Oxidovanadium complexes with tridentate aroylhydrazone as catalyst precursors for solvent-free microwave-assisted oxidation of alcohols

Aroylhydrazone oxidovanadium compounds, viz, the oxidoethoxidovanadium(V) [VO(OEt)L1] (1) (H2L =salicylaldehyde-2-hydroxybenzoylhydrazone), the salt like dioxidovanadium(V) (NH3CH2CH2OH)(+) [VO2L](-) (2), the mixed-ligand oxidovanadium(V) [VO(hq)L](Hhq = 8-hydroxyquinoline) (3) and the vanadium(IV) [VO(phen)L] (phen=1,10-phenanthroline) (4) complexes (3 and 4 obtained by the first time), have been tested as catalysts for solvent-free microwave-assisted oxidation of aromatic and alicyclic secondary alcohols with tert-butylhydroperoxide. A facile, efficient and selective solvent-free synthesis of ketones was achieved with yields up to 99% (TON= 497, TOF= 993 h(-1) for 3) and 58% (TON =291, TOF= 581 h(-1) for 2) for acetophenone and cyclohexanone, respectively, after 30 min under low power (25W) microwave irradiation. (C) 2015 Elsevier B.V. All rights reserved.

Solvent-free microwave-assisted peroxidative oxidation of alcohols catalyzed by Iron(III)-TEMPO catalytic systems

The iron(III) complexes [H(EtOH)][FeCl2(L)(2)] (1), [H(2)bipy](1/2)[FeCl2(L)(2)].DMF (2) and [FeCl2(L)(2,2'-bipy)] (3) (L = 3-amino-2-pyrazinecarboxylate; H(2)bipy = doubly protonated 4,4'-bipyridine; 2,2'-bipy = 2,2'-bipyridine, DMF = dimethylformamide) have been synthesized and fully characterized by IR, elemental and single-crystal X-ray diffraction analyses, as well as by electrochemical methods. Complexes 1 and 2 have similar mononuclear structures containing different guest molecules (protonated ethanol for 1 and doubly protonated 4,4'-bipyridine for 2) in their lattices, whereas the complex 3 has one 3-amino-2-pyrazinecarboxylate and a 2,2'-bipyridine ligand. They show a high catalytic activity for the low power (10 W) solvent-free microwave assisted peroxidative oxidation of 1-phenylethanol, leading, in the presence of TEMPO, to quantitative yields of acetophenone [TOFs up to 8.1 x 10(3) h(-1), (3)] after 1 h. Moreover, the catalysts are of easy recovery and reused, at least for four consecutive cycles, maintaining 83 % of the initial activity and concomitant rather high selectivity. 3-Amino-2-pyrazinecarboxylic acid is used to synthesize three new iron(III) complexes which act as heterogeneous catalysts for the solvent-free microwave-assisted peroxidative oxidation of 1-phenylethanol.

The impact of the implementation of the Basel III recommendations on the capital of portuguese banks

This paper analyses the impact of the implementation of the Basel III recommendations, using the standard method, in Portugal. For our study, we used the annual reports of 31st of December of 2012, and found out that out of the fourteen banks that published annual reports, only six satisfied the minimum ratios laid out by BCBS. Till 2012, Portuguese banks used an internal ratings method based on the Basel II recommendations known as notice 6/2010 of the Portuguese central bank, Banco de Portugal. As the implementation of the recommendations of Basel III in the EU via the Credit Review Directive IV is scheduled for 2014 and later years, Portuguese banks may severely contract credit upon implementation, as that is the easiest, fastest and cheapest way for banks to satisfy the minimum ratio requirements as compared to an increase of capital or credit spreads.

Desenvolvimento e capital humano no sistema de educação e avaliação do desempenho

Apresentação feita na Escola 3 / Secundária Quinta do Marquês, em Oeiras, a 27 de Janeiro de 2007.

MANFOP : um instrumento de apoio ao desenvolvimento do capital humano nas organizações

Poster apresentado no 7º Congresso Nacional da Administração Pública

O Instituto Nacional de Administração, I.P. e a política de valorização do capital humano da Administração Pública Portuguesa

Comunicação apresentada no curso avançado em gestão da formação, 2010.

Investimento no capital humano da AP, factor essencial na resolução da crise

Comunicação apresentada no 8º Congresso Nacional de Administração Pública – Desafios e Soluções, em Carcavelos de 21 a 22 de Novembro de 2011.

Monitoring the ex-vivo expansion of human mesenchymal stem/stromal cells in xeno-free microcarrier-based reactor systems by MIR spectroscopy

Human mesenchymal stem/stromal cells (MSCs) have received considerable attention in the field of cell-based therapies due to their high differentiation potential and ability to modulate immune responses. However, since these cells can only be isolated in very low quantities, successful realization of these therapies requires MSCs ex-vivo expansion to achieve relevant cell doses. The metabolic activity is one of the parameters often monitored during MSCs cultivation by using expensive multi-analytical methods, some of them time-consuming. The present work evaluates the use of mid-infrared (MIR) spectroscopy, through rapid and economic high-throughput analyses associated to multivariate data analysis, to monitor three different MSCs cultivation runs conducted in spinner flasks, under xeno-free culture conditions, which differ in the type of microcarriers used and the culture feeding strategy applied. After evaluating diverse spectral preprocessing techniques, the optimized partial least square (PLS) regression models based on the MIR spectra to estimate the glucose, lactate and ammonia concentrations yielded high coefficients of determination (R2 ≥ 0.98, ≥0.98, and ≥0.94, respectively) and low prediction errors (RMSECV ≤ 4.7%, ≤4.4% and ≤5.7%, respectively). Besides PLS models valid for specific expansion protocols, a robust model simultaneously valid for the three processes was also built for predicting glucose, lactate and ammonia, yielding a R2 of 0.95, 0.97 and 0.86, and a RMSECV of 0.33, 0.57, and 0.09 mM, respectively. Therefore, MIR spectroscopy combined with multivariate data analysis represents a promising tool for both optimization and control of MSCs expansion processes.

Knowledge management systems and intellectual capital measurement in portuguese organizations: a case study

This paper presents the results of an exploratory study on knowledge management in Portuguese organizations. The study was based on a survey sent to one hundred of the main Portuguese organizations, in order to know their current practices relating knowledge management systems (KMS) usage and intellectual capital (IC) measurement. With this study, we attempted to understand what are the main tools used to support KM processes and activities in the organizations, and what metrics are pointed by organizations to measure their knowledge assets.

A Influência da teoria da agência na estrutura de capital na indústria do calçado

apresentado ao Instituto de Contabilidade e Administração do Porto para a Dissertação de Mestrado para obtenção do grau de Mestre em Contabilidade e Finanças sob orientação do Mestre Adalmiro Álvaro Malheiro de Castro Andrade Pereira

PEC e a vertente empresarial: impacto na gestão de tesouraria das PME

Dissertação de Mestrado apresentada ao Instituto de Contabilidade e Administração do Porto para a obtenção do grau de Mestre em Contabilidade e Finanças, sob orientação de Cláudia Maria Pereira Esta versão contém as críticas e sugestões dos elementos do júri.

Reforma da administração pública, produtividade e capital social

Comunicação apresentada no 2ª Congresso Nacional de Administração Pública em Lisboa, de 3 a 4 de Novembro de 2004.

Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols

A one-pot template reaction of sodium 2-(2-(dicyanomethylene) hydrazinyl) benzenesulfonate (NaHL1) with water and manganese(II) acetate tetrahydrate led to the mononuclear complex [Mn(H2O)(6)](HL1a)(2)center dot 4H(2)O (1), where (HL1a) -= 2-(SO3-)C6H4(NH)=N=C(C N) (CONH2) is the carboxamide species derived from nucleophilic attack of water on a cyano group of (HL1) . The copper tetramer [Cu-4(H2O)(10)(-) (1 kappa N: kappa O-2: kappa O, 2 kappa N: k(O)-L-2)(2)]center dot 2H(2)O (2) was obtained from reaction of Cu(NO3)(2)center dot 2.5H(2)O with sodium 5-(2( 4,4-dimethyl-2,6-dioxocyclohexylidene) hydrazinyl)-4-hydroxybenzene-1,3-disulfonate (Na2H2L2). Both complexes were characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray diffraction. They exhibit a high catalytic activity for the solvent-and additive-free microwave (MW) assisted oxidation of primary and secondary alcohols with tert-butylhydroperoxide, leading to yields of the oxidized products up to 85.5% and TOFs up to 1.90 x 103 h(-1) after 1 h under low power (5-10 W) MW irradiation. Moreover, the heterogeneous catalysts are easily recovered and reused, at least for three consecutive cycles, maintaining 89% of the initial activity and a high selectivity.

Os determinantes da estrutura de capital das empresas exportadoras portuguesas

Este trabalho tem como objetivo verificar os determinantes da estrutura de capital das empresas exportadoras portuguesas, comparando, sempre que possível, os resultados obtidos com outros trabalhos já desenvolvidos sobre o tema. Aplicando o Modelo dos Efeitos Fixos (MEF) a uma amostra de 7.001 empresas no período 2007-2013, concluiu-se que os determinantes com maior significância no nível de endividamento empresarial são: a rendibilidade, a dimensão, o crescimento e ainda os outros benefícos fiscais. Em relação às exportações, verificou-se através da variável dummy “exportar”, que o facto de as empresas terem exportações superiores a 10% das vendas totais, têm uma relação positiva com o endividamento de médio e longo prazo mas negativa com o endividamento de curto prazo. Perante estes resultados admitimos que as empresas exportadoras ao diversificarem (na fase inicial) o seu portfólio de clientes conseguem maiores níveis de cash-flows, o que as dispensa de algum endividamento de curto prazo, mas no médio e longo prazo as necessidades de investimento para fazer face a mercados muito competitivos está associada a um maior nível de endividamento. Relativamente à importância explicativa das variáveis “peso das vendas para o mercado comunitário” e “peso das vendas para o mercado extra comunitário”, curiosamente, apresentam resultados diferentes; o peso das vendas para o mercado extra comunitário não revela relação significativa com o endividamento mas já o peso das vendas para o mercado comunitário tem uma relação positiva com endividamento a curto prazo e negativa com o endividamento de médio e longo prazo.