Hállen D. R. Calado

Metal complexes of 2-benzoylpyridine-derived thiosemicarbazones: structural, electrochemical and biological studies

Complexes of 2-benzoylpyridine thiosemicarbazone (H2Bz4DH) as well as of its N(4)-methyl (H2Bz4Me) and N(4)-phenyl (H2Bz4Ph) analogues with iron(II), nickel(II) and zinc(II) were characterized by a variety of spectroscopic techniques. Electrochemical studies revealed that the iron(II) complexes undergo oxidation giving the iron(III) analogues, which could be reduced back by cellular thiols such as thioredoxine, suggesting that this process could occur in biological media. The thiosemicarbazones have antifungal activity against Candida albicans that significantly decreases on coordination. The crystal structure 2-benzoylpyridine-N(4)-methyl thiosemicarbazone (H2Bz4Me) was determined.

Synthesis of C60(OH)18-20 in aqueous alkaline solution under O2-atmosphere

In this work we report on an alternative synthesis of water-soluble fullerenes known as fullerols, aiming for biomedical applications. The synthesis is based on a process in which polyethylene glycol (PEG400) is used as phase-transfer catalyst between fullerene/benzene and aqueous NaOH solutions. The polyhydroxylation of the fullerenes occurs in the NaOH solution under a continuous flow of O2 to enhance the reaction yield. The resulting compound was characterized with infrared spectroscopy, nuclear magnetic resonance, thermo-gravimetric analysis and optical absorption. The formation of C60(OH)18-20 in high yields was confirmed.

Synthesis and characterization of new 3-substituted thiophene copolymers

This work reports the synthesis of three polymers and two new copolymers based on 3-substituted polythiophene derivatives, all of them demonstrated photoluminescent properties. All polymers synthesized, i.e., poly(3-methoxythiophene) (PMOT), poly(3-thiopheneethanol) (PTE), poly(3-thiophenemethanol) (PTM), poly(3-methoxythiophene-co-3-thiopheneethanol) (PMOT-co-TE) and poly(3-methoxythiophene-co-3-thiophenemethanol) (PMOT-co-TM), were characterized by FT IR, UV-Vis, photoluminescence (PL), thermal analysis (TG and DSC) and X-ray diffraction (XRD). All materials emitted light in the orange region of the visible spectrum. Spectrometric analysis in the infrared region demonstrated the successful synthesis of polymers and copolymers by the presence of characteristic bands. Thermal analysis showed that the obtained materials had good thermal stability.

NANOCOMPÓSITOS DE POLIURETANA TERMOPLÁSTICA E NANOTUBOS DE CARBONO DE PAREDES MÚLTIPLAS PARA DISSIPAÇÃO ELETROSTÁTICA

Polyurethane/multi-walled carbon nanotube (MWCNT) nanocomposites have been prepared with nanotube concentrations between 0.01 wt% and 1 wt%. MWCNT as-synthesized samples with ~74 nm diameter and ~7 μm length were introduced by solution processing in the polyurethane matrix. Scanning electron microscopy (SEM) images demonstrated good dispersion and adhesion of the CNTs to the polymeric matrix. The C=O stretching band showed evidence of perturbation of the hydrogen interaction between urethanic moieties in the nanocomposites as compared to pure TPU. Differential scanning calorimetry and positron anihilation lifetime spectroscopy measurements allowed the detection of glass transition displacement with carbon nanotube addition. Furthermore, the electrical conductivity of the nanocomposites was significantly increased with the addition of CNT.

Characterization of a Sulfonated Polycarbonate Resistive Humidity Sensor

In this work; resistive moisture sensors were obtained by dip coating sulfonated polycarbonate (SPC) onto silver interdigitated electrodes. Commercial polycarbonate was sulfonated with acetyl sulphate at two different sulfonation degrees corresponding to 9.0 and 18.0 mole %. Impedance spectroscopy was used to investigate the humidity sensing properties at controlled relative humidity (RH%) environments generated from standard saline solutions in the range of 11–90 RH%. For the highest sulfonated sample; in the RH% range investigated (11 to 90%); the sensor impedance changed from 4.7 MΩ to 18 kΩ. Humidity sensors made from sulfonated polycarbonate showed exponential decay behavior of the impedance at constant frequency with the environmental relative humidity. Sample 9SPC presented dielectric relaxation response for environmental humidity between 58 and 90 RH% while sample 18SPC presented dielectric relaxation response for the entire measured range between 11 and 90 RH%. Sulfonated polycarbonate could be a promising material for the fabrication of simple and cheap humidity-sensing sensors for the assessment of relative humidity of the surrounding environment, as suggested by experimental results.

Blends of poly[2-(2′,5′-bis(2′-ethyl-hexyloxy)phenyl)-1,4-phenylenevinylene] and poly(3-hexylthiophene) as base materials for broad band light emission devices

Photoluminescence (PL) and electroluminescence (EL) emission from blended films composed by poly[2-(2′,5′-bis(2′-ethyl-hexyloxy)phenyl)-1,4-phenylenevinylene] (BEHP-PPV) and poly(3- hexylthiophene) (P3HT) conjugated polymers with different relative concentrations are investigated. The main changes observed on the PL spectra of the blended films with temperature and excitation power are associated to an increase of the emission efficiency of the P3HT constituent. The EL spectrum of a light emission device (LED) fabricated with the BEHP-PPV:P3HT blend presents a similar broad emission as in the PL measurement but shifted to higher wavelengths. The blended LEDs show a significantly higher emission efficiency than the LEDs made with the pure constituents. The apparent color of the blended LED shifts to a purer red as the applied voltage is increased. This tuning capacity was interpreted as due to a change in the effective gap of the blend caused by the redistribution of injected carriers in the BEHP-PPV:P3HT ...

Polymer nanocomposites based on P3OT, TPU and SWNT: preparation and characterization

Single walled carbon nanotubes (SWNTs) were incorporated in polymer nanocomposites based on poly(3-octylthiophene) (P3OT), thermoplastic polyurethane (TPU) or a blend of them. Thermogravimetry demonstrated the success of the purification procedure employed in the chemical treatment of SWNTs prior to composite preparation. Stable dispersions of SWNTs in chloroform were obtained by non-covalent interactions with the dissolved polymers. Composites exhibited glass transitions, melting temperatures and heat of fusion which changed in relation to pure polymers. This behavior is discussed as associated to interactions between nanotubes and polymers. The conductivity at room temperature of the blend (TPU-P3OT) with SWNT is higher than the P3OT/SWNT composite.

Oligômeros e polímeros derivados do tiofeno: síntese e aplicações

In this review we summarize recent synthetic investigations about the preparation of oligothiophenes and polythiophenes, the most important π-conjugated organic materials for applications in electrochromic and electroluminescent devices. It is showed that many interesting and novel functionalized oligothiophenes have been synthesized by convenient coupling strategies (Heck, Kumada, Negishi, Suzuki, Stille and Ullmann) and oxidative coupling methods. Synthesis of polythiophenes are also presented and described according to chemical and electrochemical polymerization methodologies. The description of these noteworthy synthetic methods illustrates how important and promising are the interdisciplinary approaches in the obtaining of oligothiophenes and polythiophenes.

Poly(3-hexythiophene)/multi-walled carbon nanotube composites: electrochemical and optical characterization

Carbon nanotubes (CNT) / conjugated polymer composites have been used for the preparation of thin film-modified electrodes. Thin, short, multi-walled CNT (MWNT) (purity higher than 95%) was completely coated by regioregular poly(3-hexylthiophene) (P3HT) through precipitation of a mixture of both in the non-solvent methanol. This work reports the electrochemical and optical characterization of P3HT and composites after dissolution in xylene and spin casting of films with thickness

Synthesis and electrochemical investigation of beta-substituted thiophene-based donor–acceptor copolymers with 3,4-ethylenedioxythiophene (EDOT)

The present work reports the synthesis of four electron-acceptor beta-substituted thiophenes that were studied as monomers for electrochemical polymerization with 3,4-ethylenedioxythiophene (EDOT), an electron-donating monomer, aiming the combination of electron-acceptor and donor monomer thiophene to a simpler and convenient build up of novel donor–acceptor copolymeric materials via electrochemical polymerization. Four novel copolymers poly(EDOT-co-3-thiophene phenylacetate), (PEDOT-co-PPhTAc-2a), poly(EDOT-co-3-thiophene(4-nitrophenyl)acetate) (PEDOT-co-PPhTAc-2b), poly(EDOT-co-3-thiophenephenylcarboxylate) (PEDOT-co-PPhTCb), and poly(EDOT-co-3-(phenoxymethyl)thiophene) (PEDOT-co-PPhOMT) were electrochemically polymerized. The monomers were characterized by spectrometric techniques (FTIR, 1H NMR, and 13C NMR), and the copolymers were identified by electrochemical analyses and FT-IR. Although the corresponding homopolymers could not be obtained, in the presence of EDOT, the copolymers were formed in a quasi-reversible electrochemical kinetics. The infrared spectra of the copolymers as well the electrochemical profile corroborates their obtaining. The mass variation during the electrosynthesis was analyzed using a quartz crystal microbalance. The film’s morphologies were investigated by SEM. Interestingly, the combination of electron-rich monomer thiophene (EDOT) and these electron-deficient carboxy-substituted thiophenes might be a convenient building block couple to increase the performance control of physic-chemical properties of mixed polythiophenes with innovative applications and they also showed a possible applicability as charge storage device.