Janete H. Yariwake

Fast supercritical fluid extraction and high-resolution gas chromatography with electron-capture and flame photometric detection for multiresidue screening of organochlorine and organophosphorus pesticides in Brazil’s medicinal plants

A description is given of a rapid and environmentally friendly method to determine organochlorine and organophosphorus pesticide multiresidues--malathion, methidathion, fenitrothion, fenthion, parathion-ethyl, parathion-methyl, lindane, hexachlorobenzene, chlorothalonil, tetradifon, alpha-endosulfan, beta-endosulfan and dieldrin-in Passiflora alata Dryander and pasiflora edulis Sims. f. flavicarpa Deg. leaves by supercritical fluid extraction and high-resolution gas chromatography with electron-capture and flame photometric detection (HRGC-ECD/FPD). The mild extraction conditions [pure CO2; 100 bar (1 bar = 10(5) Pa) and 40 degrees C (p = 0.62 g/ml); 5 min static+10 min dynamic extraction time; ODS trap and elution with 1 ml n-hexane at 2 ml/min] allow for direct analysis by HRGC-ECD/FPD with no prior cleaning procedure. The method provides. in accordance with the validation criteria of the European Pharmacopoeia, analytical results that are similar or even better than the official procedures, and is simpler, faster and cheaper. Mean recoveries of 69.8-107.1% were obtained, with 1.4-14.7% reproducibility (RSD). The method was applied to analyse commercial samples of Passiflora L. from Brazil. Twenty-three percent of the samples showed the presence of the organochlorine or organophosphorus pesticide residue investigated.

Maracujá: um alimento funcional?

Este artigo e uma revisao bibliografica sobre as especies brasileiras de Passiflora (Passiflora edulis fo. flavicarpa O. Deg., P. alata Curtis e P. edulis fo. edulis). A maioria dos artigos da literatura focaliza somente as folhas de Passiflora, enquanto que esta revisao contem informacoes sobre a polpa, cascas e sementes dos frutos do maracuja, com destaque para a composicao quimica, estudos nutricionais e farmacologicos. O enfoque nos frutos do maracuja fundamenta-se no amplo consumo do suco de maracuja (fresco ou industrializado) no Brasil e tambem nas investigacoes em andamento para avaliar o seu potencial uso como alimento funcional.

Evaluation of the antioxidant activity of passion fruit (Passiflora edulis and Passiflora alata) extracts on stimulated neutrophils and myeloperoxidase activity assays.

The antioxidant activity of methanol extracts from Passiflora edulis and Passiflora alata pulp, and P. edulis rinds, healthy or infected with the passion fruit woodiness virus (PWV), was investigated using the oxidant activities of the neutrophil and the neutrophil granule enzyme myeloperoxidase (MPO), both playing key roles in inflammation. The reactive oxygen species produced by stimulated neutrophils were evaluated by lucigenin-enhanced chemiluminescence (CL) and the activity of purified MPO was measured by SIEFED (Specific Immunological Extraction Followed by Enzymatic Detection), a technique for studying the direct interaction of a compound with the enzyme. The rind extracts of P. edulis possessed higher and dose-dependent inhibitory effects on CL response and on the peroxidase activity of MPO than total pulp extracts from both passion fruit species. The quantification of isoorientin in the extracts showed a correlation with their antioxidant activity, suggesting the potential of P. edulis rinds as functional food or as a possible source of natural flavonoids.

Study of C- and O-glycosylflavones in sugarcane extracts using liquid chromatography: exact mass measurement mass spectrometry

The flavonoids present in sugarcane (Saccharum officinarum) extracts were analyzed by liquid chromatography - mass spectrometry (LC-MS), and a study of the fragmentation patterns of selected flavonoids was conducted using orthogonal acceleration time-of-flight electrospray ionization mass spectrometry (ESI-oa-ToF MS). Seven C- and O-glycosylflavones were identified in the extracts, namely, schaftoside, isoschaftoside, luteolin-8-C-(rhamnosylglucoside), vitexin, orientin, tricin-7-O-neohesperidoside and tricin-7-O-glucoside. Of these, five were identified in the absence of direct comparison with their respective standards. The described method also permitted the differentiation of the 6-C and 8-C isomeric flavones, schaftoside and isoschaftoside. The combination of fragmentation data and exact mass measurement showed to be complimentary to the HPLC-UV-MS techniques previously utilized for isomers discrimination in sugarcane studies.

Analysis of passion fruit rinds (Passiflora edulis): isoorientin quantification by HPTLC and evaluation of antioxidant (radical scavenging) capacity

The content of isoorientin in passion fruit rinds (Passiflora edulis fo. flavicarpa O. Degener) was determined by HPTLC (high performance thin layer chromatography) with densitometric analysis. The results revealed a higher amount of isoorientin in healthy rinds of P. edulis (92.275 ± 0.610 mg L-1) than in rinds with typical symptoms of PWV (Passion fruit Woodiness Virus) infection (28.931 ± 0.346 mg L-1). The HPTLC data, allied to assays of radical scavenging activity, suggest the potential of P. edulis rinds as a natural source of flavonoids or as a possible functional food.

On-line LC/UV/MS analysis of flavonols in the three apple varieties most widely cultivated in Brazil

Este trabalho apresenta a primeira investigacao sobre a estrutura quimica dos flavonois presentes em cascas das tres variedades de macas mais cultivadas no Brasil: Gala, Golden e Fuji. As analises foram feitas por CL/UV/EM (cromatografia liquida de alta eficiencia com detector UV com arranjo de diodos acoplada a espectrometria de massas), usando adicao poscoluna de reagentes de deslocamento de UV e tambem espectrometria de massas de multiplos estagios (EM n ) com ionizacao “electrospray” no modo negativo. A identificacao “on-line” com base nos dados de CL/UV/EM demonstrou a presenca de rutina, hiperosideo, isoquercitrina, quercitrina e outros tres derivados de quercetina-3-O-pentosideo. As analises por CL/UV/EM tambem demonstraram que as tres variedades de maca tem perfis cromatograficos semelhantes. This work describes the first detailed investigation into the chemical structures of flavonols present in the three apple varieties most commonly cultivated in Brazil: Gala, Golden and Fuji. The analyses were carried out by LC/UV/MS (high-performance liquid chromatography coupled to diode array UV detection and mass spectrometry), using post-column addition of UV shift reagents, as well as multiple stage mass spectrometry (MS n ) with electrospray ionization in the negative ion mode. Rutin, hyperoside, isoquercitrin, quercitrin, quercetin and three other quercetin-3-pentoside derivatives were identified through the characterization of on-line-based LC/UV/MS data. LC/UV/MS analysis also revealed that the three apple cultivars have similar chromatographic profiles.

On-line identification of minor flavones from sugarcane juice by LC/UV/MS and post-column derivatization

Este trabalho apresenta a identificacao “on line” de flavonas minoritarias do suco da cana-deacucar (Saccharum officinarum) , por cromatografia liquida de alta eficiencia com detector UV acoplada a espectrometria de massas (CL/UV/EM) com ionizacao quimica a pressao atmosferica, dissociacao induzida por colisao (IQPA-DIC-EM/EM) e derivatizacao pos-coluna utilizando reagentes de deslocamento de UV. As analises CLAE-UV com reagentes de deslocamento forneceram informacoes sobre a posicao da substituicao no esqueleto dos flavonoides e, em combinacao com dados de EM, estas tecnicas permitiram a identificacao “on-line” de cinco flavonas da garapa: luteolina-8- C-glucosil-7-O-glucuronideo; tricina-7-O-neoesperosideo-4’O-ramnosideo; tricina-7-O-metilglucuronato-4’-O-ramnosideo; tricina-7-O-metilglucuronideo; swertisina; e outras quatro substâncias foram parcialmente identificadas como flavonas glicosiladas. Somente a swertisina (7-O-metilapigenina-6-C-glicosideo) foi anteriormente descrita no bagaco da cana-de-acucar. This work describes the on-line characterization of minor flavones from sugarcane (Saccharum officinarum ) juice by high-performance liquid chromatography coupled to diode array UV detection and mass spectrometry (LC/UV/MS) using atmospheric pressure chemical ionizationcollision-induced dissociation (APCI-CID-MS/MS) and post-column derivatization using UV shift reagents. HPLC-UV analysis with shift reagents provided information about the substitution pattern in the flavonoid skeleton and, combined with MS data, these techniques allowed for the on-line identification of five “garapa” flavones: luteolin-8- C-glucosyl-7-O-glucuronide; tricin-7-O-neohesperoside-4’-O-rhamnoside; tricin-7-O-methylglucuronate-4’-O-rhamnoside; tricin-7-O-methylglucuronide; swertisin, while four other compounds were partially identified as glycosylflavones. Only swertisin (7- O-methylapigenin-6-C-glucoside) was reported previously in sugarcane molasses.

Quantification of harman alkaloids in sour passion fruit pulp and seeds by a novel dual SBSE-LC/Flu (stir bar sorptive extraction-liquid chromatography with fluorescence detector) method

A method for the quantification of the alkaloids harmane and harmine in sour passion fruit (Passiflora edulis f. flavicarpa O. Degener, Passifloraceae) pulp and seeds by stir-bar sorptive extraction and high performance liquid chromatography with fluorescence detection (dual SBSE-LC/Flu) is described. The SBSE parameters were optimized using a fractional factorial design, and the dual SBSE-LC/Flu method was validated following the International Conference on Harmonisation of Technical Requirements for Registration of Pharmaceuticals for Human Use (ICH) guidelines. The high sensitivity and minimal sample handling of the dual SBSE-LC/Flu method make it attractive for application in phytochemical analysis or in the food industry.

Multivariate analysis of the effects of soil parameters and environmental factors on the flavonoid content of leaves of Passiflora incarnata L., Passifloraceae

The aim of the present study was to evaluate the effect of soil characteristics (pH, macro- and micro-nutrients), environmental factors (temperature, humidity, period of the year and time of day of collection) and meteorological conditions (rain, sun, cloud and cloud/rain) on the flavonoid content of leaves of Passiflora incarnata L., Passifloraceae. The total flavonoid contents of leaf samples harvested from plants cultivated or collected under different conditions were quantified by high-performance liquid chromatography with ultraviolet detection (HPLC-UV/PAD). Chemometric treatment of the data by principal component (PCA) and hierarchic cluster analyses (HCA) showed that the samples did not present a specific classification in relation to the environmental and soil variables studied, and that the environmental variables were not significant in describing the data set. However, the levels of the elements Fe, B and Cu present in the soil showed an inverse correlation with the total flavonoid contents of the leaves of P. incarnata.

Extração de β-caroteno de cenouras: uma proposta para disciplinas experimentais de química

This paper reports on the development of a simple and fast procedure for β-carotene extraction from carrots and its quantification by UV/Vis spectroscopy. Carotenoids extracted from carrots may also be used as alternative reagents for TLC (thin layer chromatography) detection of natural compounds with antioxidant properties, replacing the commercial p.a. grade β-carotene. Although this reagent had around 10% b-carotene, it proved to be as efficient for TLC analysis as the commercial p.a. grade β-carotene. This practice is a useful alternative for teaching undergraduate organic chemistry laboratory classes.