Synthesis and fluorescence properties of side-chain carboxylated 5,9-diaminobenzo[a]phenoxazinium salts

The efficient synthesis of a series of novel side-chain carboxylated 5,9-diaminobenzo[a]phenoxazinium salts is described. The ring system was prepared by the reaction of 5-alkylamino-2-nitrosophenol hydrochlorides with the appropriate N-alkylated-naphthylamine. Evaluation of the visible and fluorescence properties of the cationic dyes was carried out in ethanol and water at physiological pH. In both solvents they showed intense visible absorption maxima in the range 500-638 nm (ethanol) and 625-650 (water), and fluoresced strongly, with fluorescence maxima from 612 to 669 nm (ethanol) and from 654 to 685 nm (water). A wide variation in fluorescence quantum yields is observed, ranging from 0.051 to 0.50 and 0.065 to 0.32 in ethanol and water, respectively.Fundação para a Ciência e a Tecnologia (FCT)

Surface modification of banana-based lignocellulose fibres

Lignocellulosic raw materials were isolated from rachis of Musa acuminata Colla var. cavendish and characterised before and after chemical modification. The rachis was submitted to different mechanical treatments, milling and defibration, resulting in rachis powder and rachis fi bers, respectively. The chemical composition of these two samples was established and it was shown that rachis fibres exhibited higher polysaccharide and lignin contents and lower amounts of ash and extractives components, as compared with the rachis powder. The effects of solvent extrac tion, alkali treatment and chemical modification using phenyl isocyanate, maleic anhydride, alkenyl succinic anhydride and alkyl ketone dimer as grafting agents were studied. The materials were characterized in terms of chemical structure by ATR–FT-IR and 13C-CP-MAS-NMR spectroscopy, morphology by scanning electron microscopy and surface energies by inverse gas chromatography and contact angle measurements. The surface energy of these materials was found to be very close to other similar lignocellulosic materials. Finally, the water absorption of these materials before and after treatment was ascertained. The modified fibres showed considerable changes in ATR–FT-IR and 13C-CP-MAS-NMR spectra and surface properties, providing very convincing evidence that chemical grafting had occurred.info:eu-repo/semantics/publishedVersio

5´-alkoxy-2,2´-bithiophene azo dyes: a novel promising series of NLO chromophores

A series of bithienyl azo dyes has been prepared from their corresponding coupling components, 5-alkoxy-2,2´-bithiophenes. The solvatochromic behavior of the compounds was investigated. The hyperpolarizabilities β of derivatives 3-5 were measured using hyper-Rayleigh scattering and thermogravimetric analysis (TGA) was used to evaluate their thermal stability. The experimental results indicate that, good nonlinearity-thermal stability is well balanced for azo-bithiophene NLO-chromophores 3-5 making them good candidates for NLO applications.Fundação para a Ciência e Tecnologia

Chromophoric azo reagents for amino acid and peptide labeling

Four carboxylic azo dyes are presented as new markers with spectroscopic absorption peaks ranging from 400 to 500 nm for amino acid and peptide labeling at their N-terminus. Labeling can also be performed at side chain residues as it is exemplified with lysine and serine.Fundação para a Ciência e Tecnologia

Synthesis and characterization of the thermal and the solvatochromic properties of heterocyclic azo dyes derived from 5-N,N-dialkylamino-2,2´-bithiophene couplers

A series of heterocyclic azo dyes was synthesized by diazotation of several substituted anilines and coupling with 5-N,N-dialkylamino-2,2´-bithiophenes to give 4-phenylazo-5-N,N-dialkylamino-2,2´-bithiophenes 4-7. This reaction contrasts with the behavior of 5-alkoxy-2,2´-bithiophenes towards aryldiazonium salts which gave 5-phenylazo-5-alkoxy-2,2´-bithiophenes. The thermal stability of the derivatives was evaluated using thermogravimetric analysis. The solvatochromic behaviour of the novel bithiophene azo dyes was investigated in several solvents of different polarity. The experimental results indicate that, the heterocyclic azo dyes 4-7 could be used as thermally stable solvatochromic probes.Fundação para a Ciência e a Tecnologia (FCT

Novel photochromic 2,2´-bithiophene azo dyes

The photochromic behaviour of two series of 2,2’-bithiophene azo dyes in THF solutions was studied. The photochromic properties and colour constancy were strongly dependent on the substitution pattern of the dyes. Under visible irradiation (> 420 nm) while some dyes exhibited a significant change in the colour intensity others exhibited an almost stable absorption. The photokinetic parameters of these systems are described.Fundação para a Ciência e a Tecnologia (FCT

5-Arylazo-2,2´-bithiophenes: a novel promising series of NLO chromophores

The synthesis of 5-arylazo- substituted bithiophenes and their UV-visible, solvatochromic and nonlinear optical properties (NLO) are described. In agreement with the solvatochromic data and also with the second-order molecular NLO characterization, the new donor-acceptor systems could find application as suitable solvatochromic probes and also as new NLO materials.Fundação para a Ciência e Tecnologia (FCT

Reaction of carboxylic dyes with wool and polyamide. Part III: Effect of the activating agent

Dyes containing a carboxylic acid group had been shown to react with wool and polyamide fibres when activated with ethyl chloroformate (Parts I and II). One of the dyes, 3-aminobenzoic acid →N,N-dimethylaniline, was, in this work, activated with other chlorofirmates, so as to improve the dyeing conditions. Benzyl chloroformate was found to be a good substitute since it is not as volatile as ethyl chloroformate, which suggests that it will be easier to apply in practical dyeing conditions. The yield of the reaction with cyclohexylamine is similar to the one obtained with ethyl chloroformate, suggesting that the fixation of the dye on wool or polyamide will be much the same. The fastness results are also equivalent.FCT-Fundação para a Ciência e Tecnologi

Identification of a cytokine network sustaining neutrophil and Th17 activation in untreated early rheumatoid arthritis

© 2010 Cascão et al.; licensee BioMed Central Ltd. This is an open access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.Introduction: Rheumatoid arthritis (RA) is a chronic inflammatory autoimmune disease characterized by sustained synovitis. Recently, several studies have proposed neutrophils and Th17 cells as key players in the onset and perpetuation of this disease. The main goal of this work was to determine whether cytokines driving neutrophil and Th17 activation are dysregulated in very early rheumatoid arthritis patients with less than 6 weeks of disease duration and before treatment (VERA). Methods: Cytokines related to neutrophil and Th17 activation were quantified in the serum of VERA and established RA patients and compared with other very early arthritis (VEA) and healthy controls. Synovial fluid (SF) from RA and osteoarthritis (OA) patients was also analyzed. Results: VERA patients had increased serum levels of cytokines promoting Th17 polarization (IL-1b and IL-6), as well as IL-8 and Th17-derived cytokines (IL-17A and IL-22) known to induce neutrophil-mediated inflammation. In established RA this pattern is more evident within the SF. Early treatment with methotrexate or corticosteroids led to clinical improvement but without an impact on the cytokine pattern. Conclusions: VERA patients already display increased levels of cytokines related with Th17 polarization and neutrophil recruitment and activation, a dysregulation also found in SF of established RA. 0 Thus, our data suggest that a cytokine-milieu favoring Th17 and neutrophil activity is an early event in RA pathogenesis.This work was supported by a grant from Sociedade Portuguesa de Reumatologia/Schering-Plough 2005. RAM and RC were funded by Fundação para a Ciência e a Tecnologia (FCT) SFRH/BD/30247/2006 and SFRH/BD/40513/2007, respectively. MMS-C was funded by Marie Curie Intra-European Fellowship PERG-2008-239422 and a EULAR Young Investigator Award