). However, Stevia rebaudiana Bertoni may have other uses to be exploited, in particular due to its antioxidant capacity. This plant is already produced in Portugal but it is important to evaluate if the plant chemical composition is maintained regardless of culture conditions. Therefore, in this study, stevia samples were cultivated in Braganca (northeastern of Portugal) in a field trial with defined culture conditions. After harvesting, the plants were submitted to two different treatments: kept fresh by freezing (-20°C) and oven-dried (30°C). The antioxidant profile of the samples was studied through evaluation of free radicals scavenging activity, reducing power, phenolic compounds (HPLC-DAD-ESI/MS), tocopherols (HPLC-fluorescence) and free sugars (HPLC-RI). Significant differences were observed: while oven-dried samples showed the highest antioxidant activity and phenolic compounds concentration (mainly 5-O-caffeoylquinic acid and 3,5-O-dicaffeoylquinic acid), the frozen fresh samples had the highest values of total tocopherols and total sugars. These results confirm that the plants grown in Bragança have excellent bioactive secondary metabolites responsible for the observed antioxidant capacity.

Degradation of compounds present in cork boiling water by gamma radiation

Cork boiling water is an aqueous and complex dark liquor with high concentration of phenolic compounds such as phenolic acids and tannins [1, 2], which are considered biorecalcitrants [2]. Ionizing radiation has been widely studied as an alternative technology for the degradation of organic contaminants without the addition of any other (e.g.: Fenton technologies). The aim of this work was to identify the compounds present in cork boiling water and further evaluate the resulting stable degradation products after gamma irradiation. The irradiation experiments of standard solutions were carried out at room temperature using a Co-60 experimental equipment. The applied absorbed doses were 20 and 50 kGy at a dose rate of 1.5 kGy/h, determined by routine dosimeters [3]. The identification of radiolytic products was carried out by HPLC-DAD-ESI/MS. The phenolic compounds were identified by comparing their retention times and UV–vis and mass spectra with those obtained from standard compounds, when available, as well as by comparing the obtained information with available data reported in the literature. Concerning the obtained results and the literature review, the main cork wastewater components are: quinic, gallic, protocatechuic, vanillic, syringic and ellagic acids. Based on this, we used protocatechuic, vanillic and syringic acids as model compounds to study their degradation by gamma radiation in order to identify the corresponding radiolytic products. Standard aqueous solutions were irradiated and the derivatives of each model compound are represented in figure 1. The obtained results seem to demonstrate that the derivatives of the parent compounds could also be phenolic acids, since it was observed the loss of 44 u (CO2) from the [M-H]- ions. Gallic and protocatechuic acids are identified as derivatives of vanillic and syringic acids, and gallic acid as a protocatechuic acid derivative. Compound 5 ([M-H]- at m/z 169) was tentatively identified as 2,4,6-trihydroxybenzoic acid, since its fragmentation pattern (m/z 151, 125 and 107) is similar to that previously reported in literature [4]. The structure of compound 7 was proposed based on the molecular ion and its fragmentation and compound 6 remains unknown.

Antiangiogenic potential of yogurts added with extracts rich in apigenin derivatives

Angiogenesis is a biological process through which there is the formation of new blood vessels from preexisting ones [I]. However, in pathological cases, the abnormal growth of new blood vessels promotes the development of various diseases including cancer [2) through the production of atypically large amounts of angiogenesis factors, e.g. the vascular endothelial growth factor (VEGF) [3]. The plant secondary metabolites have been the subject of several studies to evaluate their benefits to human health. In particular, the phenolic compounds have high potential for use in the food industry, including the development of functional foods. Among these, apigenin has been associated with chemopreventive effects related to cancer [4]. In fact, chemoprevention is a present-day concept and contemplates the use of medicines, biological compounds or nutrients as an intervention strategy of cancer prevention. In this work, an Arenaria montana L hydroethanolic extract was prepared and after characterization by HPLC-DAD-ESI/MS showed to be rich in apigenin derivatives. Furthermore, it exhibited ability to inhibit the phosphorylation of VEGFR-2 (vascular endothelium growth factor receptor) through an enzymatic assay. However, for the major protection of bioactive compounds, the extract was microencapsulated by an atomization/coagulation technique with alginate as the matrix material. Posteriorly, the hydroethanolic extract, in free and microencapsulated forms, was incorporated in yogurts in order to develop a novel chemopreventer food in relation to the angiogenesis process. The functionalized yogurts with A. montana extracts (free and microencapsulated) showed a nutritional value similar to the used control (yogurt without extract); however, the samples enriched with extracts revealed added-value regarding the VEGFR-2 phosphorylation inhibition ability. This effect was more effectively preserved over time in the samples functionalized with the protected extract. Overall, this work contributes to the valorization of plants rich in flavonoids, exploring its antiangiogenic potential with VEGFR-2 as target. Moreover, the atomization/coagulation technique allowed the production of viable microspheres enriched with the plant extract. The microspheres were effectively incorporated into yogurts, protecting the extract thus envisaging the development of novel functional foods with chemopreventive effects.

The use of wild fruits of Fragaria vesca L. in preparations with bioactive properties: chemical characterization, antioxidant, antibacterial and antibiofilm activities

Wild strawberry, Fragaria vesca L., belongs to Rosaceae family and is commonly found in roadsides and slopes [1]. The most consumed parts of this plant are its sweet small fruits, which constitute a source of vitamins and phenolic compounds, being also used in infusions due to their organoleptic properties and for the treatment of some intestinal disorders [2, 3]. In the present work, F. vesca fruits were evaluated for their nutritional value and further used in the preparation of infusions. The chemical composition of the fruits and corresponding infusions was determined in terms of soluble sugars, organic acids, tocopherols, folates (by HPLC coupled to different detectors), phenolic compounds (by HPLC-DAD/ESI-MS) and mineral elements (atomic absorption spectroscopy). Some of these bioactive compounds were correlated with antioxidant and antibacterial properties evaluated either in infusions as also in hydromethanolic extracts. Carbohydrates were the main macronutrients in the fruits, followed by fat and proteins. Regarding the fatty acids, polyunsaturated fatty acids showed higher prevalence, mainly due to the presence of D-linolenic (Cl8:3n3) and y-linolenic (Cl8:3n6) acids. Sucrose and citric acid were, respectively, the main sugar and organic acid found in the fruits and in its infusions. The microelement found in higher amounts in both samples was manganese, while potassium and calcium were the macroelements present in higher levels in the fruits and infusions, respectively. Both samples presented folates and tocopherols, being ytocopherol the main isoform detected in the fruits, while a-tocopherol was the only isoform quantified in the infusion. The hydromethanolic extract prepared from the fruits gave higher antioxidant and antibacterial activities, namely against Escherichia coli and Pseudomonas aeruginosa, than the infusion; it also showed capacity to inhibit the formation of bacterial biofilm. Both bioactivities are highly correlated with the presence of phenolic compounds, in which the major are ellagic acid derivatives (sanguiin hlO) followed by tlavan 3-ols ((+)catechin) and anthocyanin compounds (pelargonidin-3-glucoside). Although fruits of wild F. vesca are mainly consumed in fresh, this study also proves the potentiality of their infusions as a source of bioactive molecules and properties.

The impact of gamma irradiation on the cytotoxic properties and phenolic composition of Thymus vulgaris L. and Menta x piperita L.

Irradiation has been increasingly recognized as an effective decontamination technique, also ensuring the chemical and organoleptic quality of medicinal and aromatic plants 1 . The use of medicinal plants in the prevention and or treatment of several diseases has revealed satisfactory results as anti-inflammatory, antimutagenic, anti-cancer and antioxidant agents 2 . The aim of the present study was to evaluate the effects of gamma irradiation on the cytotoxic properties and phenolic composition of Thymus vulgaris L. and Menta x piperita L. (methanolic extracts). Phenolic compounds were analyzed by HPLC-DAD-ESI MS, while the cytotoxicity of the samples was assessed in MCF-7 (breast adenocarcinoma), NCI-H460 (non-small cell lung cancer), HeLa (cervical carcinoma), HepG2 (hepatocellular carcinoma) cell lines, as also in non-tumor cells (PLP2). Thirteen and fourteen phenolic compounds were detected in T. vulgaris and M. piperita, respectively, but none of them was affected by the irradiation up to a dose of 10 kGy. However, despite there were no changes in the cytotoxic properties of irradiated peppermint samples in tumor cell lines, the thyme samples irradiated with 10 kGy showed higher cytotoxicity in comparison with the samples submitted to other doses (2 and 5 kGy). This highlights that 10 kGy can be a suitable dose to ensure the sanitary treatment, without modifying the bioactive composition and properties of these aromatic plants.

Análise cromatográfica de um extrato fenólico de funcho utilizado no desenvolvimento de requeijões com propriedades funcionais

Atualmente, existe uma grande procura de alimentos com ingredientes naturais em substituição de aditivos sintéticos que têm sido associados, em determinadas circunstâncias, a alguns efeitos tóxicos [1]. Neste trabalho, preparou-se um extrato aquoso por decocção de Foeniculum vulgare Mill. (funcho) que, após caracterização por HPLC-DAD-ESI/MS, revelou a presença de cinco flavonoides (sendo o maioritário o quercetin-3-O-glucósido) e doze ácidos fenólicos (sendo o maioritário o ácido 5-Ocafeoilquínico). O mesmo extrato revelou um enorme potencial antioxidante (efeito captador de radicais livres DPPH, poder redutor e inibição da peroxidação lipídica) e antimicrobiano (contra bactérias como Salmonella typhimurium e Bacillus cereus, e fungos como Aspergillus niger, A. versicolor e Penicillium funiculosum), o que suscitou o seu potencial de utilização como ingrediente bioativo na funcionalização de alimentos. Assim, procedeu-se à sua incorporação (atendendo ao EC25 =0,35 mg/mL obtido no ensaio de DPPH) em requeijões (preparados na empresa Queijos Casa Matias Lda.). Os resultados mostraram que a presença do extrato não alterou significativamente as características nutricionais (incluindo macronutrientes, valor energético e perfil em ácidos gordos) das amostras controlo (requeijão sem esse ingrediente), no entanto parece aumentar o amarelecimento (parâmetro da cor, b*) após 7 dias de armazenamento. Verificou-se ainda que, após duas semanas de armazenamento apenas as amostras controlo apresentaram sinais de degradação. Além disso, conseguiu-se provar que a incorporação do extrato de funcho conferiu propriedades antioxidantes ao requeijão. Os resultados obtidos provam assim que o extrato fenólico obtido através da decocção de funcho pode ser utilizado como conservante e agente bioativo natural em requeijões.

Phenolic profile and antimicrobial activity of dietary supplements based on Cochlospermum angolensis Welw.

Cochlospermum angolensis Welw. (borututu) is a widespread tree in Angola that belongs to the Cochlospermaceae family. Its bark infusion is used in the traditional medicine of Angola for the treatment of jaundice, hepatic diseases and for the prophylaxis of malaria [1]. In the present work, three formulations based on this plant (infusion, pills, and syrup) were characterized by HPLC-DAD-ESI/MS regarding phenolic composition, and evaluated by their in vitro antimicrobial activity against isolates of multiresistant bacteria (Escherichia coli, Escherichia coli spectrum extended producer of β-lactamases (ESBL), Proteus mirabilis, methicillin-resistant Staphylococcus aureus (MRSA) and Pseudomonas aeruginosa). The infusion and pills revealed the highest variety of phenolic compounds, with eleven compounds identified. Protocatechuic acid was only present in infusions, being the most abundant compound, while (epi)gallocatechin-O-gallate and eucaglobulin/globulusin were the main molecules identified in pills and syrup, respectively. Methyl ellagic acids, eucaglobulin/globulusin B (Fig. 1) and (epi)gallocatechin-O-gallate were found in all the formulations. The infusion revealed antimicrobial activity against all the studied bacteria with the exception of P. mirabilis whereas the pills revealed activity in E. coli ESBL and MRSA. No significant antimicrobial activity was detected in the syrup, in agreement with its low concentrations of phenolic compounds. None of the tested formulations inhibited P. mirabilis. Considering the obtained results, C. angolensis infusion can be considered a good source of phenolic compounds as well as a good antimicrobial agent.

Effects of gamma and electron-beam irradiation on the individual phenolics of Viola tricolor L. edible flowers.

Edible flowers are being used in culinary preparations to improve the sensorial and nutritional qualities of food, besides improving human health due to the profusion in bioactive compounds [1]. Nevertheless, edible flowers are highly perishable and must be free of insects, which is difficult because they are usually cultivated without using pesticides [2]. Food irradiation is an economically viable technology to extend shelf life of foods, improving their hygiene and quality, while disinfesting insects [3]. The efficiency and safety of radiation processing (using Co-60 or electronaccelerators) have been approved by legal authorities (FDA, USDA, WHO, FAO), as also by the scientific community, based on extensive research [4]. Viola tricolor L. (heartseases), from Violaceae family, is one of the most popular edible flowers. Apart from being used as food, it has also been applied for its medicinal properties, mainly due to their biological activity and phenolic composition [5]. Herein, the phenolic compounds were analyzed by HPLC-DAD-ESI/MS and linear discriminant analysis (LDA) was performed to compare the results from flowers submitted to different irradiation doses and technologies (Co-60 and electron-beam). Quercetin-3-O-(6-O-rhamnosylglucoside)-7-O-rhamnoside (Figure 1) was the most abundant compound, followed by quercetin-3-O-rutinoside and acetyl-quercetin-3-O (6-O-rhamnosylglucoside)-7-O-rhamnoside. In general, irradiated samples (mostly with 1 kGy) showed the highest phenolic compounds content. The LDA outcomes indicated that differences among phenolic compounds effectively discriminate the assayed doses and technologies, defining which variables contributed mostly to that separation. This information might be useful to define which dose and/or technology optimizes the content in a specific phenolic compound. Overall, irradiation did not negatively affect the levels of phenolic compounds, providing the possibility of its application to expand the shelf life of V. tricolor and highlighting new commercial solutions for this functional food.

Perfil fenólico individual e potencial antioxidante de partes vegetativas de Fragaria vesca L..

O morangueiro silvestre (Fragaria vesca L., Rosaceae) está disseminado por toda a Península Ibérica, podendo também ser encontrado na Coreia, América do Norte e Canadá [1]. Apesar dos frutos serem mais consumidos, as partes vegetativas têm sido tradicionalmente usadas devido às suas propriedades tónicas e diuréticas e, em particular as suas decocções são recomendadas no tratamento da hipertensão [2,3]. As propriedades bioativas dos frutos F. vesca têm sido correlacionadas com a presença de compostos fenólicos, nomeadamente ácidos elágicos, procianidinas e flavonóis [4]. No entanto, o perfil fenólico das partes vegetativas é ainda desconhecido. Assim, no presente trabalho foi analisada a composição fenólica de extratos hidrometanólicos e aquosos obtidos a partir de partes vegetativas de amostras comerciais e silvestres de F. Vesca, tendo sido também avaliada a sua atividade antioxidante. Os perfis fenólicos, obtidos por HPLC-DAD-ESI/MS, das amostras comercial e silvestre foram bastante distintos, no entanto, em termos de derivados de ácido elágico, ambas apresentaram o isómero sanguiin h10 como composto maioritário, bem como trímeros de procianidinas e ramnósido de quercetina na amostra comercial e silvestre, respetivamente. A infusão da amostra silvestre apresentou maior atividade captadora de radicais DPPH (EC50= 86.17 μg/mL) e compostos fenólicos (CF = 134.65 mg/g) comparativamente à amostra comercial. A infusão da amostra silvestre mostrou também maior poder redutor, inibição da descoloração do β- caroteno e inibição da formação de TBARS (EC50= 62.23, 12.34 e 3.12 μg/mL, respetivamente); o poder redutor mostrou maior correlação com F e F3O, enquanto o ensaio TBARS se correlacionou mais com DAE e F. A atividade antioxidante da amostra comercial (especialmente o poder redutor e a inibição da descoloração do β- caroteno) revelou uma elevada correlação com a presença de derivados de ácido elágico (DAE), flavonóis (F), flavan-3-óis (F3O) e CF. Os resultados obtidos demonstram o elevado potencial antioxidante das partes vegetativas do morangueiro silvestre, podendo constituir uma nova fonte de compostos bioativos para aplicação na área alimentar e farmacêutica.

Nova formulação de iogurtes com extratos aquosos de funcho e camomila na substituição de aditivos químicos

Existe por parte dos consumidores uma tendência crescente na escolha de alimentos designados por mais saudáveis em que a presença em aditivos sintéticos é reduzida ou até mesmo ausente. Para melhorar a aparência e/ou propriedades dos alimentos a indústria recorre ao uso de aditivos sintéticos [1], no entanto, alguns autores têm apresentado alguma relação entre o consumo excessivo de alguns desses aditivos com efeitos adversos para a saúde do consumidor [2]. Para contornar esta problemática e ir ao encontro das expectativas dos consumidores, têm sido considerados os extratos naturais obtidos a partir de plantas como excelentes ingredientes naturais para a indústria alimentar como alternativas aos aditivos sintéticos [3]. Este trabalho teve como objetivo comparar os efeitos de antioxidantes naturais (extratos aquosos de Foeniculum vulgare Mill., funcho, e Matricaria recutita L., camomila, obtidos por decocção) com um aditivo sintético (sorbato de potássio, E202) utilizado em iogurtes. Neste trabalho, as amostras de Foeniculum vulgare Mill. (funcho) e Matricaria recutita L. (camomila) foram submetidas a uma extração por decocção. A sua caracterização química foi feita por HPLC-DAD-ESI/MS. As propriedades antioxidantes foram avaliadas através de diferentes ensaios in vitro (efeito captador de radicais livres, poder redutor e inibição da peroxidação lipídica), tal como as propriedades antimicrobianas (contra bactérias e fungos). A incorporação dos extratos foi feita em iogurtes e desta forma, foram preparados quatro grupos de amostras: iogurtes controlo (sem adição de qualquer aditivo), iogurtes com decocção de funcho, iogurtes com decocção de camomila e iogurtes com E202. As amostras foram avaliadas quanto à cor, pH e ao seu valor nutricional e potencial antioxidante. O estudo foi feito no tempo zero e após sete e catorze dias de armazenamento a 4ºC. Tal como podemos observar na Figura 1, a incorporação dos aditivos quer naturais quer sintéticos, não provocou alteração no aspeto visual quando comparado com a amostra controlo sem aditivos (A). Os resultados demonstram ainda que a introdução dos aditivos não provocou alterações significativas no pH e no valor nutricional dos iogurtes quando comparados com o controlo (Tabela 1). No entanto, esta incorporação conferiu propriedades antioxidantes aos iogurtes principalmente, pela adição do extrato de camomila (Figura 2). Estes resultados permitem-nos concluir que os extratos aquosos de funcho e camomila ricos em compostos fenólicos [4,5] podem representar uma alternativa aos conservantes sintéticos melhorando desta forma as propriedades funcionais dos iogurtes sem, no entanto, provocar alterações no perfil nutricional dos mesmos.

Novel Analytical Methodologies for the Monitoring of Traditional and Non-traditional Pollutants in different Environmental Compartments of South Florida

Routine monitoring of environmental pollution demands simplicity and speed without sacrificing sensitivity or accuracy. The development and application of sensitive, fast and easy to implement analytical methodologies for detecting emerging and traditional water and airborne contaminants in South Florida is presented. A novel method was developed for quantification of the herbicide glyphosate based on lyophilization followed by derivatization and simultaneous detection by fluorescence and mass spectrometry. Samples were analyzed from water canals that will hydrate estuarine wetlands of Biscayne National Park, detecting inputs of glyphosate from both aquatic usage and agricultural runoff from farms. A second study describes a set of fast, automated LC-MS/MS protocols for the analysis of dioctyl sulfosuccinate (DOSS) and 2-butoxyethanol, two components of Corexit®. Around 1.8 million gallons of those dispersant formulations were used in the response efforts for the Gulf of Mexico oil spill in 2010. The methods presented here allow the trace-level detection of these compounds in seawater, crude oil and commercial dispersants formulations. In addition, two methodologies were developed for the analysis of well-known pollutants, namely Polycyclic Aromatic Hydrocarbons (PAHs) and airborne particulate matter (APM). PAHs are ubiquitous environmental contaminants and some are potent carcinogens. Traditional GC-MS analysis is labor-intensive and consumes large amounts of toxic solvents. My study provides an alternative automated SPE-LC-APPI-MS/MS analysis with minimal sample preparation and a lower solvent consumption. The system can inject, extract, clean, separate and detect 28 PAHs and 15 families of alkylated PAHs in 28 minutes. The methodology was tested with environmental samples from Miami. Airborne Particulate Matter is a mixture of particles of chemical and biological origin. Assessment of its elemental composition is critical for the protection of sensitive ecosystems and public health. The APM collected from Port Everglades between 2005 and 2010 was analyzed by ICP-MS after acid digestion of filters. The most abundant elements were Fe and Al, followed by Cu, V and Zn. Enrichment factors show that hazardous elements (Cd, Pb, As, Co, Ni and Cr) are introduced by anthropogenic activities. Data suggest that the major sources of APM were an electricity plant, road dust, industrial emissions and marine vessels.

High precision and selectivity for quantitation of enrofloxacin and ciprofloxacin in five chicken tissues using solid phase extraction and ESI LC-MS/MS for application in monitoring residues

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Screening and Structural Characterization of alpha-Glucosidase Inhibitors from Hawthorn Leaf Flavonoids Extract by Ultrafiltration LC-DAD-MSn and SORI-CID FTICR MS

In vitro a-glucosidase inhibition assays and ultrafiltration liquid chromatography with photodiode array detection coupled to electrospray ionization tandem mass spectrometry (ultrafiltration LC-DAD-ESI-MSn) were combined to screen a-glucosidase inhibitors from hawthorn leaf flavonoids extract (HLFE). As a result, four compounds were identified as alpha-glucosidase inhibitors in the HLFE, and their structures were confirmed to be quercetin-3-O-rha-(1-4)-glc-rha and C-glycosylflavones (vitexin-2 ''-O-glucoside, vitexin-2 ''-O-rhamnoside and vitexin) by high-resolution sustained off resonance irradiation collision-induced dissociation (SORI-CID) data obtained by Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS).