Chemistry of stable iminopropadienones, RN=C=C=C=O

The synthesis, spectroscopic properties, and chemical reactions of the stable (neopentylimino)-, (mesitylimino)-, and (o-tert-butylphenylimino)propadienones (6) are reported. Nucleophilic addition of amines affords the malonic amidoamidines 7 and 8. 3,5-Dimethylpyrazole reacts analogously to form 9b. Addition of 1,2-dimethylhydrazine produces pyrazolinones 10-12. Addition of N,Y'-dimethyldiaminoethane, -propane, and -butane gives diazepine, diazocine, and diazonine derivatives 13-15, respectively (X-ray structures of 13c, 14a, and 15a are available). The mesoionic pyridopyrimidinium olates IS are obtained by addition of 2-(methylamino)pyridine (X-ray structure of 18b available). Primary 2-aminopyridines afford the pyridopyrimidininones 20-29 and 31 (X-ray structure of 21a available), and 2-aminopyrimidines and 2-aminopyrazine afford pyrimidopyrimidinones and pyrazinopyrimidinones 33-35. Pyrimidoisoquinolinone 36 results from 1-aminoisoquinoline and pyridoquinolinone 40 from 8-aminoquinoline. 2-Aminothiazoline and 2-aminothiazole afford thiazolopyrimidinone derivatives 41-43 (X-ray structure of 43a available).

Synthesis and structural properties of patellamide a derivatives and their copper(II) compounds

The synthesis, characterization and copper(II) coordination chemistry of three new cyclic peptide ligands, PatJ(1) (cyclo-(Ile -Thr- (Gly)Thz-lle-Thr(Gly)Thz)), PatJ(2) (cyclo-(Ile-Thr(Gly)Thz-(D)-Ile-Thr-(Gly)Thz)), and PatL (cyclo-(Ile-Ser-(Gly)Thz-Ile-Ser(Gly)Thz)) are reported. All of these cyclic peptides and PatN (cyclo-(Ile-Ser(Gly)Thz-Ile-Thr-(Gly)Thz)) are derivatives of patellamide A and have a [24]azacrown-8 macrocyclic structure. All four synthetic cyclic peptides have two thiazole rings but, in contrast to patellamide A, no oxazoline rings. The molecular structure of PatJ1, determined by X-ray crystallography, has a saddle conformation with two close-to-co-parallel thiazole rings, very similar to the geometry of patellamide D. The two coordination sites of PatJ1 with thiazole-N and amide-N donors are each well preorganized for transition metal ion binding. The coordination of copper(II) was monitored by UV/Vis spectroscopy, and this reveals various (meta)stable mono- and dinuclear copper(II) complexes whose stoichiometry was confirmed by mass spectra. Two types of dinuclear copper(II) complexes, [Cu-2(H4L)(OH2)(n)](2+) (n = 6, 8) and [Cu-2(H4L)(OH2)(n)] (n=4, 6; L=PatN, PatL, PatJ1, PatJ2) have been identified and analyzed structurally by EPR spectroscopy and a combination of spectra simulations and molecular mechanics calculations (MM-EPR). The four structures are similar to each other and have a saddle conformation, that is, derived from the crystal structure of PatJ(1) by a twist of the two thiozole rings. The small but significant structural differences are characterized by the EPR simulations.

The surface chemistry of leaching coal fly ash

The utilization of coal fly ash in the construction and non-construction areas has seen a rapid growth in the last decade. As production outweighs the utilization of fly ash, its disposal as a dilute or dense slurry is still practiced in coal fired power stations. In this review the surface chemistry of leaching coal fly ash is presented to highlight the role of mass transfer in providing resistance and consequently delayed leaching of elements, when fly ash is disposed or used for value addition. (C) 2002 Elsevier Science B.V. All rights reserved.

A study of the radiation chemistry of poly(chlorotrifluoroethylene) by ESR spectroscopy

The ESR spectra of poly(chlorotrifluoroethylene) were recorded following gamma-radiolysis under vacuum at room temperature and 77 K. The very broad spectrum at 77 K revealed little fine structure with which to identity the radicals formed upon irradiation, but subsequent photobleaching and annealing studies, together with radiolytic studies at higher temperatures, afforded scope for making radical assignments. Both main-chain radicals and a range of chain-end radicals have been identified. The G-values for radical formation were 1.55, 0.36 and 0.32 at 77 K, 273 K and room temperature, respectively. (C) 2003 Elsevier Science Ltd. All rights reserved.

Tuning the spectral distribution of p-i-n a-SiC : H devices for colour detection

ZnO:Al/p (SiC:H)/i (Si:H)/n (SiC:H) large area image and colour sensor are analysed. Carrier transport and collection efficiency are investigated from dark and illuminated current-voltage (I-V) dependence and spectral response measurements under different optical and electrical bias conditions. Results show that the carrier collection depends on the optical bias and on the applied voltage. By changing the electrical bias around the open circuit voltage it is possible to filter the absorption at a given wavelength and so to tune the spectral sensitivity of the device. Transport and optical modelling give insight into the internal physical process and explain the bias control of the spectral response and the image and colour sensing properties of the devices.

Voltammetric oxidation of drugs of abuse I. Morphine and metabolites

A detailed study of the electrochemical oxidative behavior of morphine in aqueous solution is reported. Through the synthesis of several metabolites and derivatives, pseudomorphine, morphine N-oxide, normorphine, dihydromorphine and 2-(N,N-dimethylaminomethyl)morphine, and their voltammetric study it was possible to identify the oxidation peaks for morphine. The anodic waves are related with the oxidation of phenolic and tertiary amine groups. It is also possible to verify that a poorly defined peak observable during morphine oxidation is not a consequence of further oxidation of pseudomorphine but due to formation of a dimer during phenolic group oxidation. The results obtained and especially those regarding the formation of a new polymer based on a C O coupling could be useful for clarifying the discoloration phenomenon occurring during storage of morphine solutions as well as leading to a better understanding of its oxidative metabolic pathways.

Diane Arbus: the wonderful wizard of odds or the poetics of the i (eye)

Diane Arbus‘ photographs are mainly about difference. Most of the time she is trying ‗[…] to suppress, or at least reduce, moral and sensory queasiness‘ (Sontag 1977: 40) in order to represent a world where the subject of the photograph is not merely the ‗other‘ but also the I. Her technique does not coax her subjects into natural poses. Instead she encourages them to be strange and awkward. By posing for her, the revelation of the self is identified with what is odd. This paper aims at understanding the geography of difference that, at the same time, is also of resistance, since Diane Arbus reveals what was forcefully hidden by bringing it into light in such a way that it is impossible to ignore. Her photographs display a poetic beauty that is not only of the ‗I‘ but also of the ‗eye‘. The world that is depicted is one in which we are all the same. She ―atomizes‖ reality by separating each element and ‗Instead of showing identity between things which are different […] everybody is shown to look the same.‘ (Sontag 1977: 47). Furthermore, this paper analyses some of Arbus‘ photographs so as to explain this point of view, by trying to argue that between rejecting and reacting against what is standardized she does not forget the geography of the body which is also a geography of the self. While creating a new imagetic topos, where what is trivial becomes divine, she also presents the frailty of others as our own.

Preparação e análise estrutural de complexos de samário

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica - Ramo de Bioprocessos

Phenotypic impact of deregulated expression of class I histone deacetylases in urothelial cell carcinoma of the bladder

Deregulated expression of histone deacetylases (HDACs) has been implicated in tumorigenesis. Herein, we investigated class I HDACs expression in bladder urothelial cell carcinoma (BUCC), its prognostic value and biological significance. Significantly increased transcript levels of all HDACs were found in BUCC compared to 20 normal mucosas, and these were higher in lower grade and stage tumors. Increased HDAC3 levels were associated with improved patient survival. SiRNA experiments showed decrease cell viability and motility, and increased apoptosis. We concluded that class I HDACs play an important role in bladder carcinogenesis through deregulation of proliferation, migration and apoptosis, constituting putative therapeutic targets

Implementation of the i-GAME mechanism in IEEE 802.15.4 WPANs

This technical report describes the implementation details of the Implicit GTS Allocation Mechanism (i-GAME), for the IEEE 802.15.4 protocol. The i-GAME was implemented in nesC/TinyOS for the CrossBow MICAz mote, over our own implementation of the IEEE 802.15.4 protocol stack. This document provides the implementation details, including a description of the i-GAME software interfaces.