A simple and rapid liquid chromatographic method with diode-array UV-vis spectrophotometric detection has been developed for the authentication of dragon's blood resins from Dracaena and Daemonorops trees. Using this method it was discovered that the flavylium chromophores, which contribute to the red colour of these resins, differ among the species and could be used as markers to differentiate among species. A study of parameters, such as time of extraction, proportion of MeOH and pH, was undertaken to optimise the extraction of the flavyliums. This method was then used to make extracts from samples of dragon's blood resin obtained from material of known provenance. From the samples analysed 7,6-dihydroxy-5-methoxyflavylium (dracorhodin), 7,4'-dihydroxy-5-methoxyflavylium (dracoflavylium) and 7,4'-dihydroxyflavylium were selected as species markers for Daemonorops spp., Dracaena draco and Dracaena cinnabari, respectively. The chromatograms from these samples were used to build an HPLC-DAD database. The ability to discriminate among species of dragon's blood using the single marker compounds was compared with a principal components analysis of the chromatograms in the HPLC-DAD database. The results from the HPLC-DAD method based on the presence of these flavylium markers was unequivocal. The HPLC-DAD method was subsequently applied to 37 samples of dragon blood resins from the historical samples in the Economic Botany Collection, Royal Botanic Gardens, Kew. The method identified anomalies in how samples in this collection had been labelled. It is clear that the method can be used to evaluate the provenance of samples used in different areas of cultural heritage. It also could be used to monitor the trade of endangered species of dragon's blood and the species being used in complex formulations of traditional Chinese medicine. (C) 2008 Elsevier B.V. All rights reserved.

We present a new concept for the design of a polymeric conducting material that combines the chemical versatility of an organic salt ( ionic liquid) with the morphological versatility of a biopolymer ( gelatin); the resulting 'ion jelly' can be applied in electrochemical devices, such as batteries, fuel cells, electrochromic windows or photovoltaic cells.

The degradation of indigo and its water soluble derivative indigo carmine was investigated under light excitation in the presence and absence of molecular oxygen in solution (homogeneous) and gels (heterogeneous) media. Collagen and carboxymethylcellulose (CMC) aqueous gels were chosen to simulate a natural textile environment, wool and cotton, respectively. Isatin was found to be the major degradation product of indigo. In solution, the photodegradation quantum yields (Phi(R)) were in the order of 10(-4), with the exception of aqueous media (Phi(R) = 9 x 10(-6)), and dependent on the irradiation wavelength. In the case of indigo carmine the Phi(R) values were found to suffer a 2-fold increase upon going from water to gels. The results indicate the absence of degradation products involving singlet oxygen and suggest peroxides, or other oxygen based radicals, to have a key role in the degradation of indigo. Finally, the relevance of the simulation is discussed by comparing the main degradation products to those found in the blues of millenary Andean textiles.

The analysis of different historic mauve samples-mauve salts and dyed textiles-was undertaken to establish the exact nature of the iconic dye produced by W.H. Perkin in the nineteenth century. Fourteen samples from important museum collections were analyzed, and it was determined that. in contrast to the general wisdom that mauveine consists of C, and C, structures. Perkin's mauveine is a complex mixture of at least thirteen methyl derivatives (C, to C(28)) with a 7-amino5-phenyl-3-(phenylamino)phenazin-5- ium core. A fingerprint was established in which mauveines A or B were dominant, and in which mauveines B2 and C(25) were found to be important tracers to probe the original synthesis. Counterion analysis showed that all the mauve salts should be dated after 1862. Perkin's original recipe could be identified in three textile samples, and in these cases, mauveines A and C25 were found to he the major chromophores. These are now shown to be the samples containing the "original mauve".

The compound 7,4'-dihydroxy-5-methoxyflavylium (dracoflavylium) was identified as the major red colorant in samples of the resin "dragon's blood", extracted from the tree Dracaena draco. The complex network of reversible chemical reactions that dracoflavylium undergoes in aqueous solution is fully described; for the first time, all the equilibrium constants that enable a complete characterisation of the system have been obtained (K'(a)=1.6 x 10(-4), K-a1 = 1.0 x 10(-4), K-a2 = 3.2 x 10(-8), K-Ct1 = 1.0 x 10(-7), K-Ct2 = 1.3 x 10(-10)). It is concluded that the red colour is due to a stable quinoid base, A, which is the major species at pH 4-7. It is further shown that this compound does not fit the commonly accepted definitions of anthocyanidin nor 3-deoxyanthocyanidin. Similarly to synthetic flavylium salts, the natural compound 7,4'-dihydroxy-5-methoxyflavylium gives rise to several species (multistate system) reversibly interconverted by external stimuli, such as pH.

Two new components have been identified in an early sample prepared according to the original recipe of Perkin, and perhaps even by Perkin himself around 1860 - a new isomer of Perkin's mauveine B (designated as mauveine B2) together with a new mauveine compound (mauveine C) - and these compounds were synthesized again using starting materials chosen to reproduce Perkin's original synthesis and isolated by HPLC-DAD, identified by H-1 NMR, MS and their spectroscopic (UV/Vis and emission) and photophysical behaviour investigated.

The synthesis, potentiometric studies and photophysical properties of two new polyamine ligands (L1 and L2) possessing the dansyl chromophore were studied in aqueous 0.15 M NaCl. The compounds show the absorption and emissions bands characteristic of the dansylamide fluorophore and both present intramolecular excited state proton transfer at intermediate pH ranges. One of the ligands (L2) strongly coordinates Zn(II) leading to fluorescence quenching. A model compound (L3) of the dansyl moiety was also investigated. (c) 2006 Elsevier B.V. All rights reserved.

Among the Krebs cycle components, just citrate enhances the fluorescence of a new bi(brachial) lariat aza-crown containing appended naphthalene fluorophores.