Biomonitoring of polybrominated diphenyl ether (PBDE) pollution: A field study

Polybrominated diphenyl ethers (PBDEs) and cytochrome P450 enzyme activities were investigated in European eels (Anguilla anguilla) collected from seven sites in a coastal lagoon in the north-western Mediterranean Sea, Orbetello lagoon (Italy). Twelve PBDE congeners were measured in muscle and two CYP1A enzyme activities, 7-ethoxyresorufin-O-deethylase (EROD) and benzo(a)pyrene monooxygenase (BP (a)PMO), were investigated in liver microsomal fraction in order to obtain insights into the health of the lagoon environment. PBDE muscle levels were low and the most abundant congeners were 2,2',4,4'-tetrabronnodiphenylether (BDE-47), 2,2',4,4',5,5'-hexaBDE (BDE-153) and 2,2',4,5'-tetraBDE (BDE-49). EROD and B(a)PMO activities were also low and no differences were observed between eels from different sites. Multivariate analysis (PCA) did not indicate correlations between PBDEs and either P450 activities. (c) 2008 Elsevier Inc. All rights reserved.

An optimized process design for oxymethylene ether production from woody-biomass-derived syngas

The conversion of biomass for the production of liquid fuels can help reduce the greenhouse gas (GHG) emissions that are predominantly generated by the combustion of fossil fuels. Oxymethylene ethers (OMEs) are a series of liquid fuel additives that can be obtained from syngas, which is produced from the gasification of biomass. The blending of OMEs in conventional diesel fuel can reduce soot formation during combustion in a diesel engine. In this research, a process for the production of OMEs from woody biomass has been simulated. The process consists of several unit operations including biomass gasifi- cation, syngas cleanup, methanol production, and conversion of methanol to OMEs. The methodology involved the development of process models, the identification of the key process parameters affecting OME production based on the process model, and the development of an optimal process design for high OME yields. It was found that up to 9.02 tonnes day1 of OME3, OME4, and OME5 (which are suitable as diesel additives) can be produced from 277.3 tonnes day1 of wet woody biomass. Furthermore, an optimal combination of the parameters, which was generated from the developed model, can greatly enhance OME production and thermodynamic efficiency. This model can further be used in a techno- economic assessment of the whole biomass conversion chain to produce OMEs. The results of this study can be helpful for petroleum-based fuel producers and policy makers in determining the most attractive pathways of converting bio-resources into liquid fuels.

Síntese e potencialidades de aplicação de novos derivados porfirínicos

A presente dissertação colige os resultados obtidos em estudos de funcionalização de porfirinas, nomeadamente de derivados da 5,10,15,20- tetrafenilporfirina. Nestes estudos foram estabelecidas novas rotas sintéticas para a preparação de moléculas adequadamente funcionalizadas e com possíveis aplicações em química medicinal ou em sistemas supramoleculares. Esta dissertação encontra-se dividida em quatro partes: Após uma breve introdução às porfirinas, descrita na primeira parte, segue-se uma segunda parte centrada em reacções em dominó envolvendo 2-aminomeso- tetra-arilporfirinas, meso-(p-aminofenil)porfirinas e éteres enólicos cíclicos. Os resultados obtidos demonstram que porfirinas reagem como heterodienos com dienófilos ricos em electrões tais como os éteres enólicos cíclicos 3,4-di-hidro-2H-pirano e 2,3-di-hidrofurano na presença de triflato de lantânio. Os produtos formados são pirido[2,3-b] porfirinas e meso-quinolin-6- ilporfirinas com dois grupos hidroxilos terminais. A terceira parte desta dissertação é dedicada a estudos de funcionalização da posição β-pirrólica da 5,10,15,20-tetrafenilporfirina com um éter coroa segundo reacções de metátese, reacções de Heck e reacções de ciclo-adição 1,3- dipolar. Nas reacções de ciclo-adição obtiveram-se apenas produtos resultantes do acoplamento de porfirinas ao aminoácido. Para culminar estes estudos usou-se a 2-formil-5,10,15,20-tetra-arilporfirina e diversos aminoácidos como precursores de iletos de azometino porfirínicos. Segundo esta abordagem, verificou-se que a cadeia lateral do aminoácido influencia o tipo de produto formado, tendo-se obtido novas clorinas, β-imidoporfirinas e porfirinas funcionalizadas na posição β-pirrólica com grupos amino. A estrutura dos compostos sintetizados foi estabelecida recorrendo a Espectroscopia de Ressonância Magnética Nuclear (RMN de 1H, 13C, COSY, HSQC, HMBC e NOESY), Espectrometria de Massa em MALDI, UV-Vis e, em alguns casos, Difractometria de raios-X. Já na quarta parte desta dissertação, o leitor é introduzido ao conceito de química supramolecular e à utilização de meso-(p-carboxifenil)porfirinas em sistemas auto-organizados. É descrita a formação de agregados J distintos a partir dos isómeros 5,10-bis-(4-carboxifenil)-15,20-difenilporfirina e 5,15-bis-(4- carboxifenil)-10,20-difenilporfirina e comprova-se que o tipo de arquitectura e a extensão deste sistema são impostas pela estrutura do cromóforo. A avaliação da formação destes sistemas foi efectuada recorrendo a técnicas de UV-vis, Fluorescência, CD, RLS e FLIM.

Investigation of structural effects on the reactivity of heterocyclic bioactive compounds

Tese de dout., Química, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2008

Rearranjos 3-aza-cope de N-alil-N-sililoxi enaminas

O rearranjo [3,3]-sigmatrópico térmico (180ºC) de diferentes N-alil-N-sililoxi enaminas foi estudado. Os respectivos produtos de rearranjo (éteres de óxima) foram obtidos com rendimentos elevados (80%). A regiosselectividade, [3,3] vs [1,3], e a diastereosselectividade do processo foram elevadas, superior a 99% e aproximadamente 80%, respectivamente. Foi demonstrada a importância do grupo sililoxilo na promoção do rearranjo face a substratos sem este tipo de substituição. Posteriormente, foi estudada a possibilidade de aceleração aniónica deste tipo de rearranjo por formação de oxianião ligado ao átomo de azoto. A estratégia seguida para a formação do mesmo, consistiu na O-dessililação de diferentes N-alil-N-sililoxi enaminas tendo-se obtido as nitronas correspondentes ou produtos de ciclização. Num exemplo envolvendo um derivado de isoxazole-5-(2H)-ona foi observado um aumento de velocidade do rearranjo por reacção com ião etoxilo. Este aumento de velocidade foi atribuído à abertura de anel do N-O éster cíclico para o N-oxianião, seguida de rearranjo e posterior fecho. Métodos alternativos de aceleração do rearranjo por geração de carga positiva, parcial ou completa, no átomo de azoto levaram apenas à dessililação das N-alil-N-sililoxi enaminas. ABSTRACT - [3,3]-sigmatropic rearrangement of a variety of N-allyl-N-silyloxy enamines was studied. The corresponding rearrangement products (oxime-ethers) were obtained in high yields (80%). High regioselectivity, [3,3] vs [1,3] (> 99%) and in appropriate cases, diastereoselectivity (80%) were observed. The importance of the silyloxy group in promoting the rearrangement, in relation to substrates lacking this functionality, is underlined. The possible anionic acceleration of the rearrangements was next examined by O-desilylation the N-silyloxy group bonded to the nitrogen. Attempted generation of these species however, was found to lead either to the corresponding nitrones or to cyclization products. In one particular example involving an isoxazol-5-(2H)-one derivative rate enhancement of rearrangement was indeed observed with ethoxide ion. It is tentatively attributed to ring opening of the cyclic N-O ester to the N-oxyanion ethyl ester followed by rearrangement and subsequent reclosure. Alternative methods to accelerate the process by generating a partial or complete positive charge on the nitrogen atom led only to desilylation.

Hazardous substances in frequently used professional cleaning products.

A growing number of studies have identified cleaners as a group at risk for adverse health effects of the skin and the respiratory tract. Chemical substances present in cleaning products could be responsible for these effects. Currently, only limited information is available about irritant and health hazardous chemical substances found in cleaning products. We hypothesized that chemical substances present in cleaning products are known health hazardous substances that might be involved in adverse health effects of the skin and the respiratory tract. We performed a systematic review of cleaning products used in the Swiss cleaning sector. We surveyed Swiss professional cleaning companies (n = 1476) to identify the most used products (n = 105) for inclusion. Safety data sheets (SDSs) were reviewed and hazardous substances present in cleaning products were tabulated with current European and global harmonized system hazard labels. Professional cleaning products are mixtures of substances (arithmetic mean 3.5 +/- 2.8), and more than 132 different chemical substances were identified in 105 products. The main groups of chemicals were fragrances, glycol ethers, surfactants, solvents; and to a lesser extent, phosphates, salts, detergents, pH-stabilizers, acids, and bases. Up to 75% of products contained irritant (Xi), 64% harmful (Xn) and 28% corrosive (C) labeled substances. Hazards for eyes (59%) and skin (50%), and hazards by ingestion (60%) were the most reported. Cleaning products potentially give rise to simultaneous exposures to different chemical substances. As professional cleaners represent a large workforce, and cleaning products are widely used, it is a major public health issue to better understand these exposures. The list of substances provided in this study contains important information for future occupational exposure assessment studies.

Biosynthesis of benzyliasoquinoline alkaloids

This research was carried out to obtain a convenient route for the synthesis of [7_ 14C]-p-hydroxy benzaldehyde. Section 1 of the thesis includes a route involving intermediates with protecting groups like benzyl and methyl ethers of the phenols. The benzyl ethers afforded the product in relatively better yield. The overall synthesis involves four steps. Section 2 describes the reactions carried out directly on phenols, and a three step pathway is obtained for the synthesis of p-hydroxy benzaldehyde, which was repeated on labelled compounds to obtain [7_14C]p- hydroxy benzaldehyde. The synthesis involves the reaction of p-bromophenol with Cu14CN to yield [7_ 14C]-p-cyano phenol, which is then reduced to the aldehyde by means of a simple and clean photolysis method. The same route was tried out to get 3,4-dihydroxybenzaldehyde and was found to work equally well for the synthesis of this compound. Section 3 deals with the isolation of labelled alkaloids, corydaline, protopine and reticu1ine from [2-3H,1-14C]-dopamine (3H/ 14C ratio = 4) fed Corydalis solida. 3H/14C ratios in the labelled alkaloids were determined. The uncorrected values showed almost 50% loss of 3H relative to 14C in reticuline, and roughly 75% loss of the 3H relative to 14C in corydaline and protopine.

NMR studies of the exchange reactions of CH3CN.BX3 with excess CH3CN /|nJoseph Fogelman. -- 260 St. Catharines, Ont. : [s. n.],

Exchange reactions between molecular complexes and excess acid or base are well known and have been extensively surveyed in the literature(l). Since the exchange mechanism will, in some way involve the breaking of the labile donor-acceptor bond, it follows that a discussion of the factors relating to bonding in molecular complexes will be relevant. In general, a strong Lewis base and a strong Lewis acid form a stable adduct provided that certain stereochemical requirements are met. A strong Lewis base has the following characteristics (1),(2) (i) high electron density at the donor site. (ii) a non-bonded electron pair which has a low ionization potential (iii) electron donating substituents at the donor atom site. (iv) facile approach of the site of the Lewis base to the acceptor site as dictated by the steric hindrance of the substituents. Examples of typical Lewis bases are ethers, nitriles, ketones, alcohols, amines and phosphines. For a strong Lewis acid, the following properties are important:( i) low electron density at the acceptor site. (ii) electron withdrawing substituents. (iii) substituents which do not interfere with the close approach of the Lewis base. (iv) availability of a vacant orbital capable of accepting the lone electron pair of the donor atom. Examples of Lewis acids are the group III and IV halides such (M=B, AI, Ga, In) and MX4 - (M=Si, Ge, Sn, Pb). The relative bond strengths of molecular complexes have been investigated by:- (i) (ii) (iii) (iv) (v] (vi) dipole moment measurements (3). shifts of the carbonyl peaks in the IIIR. (4) ,(5), (6) .. NMR chemical shift data (4),(7),(8),(9). D.V. and visible spectrophotometric shifts (10),(11). equilibrium constant data (12), (13). heats of dissociation and heats of reactions (l~), (16), (17), (18), (19). Many experiments have bben carried out on boron trihalides in order to determine their relative acid strengths. Using pyridine, nitrobenzene, acetonitrile and trimethylamine as reference Lewis bases, it was found that the acid strength varied in order:RBx3 > BC1 3 >BF 3 • For the acetonitrile-boron trihalide and trimethylamine boron trihalide complexes in nitrobenzene, an-NMR study (7) showed that the shift to lower field was. greatest for the BB~3 adduct ~n~ smallest for the BF 3 which is in agreement with the acid strengths. If electronegativities of the substituents were the only important effect, and since c~ Br ,one would expect the electron density at the boron nucleus to vary as BF3

Addition stéréosélective de nucléophiles sur un centre acétal : synthèse de nucléosides 1’,2’-cis

Plusieurs analogues de nucléosides thérapeutiques (Ara-C, Clofarabine), utilisés pour le traitement de leucémies, présentent un arrangement 1’,2’-cis entre la nucléobase reliée au centre anomère et le substituant (électroattracteur) en C-2’. Récemment, notre laboratoire a développé une approche synthétique pour former sélectivement des analogues de nucléosides et de thionucléosides 1’,2’-trans et 1’,2’-cis à partir de précurseurs acycliques. Ce mémoire présente une nouvelle méthodologie pour accéder efficacement aux analogues de nucléosides 1’,2’-cis à partir de furanosides. Différents groupements en position anomérique ont été examinés, sous conditions cinétiques en utilisant le bromure de diméthylbore pour générer sélectivement des produits acycliques ou cycliques. Les intermédiaires cinétiques de différents furanosides de méthyle formés en présence de Me2BBr ont été piégés in situ par un thiol pour générer des thioacétals acycliques avec de bonnes voire d’excellentes diastéréosélectivités. Les produits générés sont en accord avec une rétention globale de l’information stéréochimique du centre acétal et deux déplacements SN2 consécutifs ont été suggérés pour rationaliser ces résultats. Toutefois, l’objectif de synthétiser des analogues de nucléosides à partir de furanosides de méthyle a échoué. Tel que démontré par le Dr Michel Prévost, l’activation par Me2BBr des lactols des quatres différents furanosides suivie d’une addition in situ d’une base silylée a permis de former diastéréosélectivement les analogues de nucléosides 1’,2’-cis correspondants avec d’excellents rendements. Nous avons démontré que d’autres substrats peuvent être employés et que l’induction stéréochimique est sous contrôle du substituant électroattracteur en C-2. D’autres acides de Lewis, tel que TMSBr, peuvent également être utilisés. Cette méthodologie a également été étendue à d’autres nucléophiles tels que des Grignards ou des éthers d’énols silylés, conduisant à de bonnes sélectivités.

Développement de modèles prédictifs de la toxicocinétique de substances organiques

Les modèles pharmacocinétiques à base physiologique (PBPK) permettent de simuler la dose interne de substances chimiques sur la base de paramètres spécifiques à l’espèce et à la substance. Les modèles de relation quantitative structure-propriété (QSPR) existants permettent d’estimer les paramètres spécifiques au produit (coefficients de partage (PC) et constantes de métabolisme) mais leur domaine d’application est limité par leur manque de considération de la variabilité de leurs paramètres d’entrée ainsi que par leur domaine d’application restreint (c. à d., substances contenant CH3, CH2, CH, C, C=C, H, Cl, F, Br, cycle benzénique et H sur le cycle benzénique). L’objectif de cette étude est de développer de nouvelles connaissances et des outils afin d’élargir le domaine d’application des modèles QSPR-PBPK pour prédire la toxicocinétique de substances organiques inhalées chez l’humain. D’abord, un algorithme mécaniste unifié a été développé à partir de modèles existants pour prédire les PC de 142 médicaments et polluants environnementaux aux niveaux macro (tissu et sang) et micro (cellule et fluides biologiques) à partir de la composition du tissu et du sang et de propriétés physicochimiques. L’algorithme résultant a été appliqué pour prédire les PC tissu:sang, tissu:plasma et tissu:air du muscle (n = 174), du foie (n = 139) et du tissu adipeux (n = 141) du rat pour des médicaments acides, basiques et neutres ainsi que pour des cétones, esters d’acétate, éthers, alcools, hydrocarbures aliphatiques et aromatiques. Un modèle de relation quantitative propriété-propriété (QPPR) a été développé pour la clairance intrinsèque (CLint) in vivo (calculée comme le ratio du Vmax (μmol/h/kg poids de rat) sur le Km (μM)), de substrats du CYP2E1 (n = 26) en fonction du PC n octanol:eau, du PC sang:eau et du potentiel d’ionisation). Les prédictions du QPPR, représentées par les limites inférieures et supérieures de l’intervalle de confiance à 95% à la moyenne, furent ensuite intégrées dans un modèle PBPK humain. Subséquemment, l’algorithme de PC et le QPPR pour la CLint furent intégrés avec des modèles QSPR pour les PC hémoglobine:eau et huile:air pour simuler la pharmacocinétique et la dosimétrie cellulaire d’inhalation de composés organiques volatiles (COV) (benzène, 1,2-dichloroéthane, dichlorométhane, m-xylène, toluène, styrène, 1,1,1 trichloroéthane et 1,2,4 trimethylbenzène) avec un modèle PBPK chez le rat. Finalement, la variabilité de paramètres de composition des tissus et du sang de l’algorithme pour les PC tissu:air chez le rat et sang:air chez l’humain a été caractérisée par des simulations Monte Carlo par chaîne de Markov (MCMC). Les distributions résultantes ont été utilisées pour conduire des simulations Monte Carlo pour prédire des PC tissu:sang et sang:air. Les distributions de PC, avec celles des paramètres physiologiques et du contenu en cytochrome P450 CYP2E1, ont été incorporées dans un modèle PBPK pour caractériser la variabilité de la toxicocinétique sanguine de quatre COV (benzène, chloroforme, styrène et trichloroéthylène) par simulation Monte Carlo. Globalement, les approches quantitatives mises en œuvre pour les PC et la CLint dans cette étude ont permis l’utilisation de descripteurs moléculaires génériques plutôt que de fragments moléculaires spécifiques pour prédire la pharmacocinétique de substances organiques chez l’humain. La présente étude a, pour la première fois, caractérisé la variabilité des paramètres biologiques des algorithmes de PC pour étendre l’aptitude des modèles PBPK à prédire les distributions, pour la population, de doses internes de substances organiques avant de faire des tests chez l’animal ou l’humain.

INVESTIGATIONS ON THE SOLVENT EXTRACTION AND LUMINESCENCE OF LANTHANOIDS WITH MIXTURES OF HETEROCYCLIC β- DIKETONE S AND VARIOUS NEUTRAL OXO-DONORS

The thesis entitled “ Investigations on the solvent extraction and luminescence of lanthanoids with mixtures of heterocyclic β-diketone S and various neutral oxo-donors” embodies the results of investigations carried out on the solvent extraction of trivalent lanthanoids with various heterocyclic β-diketones in the presence and absence of neutral oxo-donors and also on the luminescent studies of Eu3+-heterocyclic β-diketonate complexes with Lewis bases. The primary objective of the present work is to generate the knowledge base, especially to understand the interactions of lanthanoid-heterocyclic β-diketonates with various macrocyclic ligands such as crown ethers and neutral organophosphorus extractants , with a view to achieve better selectivity. The secondary objective of this thesis is to develop novel lanthanoid luminescent materials based on 3-phenyl-4-aroyl-5-isoxazolones and organophosphorus ligands, for use in electroluminescent devices. In the beginning it describes the need for the development of new mixed-ligand systems for the separation of lanthanoids and the development and importance of novel luminescent lanthanoid- β-diketonate complexes for display devices. The syntheses of various para substituted derivatives of 4-aroyl-5-isoxazolones and their characterization by various spectroscopic techniques are described. It also investigate the solvent extraction behaviour of trivalent lanthanoids with 4-aroyl-5-isoxazolones in the presence and absence of various crown ethers such as 18C6, DC18C6, DB18C6 and B18C6. Elemental analysis, IR and H NMR spectral studies are used to understand the interactions of crown ethers with 4-aroyl-5-isoxazolonate complexes of lanthanoids. The synergistic extraction of trivalent lanthanoids with sterically hindered 1-phenyl-3-methyl-4-pivaloyl-5-pyrazolone in the presence of various structurally related crown ethers are studied. The syntheses, characterization and photyphysical properties of Eu3+-4-aroyl-5-isoxazolonate complexes in the presence of Lewis bases like trictylphosphine oxide or triphenylphosphine oxide were studied.

Synergistic solvent extraction of Thorium(IV) and Uranium(VI) with β-diketones in presence of oxo-donors

The thesis entitled “Synergistic solvent extraction of Thorium(IV) and Uranium(VI) with β-diketones in presence of oxo-donors” embodies the results of the investigations carried out on the extraction of thorium(IV) an uranium(VI) with heterocyclic β-diketones in the presence and absence of various macrocyclic ligands and neutral organophosphorus extractants. The objective of this work is to generate the knowledge base to achieve better selectivity between thorium(IV) and uranium(VI) by understanding the interactions of crown ethers or neutral organophosphorus extractants with metal-heterocyclic β-diketonate complexes. Para-substituted 1-phenyl-3-methyl-4-aroyl-5-pyrazolones, namely,1-phenyl-3-methyl-4-(4-fluorobenzoyl)-5-pyrazolone (HPMFBP) and 1-phenyl-3-methyl-4-(4-toluoyl)-5-pyrazolone (HPMTP) were synthesized and characterized by elemental analysis, IR and H NMR spectral data. The synthesized ligands have been utilized for the extraction of thorium(IV) and uranium(VI) from nitric acid solutions in the presence and absence of various crown ethers. Thorium(IV) and uranium(VI) complexes with HPMPP(1-Phenyl-3-methyl-4-pivaloyl-5-pyrazolone) and neutral organophosphorus extractants were synthesized and characterized by IR and P NMR spectral data to further understand the interactions of neutral organophosphorus extractants with metal-chelates. Solid complexes of thorium(IV) and uranium(VI) with para-substituted 4-aroyl-5-isoxazolones and crown ethers were isolated and characterized by various spectroscopic techniques to further clarify the nature of the extracted complexes.

Novel Reactions of TRIS(2-Thienyl)Methane and TRIS(2-Furyal)Methane

A systematic investigation of the reactivity and functionalization of two heterocyclic analogs of triphenylmethane , namely tris(2-thienyl)methane and tris(2-furyl)methane have been carried out and the results are presented in this thesis entitled "NOVEL REACTIONS OF TRIS(2-THIENYL)METHANE AND TRIS(2-FURYL)METHANE.". The history of organic free radicals dates back to Gomberg's monumental discovery of the triphenylmethyl radical in 1900. The heterocyclic analogs of triarylmethane are also interesting from the vantage point of their transformation to the corresponding radicals akin to Gomberg ' s triphenylmethyl radical and also they are prone to further transformation leading to three dimensionally elongated molecules such as dendrimers. Dendritic architectures are one of the most pervasive topologies observed in nature at the macro- and microdimensional length devices. Because of their ability to combine both organic and inorganic compounds and their propensity to either encapsulate or be engineered into unimolecular functional devices , dendrimers are versatile amongst existing nanoscale building blocks and materials.

Synthese und Charakterisierung neuer Stärkederivate für die klinische Anwendung

Ein neuartiges, mehrstufiges Syntheseverfahren wurde zur Darstellung von unterschiedlichen Stärkederivaten (Ether und Ester) entwickelt, die hinsichtlich ihres Eigenschaftsprofils und ihrer Reinheit für die klinische Anwendung als Blutvolumenersatzmittel geeignet sind. Die Synthesen wurden dahingehend gestaltet, dass Produkte mit einer hohen Regioselektivität resultierten. Dabei konnten sämtliche Reaktionsschritte, die zur Modifikation der ursprünglich eingesetzten Wachsmais- und Kartoffelstärken notwendig waren, in einem homogenen, wäss-rigen System ohne zwischenzeitliche Aufarbeitung in einem Eintopfverfahren durchgeführt werden. Die auf diese Weise bevorzugt synthetisierten Carboxymethylstärken wurden mit NMR-spektroskopischen Methoden und GPC-MALLS strukturell eingehend charakterisiert. Mit eigens entwickelten Enzym-Assays konnten essentielle Informationen über die physiolo-gische Wirksamkeit der verschiedenen Stärkederivate in vitro gewonnen werden. Die Ergebnisse konnten mit Untersuchungen an Humanblut verifiziert werden.

Identification of lipophilic flavones and flavonols by comparative HPLC, TLC and UV spectral analysis

The identification of lipophilic flavones and flavonols using a combination of high performance liquid chromatography, thin layer chromatography and UV spectral analysis is discussed. Data are provided for the flavones, apigenin, luteolin and tricetin and twelve of their methyl ethers, 8-hydroxyluteolin, 6-hydroxyluteolin and scutellarein and fourteen of their methyl ethers, and some 6,8-dihydroxyapigenin and 6,8-dihydroxyluteolin derivatives. Data for some forty two flavonols with extra 6- and/or 8-hydroxylation, mostly 6-hydroxykaempferol and quercetagetin derivatives, are also presented. The remaining compounds analysed include fourteen 5-deoxyflavones, four 5-methoxyflavones and five 5-deoxyflavonols plus further 5-hydroxylated flavones and flavonols without B-ring oxidation or with 2-, 5- or 6-hydroxylation. Copyright © 2003 John Wiley & Sons, Ltd.