Abstract This work reports the spectroelectrochemical and electrical behavior of electropolymerized donor-acceptor like (D-A) copolymer films, based on 3,4-ethylenedioxythiophene (EDOT) and beta-substituted electron-acceptor thiophenes. Initially, the copolymer films were deposited on indium tin oxide substrates, which spectroelectrochemistry measurements were carried out with an UV-Vis spectrophotometer. Hence, it was possible to observe the electrochromic properties of these materials, visualizing the color changing towards different potentials applied. The experiments have shown that these D-A like copolymers presented good electrochromic properties, such as optical contrast, coloration efficiency, and switching times. Additionally, films prepared on a platinum working electrode were investigated by electrochemical impedance spectroscopy, which has shown the electrical behavior of those copolymers and their potential as candidates to capacitive devices building. Therefore, the combination of electron-donor EDOT with those electron-acceptor monomers is indeed a useful strategy to tailoring and fine-tuning the physicochemical properties of polythiophenes with innovative applications.

Resumo O rápido desenvolvimento da química de polímeros nos últimos anos tem acompanhado a introdução dos materiais poliméricos no campo da medicina. Polímeros com aplicações médicas podem ser subdivididos em dois grandes grupos: materiais usados em próteses e a produção de polímeros biologicamente ativos. Neste trabalho foram sintetizados copolímeros possuindo cadeia principal de poli (metacrilato de metila) e cadeias enxertadas de polietilenoglicol (COP GRAFT). A partir da síntese do copolímero enxertado inicial foram realizadas modificações em suas cadeias de modo a aumentar a possibilidade de incorporação de um fármaco que será utilizado em sistema de liberação controlada de medicamentos. Os novos compostos foram obtidos através de duas rotas sintéticas e os produtos formados ao final de cada etapa foram purificados e caracterizados. Através da técnica de infravermelho (FITIR) foi possível observar as bandas de absorções características das ligações P-H, P=O e P-O, que foram inseridas na cadeia do COP GRAFT durante a fosforilação, além das bandas de absorções características do copolímero, antes da fosforilação, como C=O e C-O. A caracterização térmica das amostras utilizando termogravimetria (TGA) e calorimetria diferencial de varredura (DSC) mostrou que apenas o copolímero de diisobutila apresentou temperatura de transição endotérmica e comportamentos de degradação compatíveis a de um polímero. Através da técnica de difração de raios X (XRD) foi possível observar uma modificação da cristalinidade das amostras, provavelmente devido a uma variação da conformação das cadeias após a inserção de novos grupos químicos. Nos cromatogramas obtidos pela técnica de cromatografia de permeação em gel (GPC) percebeu-se aumento de massa após a fosforilação com o grupo diisobutila no COPGRAFT. A reação de fosforilação foi eficiente na obtenção do copolímero de diisobutila e as técnicas aplicadas demonstraram que houve a modificação no copolímero enxertado.

Abstract The rapid development in polymer chemistry has, in recent years, led to the introduction of polymeric materials in the field of medicine. Two major groups of polymers are used for medical applications: prosthetic and biologically active materials. We synthesized copolymers with the main chain consisting of poly (methyl methacrylate) and graft chains of poly(ethylene glycol) (COP GRAFT). Changes were made in the graft copolymer chains for a possible incorporation of a drug, such that it may be used for the controlled release of drugs. The synthesis of these new compounds is based on two synthetic routes and FTIR, differential scanning calorimetry (DSC), thermogravimetry (TGA) and X-ray diffraction (XRD) characterized the products formed at the end of each stage. Through FTIR we observed absorption bands characteristic of P-H, P=O and P-O bonds that were inserted into the polymer chain during phosphorylation of the COP GRAFT, beyond the absorption bands characteristic of the copolymer before phosphorylation, such as C=O and C-O. By TGA and DSC we observed that only the diisobutyl copolymer has endothermic transition temperature and degradation behavior consistent with a polymer. XRD results showed a structural and conformational change in crystallinity of modified chains. Molecular weight and polydispersity of COPGRAFT obtained by GPC increased after phosphorylation with diisobutyl group. The phosphorylation reaction was efficient in obtaining diisobutyl copolymer and the applied techniques confirmed the modification of the COPGRAFT chains.

Atualmente, a gestão de resíduos sólidos e águas residuais é uma grande preocupação para a humanidade. Na ultima década, a detecção de traços de medicamentos no ciclo da água tem sido reportada e tem gerado preocupação entre os agentes reguladores, fornecedores de água e público devido os riscos potenciais para a saúde humana. As empresas farmacêuticas, em Minas Gerais, aplicam tratamentos convencionais para as águas residuais e não há praticamente avaliação sobre a eficiência de remoção de resíduos de antibióticos. Este estudo avaliou a gestão de resíduos sólidos e concluiu que o destino principal foi, para o caso de resíduos perigosos, a incineração e, para os não perigosos, a reciclagem e o aterro sanitário. No entanto, denúncias apresentadas à Agência Ambiental - FEAM indicam que número significativo de empresas envia seus resíduos perigosos para aterros sanitários e até mesmo para lixões, ressaltando, assim, a necessidade urgente de adequada gestão dos resíduos gerados. A espectrometria de massas com ionização electrospray (ESI-MS) mostrou que a rota de tratamento convencional adotada por duas empresas do setor selecionadas não foi suficientemente eficaz, uma vez que resíduos e fragmentos de antibióticos foram detectados. Os resultados da caracterização físico-química de efluentes evidenciaram suas características variáveis, que podem influenciar a sua tratabilidade. O ensaio de degradação com o reagente Fenton destaca-se como caminho promissor para alcançar maior remoção. Este estudo contribuiu para elevar o nível de conhecimento no gerenciamento de águas residuais e resíduos sólidos da indústria farmacêutica no estado de Minas Gerais e evidenciou a necessidade de estudos mais detalhados.

Today the management of solid waste and wastewater is a major concern for humanity. In the last decade, traces of pharmaceuticals have been reported in the water cycle and have raised concerns among regulators, water suppliers and the public regarding the potential risks to human health. This study evaluated solid waste management in the state of Minas Gerais and concluded that the main fate of hazardous waste has been incineration, while the non-hazardous waste has been recycled or sent to landfills. However, complaints to the Environmental Agency - FEAM have indicated that a significant number of companies just send their hazardous wastes to landfills or even to garbage dumps, thus highlighting the urgent need for adequate waste management in Minas Gerais. Most of the pharmaceutical companies in Minas Gerais use conventional wastewater treatment. Mass spectrometry with electrospray ionization (ESI-MS) showed that the treatment routes adopted by the two 2 selected pharmaceutical industries were not effective enough since residues and degradation products of antibiotics were detected. The physicochemical analysis of the effluents showed variability in their characteristics, which may influence their treatability. The degradation assay with Fenton's reagent stood out as a promising route in achieving a higher removal capacity compared to the conventional treatment. This study contributes to enhancing our knowledge of the management of wastewater as well as of solid waste from the pharmaceutical industry in Minas Gerais and points out the need for further research.

Biscationic amidines bind in the DNA minor groove and present biological activity against a range of infectious diseases. Two new biscationic compounds (bis-α,ω-S-thioureido, amino and sulfide analogues) were synthesized in good yields and fully characterized, and their interaction with DNA was also investigated. Isothermal titration calorimetry (ITC) was used to measure the thermodynamic properties of binding interactions between DNA and these ligands. A double stranded calf thymus DNA immobilized on an electrode surface was used to study the possible DNA-interacting abilities of these compounds towards dsDNA in situ. A remarkable interaction of these compounds with DNA was demonstrated and their potential application as anticancer agents was furthered.

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.

This paper presents a revision of the history, definitions, and classification of tracers (natural and artificial, internal and external). The fundamental ideas concerning tracers are described, followed by their application illustrated by typical examples. The advantages and disadvantages of five classes among the most frequently used external tracers (fluorescent, microbial, chemical, radioactive and activable isotopes) are also described in detail. This review also presents some interesting and modern applications of tracers in the areas of diagnostics in medical practice, environmental pollution, hydrology and petroleum chemistry.

This paper is a review of the history, synthesis and application of organophosphorus compounds, especially of those of pentavalent phosphorus, such as phosphoramidates, phosphorothioates, phosphonates and phosphonic acids with insecticide and anticancer activities. The organophosphorus compounds with agrochemical applications show great structural variety, They include not only insecticides, but also fungicides, herbicides, and others. The large variety of commercially available organophosphorus pesticides is remarkable. Even more interesting is the high efficiency of some organophosphorus compounds as anticancer agents such as cyclophosphamide and its derivatives.

The 1,2,3-triazole, known since the end of 19th century, is a very widely used heterocyclic system present in many synthetic substances and commercial pharmaceutical compounds. In fact, 1,2,3-triazoles show several applications in many areas especially as medicines against many diseases like cancer, AIDS, Parkinson and Alzheimer. Nowadays there is a large variety of known methods to obtain these heterocyclic compounds comprising mainly three synthetic routes. Nevertheless, there is no article that gives an objective overview of the synthetic methods for obtaining these kinds of azoheterocycles. This paper presents a brief history of this class of compounds, and a synthetic discussion concerning the main synthetic methods for its preparation, such as cyclization through hydrazones, concerted cycloadditon [2+3] and pseudopericyclic cyclization - and some others of restricted application, but also important. Finally, this paper also provides a brief overview on pharmacological applications of some 1,2,3-triazoles.

The chemotherapy agents against cancer may be classified as "cell cycle-specific" or "cell cycle-nonspecific". Nevertheless, several of them have their biological activity related to any kind of action on DNA such as: antimetabolic agents (DNA synthesis inhibition), inherently reactive agents (DNA alkylating electrophilic traps for macromolecular nucleophiles from DNA through inter-strand cross-linking - ISC - alkylation) and intercalating agents (drug-DNA interactions inherent to the binding made due to the agent penetration in to the minor groove of the double helix). The earliest and perhaps most extensively studied and most heavily employed clinical anticancer agents in use today are the DNA inter-strand cross-linking agents.

In this work the surface of activated carbon was chemically modified in order to introduce O, S and N containing groups. The activated carbon surface was selectively oxidized with concentrated HNO3 under controlled conditions. Characterization by thermogravimetric analyses, infrared spectroscopy and NaOH titration suggested the formation of mainly -COOH and small amounts of -OH groups, with concentration of approximately 4.10(21) groups/g of carbon. These -COOH functionalized carbons showed high adsorption capacity for metal cations in aqueous solution in the following order: Pb+2>Cu+2>Ni+2 >Cd+2~Co+2>Ca+2 , suggesting a cation exchange mechanism via a surface complex [COO-M+2]. These -COOHsurf groups can be reacted with SOCl2 to produce a surface acylchloride group, -COCl. This surface -COCl group proved to be a very reactive and versatile intermediate for the grafting of different S and N containing molecules onto the carbon surface, such as 1,2-ethaneditiol (EDT-, HSCH2CH2SH) 1,7-dimercapto-4-thioheptane (DMTH-HSCH2CH2CH2SCH2CH 2CH2SH) or 1,2-ethylenediamine (EDA- NH2CH2CH2NH2 ) and triethyltetraamine, TEA (H2NCH2CH2NHCH2CH 2NHCH2CH2 NH2). The characterization of these materials was carried out by TG, IR and TPDMS (Temperature Programmed Decomposition Mass Spectrometry) experiments suggesting the formation of thioesther and amide surface groups, i.e. -COSR and -CONHR, with yields of approximately 50 and 75% for the reaction with DME and EDA, respectively. Preliminary adsorption experiments showed that these materials can efficiently remove metals such as Pb+2, Cu+2 and Ni+2 from aqueous medium.

The importance of chiral alcohols as starting materials for the production of fine chemicals and as useful chirons for the building of several interesting molecules or natural products is reported. The useful and common methods of asymmetric reduction such as the chemical (with organoboron or organoaluminum reagents) and the catalytic ones (with ruthenium or rhodium complexes) for preparation of chiral alcohols are described; even the newer and much more rare electrocatalytic methods are reported.

The 2,2'-bipyridine has been entitled as the most widely used ligand. Nowadays there is a large variety of known molecules comprising at least two 2,2'-bipyridine units and the number of applications in many areas such as catalysis, new materials, optoeletronics and electrochemistry have increased very much in the past decades. Nevertheless, there is no article that gives an overview of the main synthetic methods for obtaining the substituted 2,2'-bipyridines, generally non available. This article presents a synthetic discussion about the three different methods (coupling reaction, ciclo-functionalization and functionalization of the heteroaromatic rings of 2,2'-bipyridine) for preparing these heterocyclic compounds and also provides a practical and fundamental guide, for obtaining more than eighty different symmetric and unsymmetrical substituted 2,2'-bipyridines, shown in a table with the corresponding references.

Organosulfur compounds present in garlic and onion have been evaluated as inhibitors of chemical carcinogenesis. Among them diallylsulfide was mainly investigated and studies demonstrated its metabolization to the corresponding sulfoxide and sulfone. In this work, we report the investigation of the interaction between the diallylsulfide and its oxidized derivatives, through cyclic voltammetry, with horse heart cytocrome-c (on a modified electrode with 4-mercaptopyridine). Our results suggest that there is a reversible interaction between cytocrome-c and diallylsulfide and diallylsulfone and an irreversible interaction with the diallylsulfoxide.

Neste trabalho relatamos a preparação, por métodos mais eficientes e práticos, de derivados da 2,2’-bipiridina, que são importantes precursores para outros, tais como: 4,4’-dicarbóxi-2,2’-bipiridina (I), 6,6’-dicarbóxi-2,2’-bipiridina (II), 6,6’-dicarbotiamida - 2,2’-bipiridina (III), 4,4’-dinitro-N,N’-dióxido-2,2’-bipiridina (IV) e mono-N-óxido-2,2’-bipiridina (VII). A síntese dos ligantes inéditos 4,4’-diácido hidroxâmico-2,2’-bipiridina (V) e 6,6’-diácido hidroxâmico-2,2’-bipiridina (VI) é também relatada.

The preparation of key precursors for many 2,2’-bipyridine derivatives such as 4,4’-dicarboxy- 2,2’-bipyridine (I), 6,6’-dicarboxy-2,2’-bipyridine- acid (II), 4,4’-dinitro-2,2’-bipyridine-N,N-dioxide (III), 6,6’-dicarbothioamide-2,2’-bipyridine (IV) and mono-N-oxide-2,2’-bipyridine (VII) through more efficient methods is described. The syntheses of the novel ligands 4,4’-dihydroxamic-2,2’-bipyridine (V) and 6,6’-dihydroxamic-2,2’-bipyridine (VI) are also reported.