Organometallic ruthenium complexes with thiosemicarbazone ligands: Synthesis, structure and cytotoxicity of [(η\u3csup\u3e6\u3c/sup\u3e-p-cymene)Ru(NS)Cl]\u3csup\u3e+\u3c/sup\u3e (NS = 9-anthraldehyde thiosemicarbazones)

A series of half-sandwich arene ruthenium complexes containing bidentate thiosemicarbazone ligands have been synthesized and their biological activity investigated. The compounds have the general formula [(6-p-cymene)Ru(R-ATSC)Cl]X (ATSC = 9-anthraldehyde thiosemicarbazone and R = H, CH3 and C6H5). The crystal structure of [(6-p-cymene) Ru(MeATSC)Cl]Cl have been determined and represents the first structurally characterized arene–ruthenium half-sandwich complex with a thiosemicarbazone ligand. The complexes show good cytotoxic profiles against MCF-7 and MDA-MB-231 (breast adenocarcinoma) as well as HCT 116 and HT-29 (colorectal carcinoma) cell lines. [Refer to PDF for graphical abstract

Anticancer Activity and Biophysical Reactivity of Copper Complexes of 2-(benzo[d][1,3]dioxol-5-ylmethylene)-N-Alkylhydrazinecarbothioamides

A series of copper complexes were synthesized from benzo[d][1,3]dioxole-5-carbaldehyde (piperonal) thiosemicarbazones (RHpTSC where R = H, CH3, C2H5 or C6H5 (Ph)). The complexes show interesting variations in geometry depending on the thiosemicarbazone; a dinuclear complex [Cu(HpTSC)Cl]2, a mononuclear complex [Cu(RHpTSC)2Cl2] (R = CH3 or C2H5) and another mononuclear complex [Cu(PhHpTSC)(PhpTSC)Cl] was generated. The complexes bind in a moderately strong fashion to DNA with binding constants on the order of 104 M− 1. They are also strong binders of human serum albumin with binding constants near 104 M− 1. The complexes show good in vitro cytotoxic profiles against two human colon cancer cell lines (HCT-116 and HT29) and two human breast cancer cell lines (MCF-7 and MDA-MB-231) with IC50 values in the low millimolar concentration range

No experimental evidence for local competition in the nestling phase as a driving force for density-dependent avian clutch size

1. In birds, local competition for food between pairs during the nestling phase may affect nestling growth and survival. A decrease in clutch size with an increase in breeding density could be an adaptive response to this competition. To investigate whether breeding density causally affected the clutch size of great tits (Parus major), we manipulated breeding density in three out of eight study plots by increasing nest-box densities. We expected clutch size in these plots to be reduced compared to that in control plots. 2. We analysed both the effects of variation in annual mean density (between-year comparisons) and experimental density (within-year comparison between plots) on clutch size variation, the occurrence of second broods and nestling growth. We examined within-female variation in clutch size to determine whether individual responses explain the variation over years. 3. Over the 11 years, population breeding density increased (from 0·33 to 0·50 pairs ha–1) while clutch size and the occurrence of second broods decreased (respectively from 10·0 to 8·5 eggs and from 0·39 to 0·05), consistent with a negative density-dependent effect for the whole population. Nestling growth showed a declining but nonsignificant trend over years. 4. The decline in population clutch size over years was primarily explained by changes occurring within individuals rather than selective disappearance of individuals laying large clutches. 5. Within years, breeding density differed significantly between manipulated plots (0·16 pairs ha–1 vs. 0·77 pairs ha–1) but clutch size, occurrence of second broods and nestling growth were not affected by the experimental treatment, resulting in a discrepancy between the effects of experimental and annual variation in density on reproduction. 6. We discuss two hypotheses that could explain this discrepancy: (i) the decline in breeding performance over time was not due to density, but resulted from other, unknown factors. (ii) Density did cause the decline in breeding performance, but this was not due to local competition in the nestling phase. Instead, we suggest that competition acting in a different phase (e.g. before egg laying or after fledgling) was responsible for the density effect on clutch size among years.

Half-sandwich ruthenium–arene complexes with thiosemicarbazones: Synthesis and biological evaluation of [(η6-p-cymene)Ru(piperonal thiosemicarbazones)Cl]Cl complexes

The synthesis and characterization of a number of organometallic ruthenium(II) complexes containing a series of bidentate thiosemicarbazone ligands derived from piperonal is reported. The structure of compounds have been confirmed by spectroscopic analysis (IR and NMR) as well as X-ray crystallographic analysis of [(η6-p-cymene)Ru(pPhTSC)Cl]Cl (4) (pPhTSC is piperonal-N(4)-phenylthiosemicarbazone). The interaction of the complexes ([(η6-p-cymene)Ru(pEtTSC)Cl]Cl) (3) (pEtTSC is piperonal-N(4)-ethylthiosemicarbazone) and 4 with calf thymus DNA, human serum albumin (HSA) and pBR322 plasmid DNA were studied by spectroscopic, gel electrophoresis and hydrodynamic methods. The apparent binding constant for the interaction with DNA was determined to be 3.97 × 103 M− 1 and 4.07 × 103 M− 1 at 293 K for 3 and 4 respectively. The complexes bind strongly to HSA with binding constants of 2.94 × 104 M− 1 and 12.2 × 104 M− 1 at 296 K for 3 and 4 respectively. The in vitro anticancer activity of 3 and 4 has been evaluated against two human colon cancer cell line (HCT-116 and Caco-2) with IC50 values in the range of 26–150 μM. Both 3 and 4 show good activity as a catalytic inhibitor of human topoisomerase II at concentrations as low as 20 μM. The proficiency of 3 and 4 to act as antibacterial agents was also evaluated against six pathogenic bacterial strains with the best activity seen against Gram-positive strains. [Refer to PDF for graphical abstract

Synthesis and characterization of mixed-ligand diimine-piperonal thiosemicarbazone complexes of ruthenium(II): Biophysical investigations and biological evaluation as anticancer and antibacterial agents

We have used a novel microwave-assisted method developed in our laboratories to synthesize a series of ruthenium-thiosemicarbazone complexes. The new thiosemicarbazone ligands are derived from benzo[d][1,3]dioxole-5-carbaldehyde (piperonal) and the complexes are formulated as [(diimine)2Ru(TSC)](PF6)2 (where the TSC is the bidentate thiosemicarbazone ligand). The diimine in the complexes is either 2,2′-bipyridine or 1,10-phenanthroline. The complexes have been characterized by spectroscopic means (NMR, IR and UV–Vis) as well as by elemental analysis. We have studied the biophysical characteristics of the complexes by investigating their anti-oxidant ability as well as their ability to disrupt the function of the human topoisomerase II enzyme. The complexes are moderately strong binders of DNA with binding constants of 104 M−1. They are also strong binders of human serum albumin having binding constants on the order of 104 M−1. The complexes show good in vitro anticancer activity against human colon cancer cells, Caco-2 and HCT-116 and indeed show some cytotoxic selectivity for cancer cells. The IC50 values range from 7 to 159 μM (after 72 h drug incubation). They also have antibacterial activity against Gram-positive strains of pathogenic bacteria with IC50 values as low as 10 μM; little activity was seen against Gram-negative strains. It has been established that all the compounds are catalytic inhibitors of human topoisomerase II

Growth and heritability of size traits of Willow Tit Parus montanus nestlings-a supplementary feeding experiment

Growth and final body size of passerine birds may be influenced by both genetic and environmental factors, growth often being constrained by food limitation . This study investigates whether the growth of nestling Willow Tits Parus montanus is constrained due to food shortage and if offspring resemble their parents more in body size when parents are given access to additional amount of food (maggots). This was studied by comparing nestling growth in food-supplemented and control broods. During the study year nestling period coincided very well with peak abundance of caterpillars, the main prey of Willow Tits . This resulted in a very good growth of nestlings in the control group. Of the morphometric measurements, only wing length at 13 days of age differed between nestlings in fed broods and unfed controls . To control for the influence of heritable variation in growth a cross-fostering experiment was carried out with six broods. When eliminating the genetic factor, additional food showed a tendency to affect body mass at 13 days. The heritability of tarsus length was very high (h2 = 0.89 ± 0.28) . It is proposed that fast growth rather than large body size per se, is a life history strategy enabling an early nest-leaving and early establishment as a member of a winter flock, which increases an individual's survival chances during the first winter

Educação linguística na formação humana de sujeitos de classes populares: apropriação conceitual e perspectiva interdisciplinar

Dissertação (mestrado) - Universidade Federal de Santa Catarina, Centro de Comunicação e Expressão, Programa de Pós-Graduação em Linguística, Florianópolis, 2019.A pesquisa está pautada na concepção dialética do materialismo histórico, com filiação à Escola de Vigotski (2013 [1982]) e consiste em uma pesquisa-participante, tendo por objetivo problematizar o trabalho com a Educação Linguística em uma perspectiva que se quer interdisciplinar e em um contexto de educação popular, assumindo tal trabalho em aproximação à formação integral dos sujeitos, para o qual a dimensão conceitual que acompanha a aprendizagem da língua deve ser mantida. Norteados por ele, procuramos (i) identificar como/se a Educação Linguística estabelece diálogo com os outros componentes na ação formativa levada a efeito; (ii) apresentar e discutir de que forma a Educação Linguística é evocada na relação com as outras disciplinas nessa ação formativa; (iii) analisar em que medida o trabalho com a especificidade da língua em diálogo com as outras disciplinas numa configuração de trabalho como a posta é garantida. Tais objetivos dialogam com a questão geral de pesquisa: Há lugar para a Educação Linguística, orientada à formação integral dos sujeitos, em uma perspectiva que se quer interdisciplinar e em um contexto de educação popular? A presente questão desdobra-se em três questões-suporte: (i) Se/Como a Educação Linguística estabelece diálogo com os outros componentes curriculares em uma perspectiva interdisciplinar tal qual posta no campo em estudo? (ii) De que forma a Educação Linguística é evocada na relação com as outras disciplinas? (iii) É possível garantir o trabalho com a especificidade da língua em diálogo com as outras disciplinas numa configuração de trabalho como a posta? Movidos pela busca de resposta à questão geral de pesquisa, a dissertação está dividida em três capítulos, sendo o primeiro deles ocupado com a fundamentação teórico-epistemológica e as implicações teórico-metodológicas (SUCHODOLSKI, 2002 [1978]; LÖWY, 2013 [1987]; SAVIANI, 2012 [1983]; VIGOTSKI, 2012 [1983]; 2013 [1982]; MARTINS, 2015; TONET, 2011; HELLER, 2016 [1970]; DUARTE; MARTINS, 2013; DUARTE, 2016; BRITTO, 2012). No segundo capítulo, explicitamos a descrição dos procedimentos metodológicos, incluindo a caracterização do estudo e a caracterização do campo, que se assume efetivamente como um projeto de educação popular e que possui compromisso com a formação de sujeitos da classe trabalhadora. No terceiro e último capítulo, apresentamos o percurso analítico, que compreende a dialética marxista, assumindo o trabalho com a Educação Linguística em uma perspectiva que se quer interdisciplinar em um contexto de educação popular, em favor de uma formação humana integral. A elaboração teórica produzida nesta pesquisa é relevante para a Educação, pela discussão de concepções fundamentais ao trabalho do professor, e para a Educação Linguística, na medida em que subsidiam a reflexão e os potenciais avanços no processo de formação humana devido aos encontros de planejamento docente coletivo e da tentativa de apropriação conceitual que se deu em encontros de formação continuada.Abstract : The research is based on the dialectics conceptualization of the historical materialism, affiliated to Vygotsky?s Legacy (2013 [1982]), and it is participant-based research. This work aims at problematizing the work of language education, under an attempt of interdisciplinary perspective in a context of popular education, by unifying it towards the comprehensive human development, in which the conceptual dimension of language learning should be sustained. The objectives of this research are (i) identify how/if language education dialogues with other components in the formative assessment in action; (ii) present and discuss how language education is brought up in relation to other subjects in the formative assessment; (iii) analyze to what extent the work with the specificity of the language with other subjects under this configuration is maintained. Such objectives communicate with the main research question: is there a place for language education focused on comprehensive human development, under an attempt to an interdisciplinary perspective, and a context of popular education? The main question evolves in three other questions: (i) if/how does language education dialogue with other components from the curriculum under an interdisciplinary perspective, such as presented in this study? (ii) in which way is language education brought up in relation to other subjects? (iii) is it possible to guarantee the work with the specificities of the language by communicating with other subjects under the present configuration of work? Aiming at answering the main research question, this dissertation has three chapters. The first one presents the theoretical and epistemological foundation, and the theoretical and methodological implications (SUCHODOLSKI, 2002 [1978]; LÖWY, 2013 [1987]; SAVIANI, 2012 [1983]; VIGOTSKI, 2012 [1983]; 2013 [1982]; MARTINS, 2015; TONET, 2011; HELLER, 2016 [1970]; DUARTE; MARTINS, 2013; DUARTE, 2016; BRITTO, 2012). The second chapter introduces the method and procedures of this work, including the type of the study and field of research, which is a project of popular education, in which has a commitment to the formation of the working class. The third chapter presents the analytical process, under the Marxist dialectic, along with the work with language education in an attempt of interdisciplinary education of popular education, in favor of comprehensive human development. The theoretical material of this research is relevant to education, as the discussion of fundamental conceptions for the work of a teacher, and language education, to the extent of promoting reflection and promising growth in the process of human development due to encounters of unified teacher planning, and the attempt of conceptual appropriation that resulted from continuous training meetings