Y Trinuclear Cu-II structural isomers coordination, magnetism, electrochemistry and catalytic activity towards the oxidation of alkanes

The reaction of the Schiff base (3,5-di-tert-butyl-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (H3L) with copper(II) nitrate, acetate or metaborate has led to the isomeric complexes [Cu-3(L)(2)(MeOH)(4)] (1), [Cu-3(L)(2)(MeOH)(2)]2MeOH (2) and [Cu-3(L)(2)(MeOH)(4)] (3), respectively, in which the ligand L exhibits dianionic (HL2-, in 1) or trianionic (L3-, in 2 and 3) pentadentate 1O,O,N:2N,O chelation modes. Complexes 1-3 were characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography, electrochemical methods and variable-temperature magnetic susceptibility measurements, which indicated that the intratrimer antiferromagnetic coupling is strong in the three complexes and that there exists very weak ferromagnetic intermolecular interactions in 1 but weak antiferromagnetic intermolecular interactions in both 2 and 3. Electrochemical experiments showed that in complexes 1-3 the Cu-II ions can be reduced, in distinct steps, to Cu-I and Cu-0. All the complexes act as efficient catalyst precursors under mild conditions for the peroxidative oxidation of cyclohexane to cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone, leading to overall yields (based on the alkane) of up to 31% (TON = 1.55x10(3)) after 6 h in the presence of pyrazinecarboxylic acid.

Sulfonated Schiff base copper(ii) complexes as efficient and selective catalysts in alcohol oxidation: syntheses and crystal structures

The reaction between 2-aminobenzenesulfonic acid and 2-hydroxy-3-methoxybenzaldehyde produces the acyclic Schiff base 2-[(2-hydroxy-3-methoxyphenyl) methylideneamino] benzenesulfonic acid (H2L center dot 3H(2)O) (1). In situ reactions of this compound with Cu(II) salts and, eventually, in the presence of pyridine (py) or 2,2'-bipyridine (2,2'-bipy) lead to the formation of the mononuclear complexes [CuL(H2O)(2)] (2) and [CuL(2,2'-bipy)]center dot DMF center dot H2O (3) and the diphenoxo-bridged dicopper compounds [CuL(py)](2) (4) and [CuL(EtOH)](2)center dot 2H(2)O (5). In 2-5 the L-2-ligand acts as a tridentate chelating species by means of one of the O-sulfonate atoms, the O-phenoxo and the N-atoms. The remaining coordination sites are then occupied by H2O (in 2), 2,2'-bipyridine (in 3), pyridine (in 4) or EtOH (in 5). Hydrogen bond interactions resulted in R-2(2) (14) and in R-4(4)(12) graph sets leading to dimeric species (in 2 and 3, respectively), 1D chain associations (in 2 and 5) or a 2D network (1). Complexes 2-5 are applied as selective catalysts for the homogeneous peroxidative (with tert-butylhydroperoxide, TBHP) oxidation of primary and secondary alcohols, under solvent-and additive-free conditions and under low power microwave (MW) irradiation. A quantitative yield of acetophenone was obtained by oxidation of 1-phenylethanol with compound 4 [TOFs up to 7.6 x 10(3) h(-1)] after 20 min of MW irradiation, whereas the oxidation of benzyl alcohol to benzaldehyde is less effective (TOF 992 h(-1)). The selectivity of 4 to oxidize the alcohol relative to the ene function is demonstrated when using cinnamyl alcohol as substrate.

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.

Optimização da produtividade lipídica da microalga Arthrospira platensis como matéria-prima para biocombustíveis

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Bioenergia

Novel Prostate Specific Antigen plastic antibody designed withcharged binding sites for an improved protein binding and itsapplication in a biosensor of potentiometric transduction

This work shows that the synthesis of protein plastic antibodies tailored with selected charged monomersaround the binding site enhances protein binding. These charged receptor sites are placed over a neutralpolymeric matrix, thus inducing a suitable orientation the protein reception to its site. This is confirmed bypreparing control materials with neutral monomers and also with non-imprinted template. This concepthas been applied here to Prostate Specific Antigen (PSA), the protein of choice for screening prostate can-cer throughout the population, with serum levels >10 ng/mL pointing out a high probability of associatedcancer.Protein Imprinted Materials with charged binding sites (C/PIM) have been produced by surfaceimprinting over graphene layers to which the protein was first covalently attached. Vinylben-zyl(trimethylammonium chloride) and vinyl benzoate were introduced as charged monomers labellingthe binding site and were allowed to self-organize around the protein. The subsequent polymerizationwas made by radical polymerization of vinylbenzene. Neutral PIM (N/PIM) prepared without orientedcharges and non imprinted materials (NIM) obtained without template were used as controls.These materials were used to develop simple and inexpensive potentiometric sensor for PSA. Theywere included as ionophores in plasticized PVC membranes, and tested over electrodes of solid or liq-uid conductive contacts, made of conductive carbon over a syringe or of inner reference solution overmicropipette tips. The electrodes with charged monomers showed a more stable and sensitive response,with an average slope of -44.2 mV/decade and a detection limit of 5.8 × 10−11mol/L (2 ng/mL). The cor-responding non-imprinted sensors showed lower sensitivity, with average slopes of -24.8 mV/decade.The best sensors were successfully applied to the analysis of serum, with recoveries ranging from 96.9to 106.1% and relative errors of 6.8%.

Oriented Tailoring of Plastic Antibodies for Prostate Specific Antigen and Application of the Imprinted Material as Ionophore in Potentiometric Detection

Prostate Specific Antigen (PSA) is the biomarker of choice for screening prostate cancer throughout the population, with PSA values above 10 ng/mL pointing out a high probability of associated cancer1. According to the most recent World Health Organization (WHO) data, prostate cancer is the commonest form of cancer in men in Europe2. Early detection of prostate cancer is thus very important and is currently made by screening PSA in men over 45 years old, combined with other alterations in serum and urine parameters. PSA is a glycoprotein with a molecular mass of approximately 32 kDa consisting of one polypeptide chain, which is produced by the secretory epithelium of human prostate. Currently, the standard methods available for PSA screening are immunoassays like Enzyme-Linked Immunoabsorbent Assay (ELISA). These methods are highly sensitive and specific for the detection of PSA, but they require expensive laboratory facilities and high qualify personal resources. Other highly sensitive and specific methods for the detection of PSA have also become available and are in its majority immunobiosensors1,3-5, relying on antibodies. Less expensive methods producing quicker responses are thus needed, which may be achieved by synthesizing artificial antibodies by means of molecular imprinting techniques. These should also be coupled to simple and low cost devices, such as those of the potentiometric kind, one approach that has been proven successful6. Potentiometric sensors offer the advantage of selectivity and portability for use in point-of-care and have been widely recognized as potential analytical tools in this field. The inherent method is simple, precise, accurate and inexpensive regarding reagent consumption and equipment involved. Thus, this work proposes a new plastic antibody for PSA, designed over the surface of graphene layers extracted from graphite. Charged monomers were used to enable an oriented tailoring of the PSA rebinding sites. Uncharged monomers were used as control. These materials were used as ionophores in conventional solid-contact graphite electrodes. The obtained results showed that the imprinted materials displayed a selective response to PSA. The electrodes with charged monomers showed a more stable and sensitive response, with an average slope of -44.2 mV/decade and a detection limit of 5.8X10-11 mol/L (2 ng/mL). The corresponding non-imprinted sensors showed smaller sensitivity, with average slopes of -24.8 mV/decade. The best sensors were successfully applied to the analysis of serum samples, with percentage recoveries of 106.5% and relatives errors of 6.5%.

Conteúdo em Polifenóis totais do vinho em contacto com aparas de madeira e subsequentes características colorimétricas

Neste trabalho fez-se o estudo do conteúdo de polifenóis totais (PT) por reação de Folin-Ciocalteau e das características colorimétricas por espetrofotometria e colorimetria de dois tipos de vinho: branco (Vb) e tinto (Vt) e o estudo evolutivo das mesmas características em soluções hidroalcoólicas (SH), miméticas ao vinho em teor alcoólico e pH. Tanto os vinhos como as soluções estiveram em contacto com vários tipos de espécies botânicas com potencial interesse enológico: Acácia (AC), Cerejeira (CJ), Castanheiro (CT) e Carvalho (CN) em concentrações de 50 g/L, 2 g/L e 6 g/L para as SH, Vb e Vt respetivamente todas elas com quatro graus de queima e duas morfologias: aparas e dominós (apenas SH). As SH-aparas estiveram 11 dias em contacto com as madeiras onde ao final do dia 9 se registou um teor de PT de 1128 (AC), 321 (CJ), 2346 (CT) e 1815 (CN) mg GEA/L para todos com queima ligeira, à exceção de castanheiro, que obteve o máximo na madeira sem queima. Nas SH-dominós o máximo de PT registou-se em carvalho sem queima com 1897 mg GAE/L, quando em contacto com a madeira num período superior a 9 meses. O estudo dos PT nos vinhos mostrou que as madeiras são capazes de os enriquecer com este tipo de compostos registando-se um aumento máximo de 74,44 mg GAE/L e de 979,93 mg GAE/L para os Vb e Vt respetivamente. No estudo colorimétrico por espetrofotometria foram avaliados os parâmetros CIELab de todas as SH e observou-se que L* (luminosidade) tende a diminuir com o grau de queima e com o tempo para todas as madeiras. O parâmetro a* (verde/vermelho) em AC e CJ diminui com os dias e com o grau de queima representando uma diminuição da componente vermelha. O inverso é observado em CT e CN. Por fim, b* (azul/amarelo) tende a aumentar em todas as SH com os dias e a queima tornando a solução mais amarela. Comparando os vinhos com as suas testemunhas, em Vb L* e b* aumentam refletindo-se num aumento da cor amarela e a* é mantido. Nos Vt, L* diminui quando na presença das madeiras e a* e b* aumentam acrescendo a sua componente vermelha. Fez-se a avaliação de alguns voláteis das SH por GC/MS onde foram encontrados compostos com interesses organoléticos como é o caso da lactona do whisky nalgumas graus de queima para as espécies botânicas de cerejeira e carvalho.

Calogênese do híbrido Theobroma grandiflorum x T. obovatum (Sterculiaceae)

O declínio da cacauicultura na amazônia tem sido causado pela doença vassoura-de-bruxa (Crinipellis perniciosa). Um híbrido interespecífico do mesmo gênero (Theobroma grandiflorum x T. obovatum) tem demonstrando resistência a esta doença. Avaliou-se a calogênese deste híbrido com a finalidade de sua propagação massiva. Os explantes usados (tegumento, cotilédone e embrião) foram postos para desenvolver em condições estéreis em meio de cultura LPm mais água de coco (50 ml/l), glucose (20 g/l), 2,4 - D (2 mg/l), Thidiazuron - TDZ nas concentrações de 0, 5 e 10 µg/l, carvão ativado (2 g/l) em gelrite (2 g/l) a um pH de 5,8. Cada concentração de TDZ x tipo de tecido foi considerado um tratamento. As culturas foram mantidas no escuro, à temperatura de 22 ± 2 ºC. Os tecidos não mostraram diferenças significativas quanto a proporção do explante recoberto por calos (p= 0,14) embora notou-se que nos cotilédones tenha sido maior. A dosagem de TDZ nitidamente não influenciou no recobrimento de calos (p= 0,94). Quanto a freqüência, os tecidos mostraram diferentes capacidades de desenvolver calos (p= 0,02) sem mostrar-se influenciados pela dosagem de TDZ (p = 0,66). Os explantes de cotilédones foram os que formaram calos em maior freqüência. Houve uma leve tendência de que quanto menor a dosagem de TDZ maior a freqüência de calos obtidos. Não foi constatada interação entre tipo de calo/frasco x dosagem de TDZ (p = 0,32).

Homocisteína, folato e vitamina B12 em pacientes colombianos portadores de coronariopatia

OBJETIVO: Determinar a existência de associação entre os níveis plasmáticos de homocisteína, folato ou vitamina B12 e síndrome coronariana aguda em pacientes colombianos. MÉTODOS: Estudo caso-controle: foram 50 pacientes portadores de síndrome coronariana aguda e 50 pacientes ambulatoriais sem síndrome coronariana. Foram medidos os níveis de homocisteína, folato e vitamina B12 por meio de imunoensaio por quimioluminescência. Foram também medidos os níveis de colesterol e frações, triglicérides, uréia, creatinina, hemoglobina e hematócrito. RESULTADOS: As concentrações plasmáticas médias de homocisteína foram significativamente diferentes entre os casos (12,4 µmol/l ± 6,0) e os controles (9,7 µmol/l ± 2,4), p=0,01. Os níveis de ácido fólico dos casos foram menores que os dos controles (respectivamente 10,5 ng/ml ± 3,5 x 12,6 ng/ml ± 3,6; p=0,01). Foi observada relação inversa entre os níveis de folato e os de homocisteína. Não houve relação entre os níveis de vitamina B12 e os de homocisteína. Houve diferença significativa nos níveis de triglicérides entre os grupos caso e controle (respectivamente 136,91 ± 67,27 x 174,3 ± 77,6; p=0,01). A razão das chances para hiper-homocisteinemia na síndrome coronariana aguda foi de 4,45 (intervalo de confiança de 95%: 1,5 - 13,3). CONCLUSÃO: O presente estudo demonstrou associação significativa entre os níveis de homocisteína e síndrome coronariana aguda em pacientes colombianos semelhante à encontrada em populações européias e norte-americanas. Houve correlação negativa entre os níveis plasmáticos de homocisteína e os de folato. Não houve associação entre os níveis plasmáticos de homocisteína e os de vitamina B12.

Solução salina hipertônica para prevenção de insuficiência renal em pacientes com insuficiência cardíaca descompensada e hiponatremia

FUNDAMENTO: Hiponatremia e fenômenos congestivos indicam mau prognóstico na insuficiência cardíaca descompensada. A ocorrência de insuficiência renal está associada a aumento do risco de morte. OBJETIVO: Avaliar a segurança e a eficácia da solução hipertônica em pacientes com insuficiência cardíaca descompensada para prevenção de insuficiência renal. MÉTODOS: Participaram do estudo pacientes com insuficiência cardíaca descompensada, congestão e hiponatremia. Além do tratamento padrão, os pacientes receberam solução salina hipertônica, e foram submetidos a avaliação tanto clínica como laboratorial. RESULTADOS: Foram incluídos 9 pacientes. A média das idades dos pacientes foi de 55 + 14,2 anos, sendo 5 (55,5%) do sexo masculino e 4 (44,5%), do feminino. Todos apresentavam classe funcional III-IV da New York Heart Association (NYHA), e 5 (55,5%) recebiam dobutamina. Todos apresentaram creatinina inicial acima de 1,4 mg/dl. A tonicidade média da solução foi de 4,39% + 0,018% (2,5% a 7,5%) e a duração do tratamento foi de 4,9 dias + 4,1 dias (1 dia a 15 dias). Não houve efeitos adversos graves; em nenhum caso houve piora clínica ou distúrbios neurológicos; hipocalemia ocorreu em 4 (44,5%) casos. A comparação das variáveis pré- e pós-tratamento demonstrou queda da uréia (105 mg/dl + 74,8 mg/dl vs. 88 mg/dl + 79,4 mg/dl; p = 0,03) e aumento do volume urinário (1.183 ml/dia vs. 1.778 ml/dia; p = 0,03); houve tendência a redução da creatinina (2,0 mg/dl + 0,8 mg/dl vs. 1,7 mg/dl + 1,0 mg/dl; p = 0,08). Apesar da elevação do valor do sódio (131 mEq/l + 2,8 mEq/l vs. 134 mEq/l + 4,9 mEq/l) e da redução do peso (69,5 kg + 18,6 kg vs. 68,2 kg + 17,1 kg), não houve diferença estatisticamente significante. CONCLUSÃO: O uso de solução salina hipertônica em pacientes com insuficiência cardíaca descompensada pode ser método terapêutico seguro e potencialmente relacionado a melhora clínica e de prevenção da insuficiência renal.

Ecology and natural history of Akodon lindberghi (Rodentia, Sigmodontinae) in southeastern Brazil

We studied the ecology and natural history of the globally threatened and poorly known Akodon lindberghi Hershkovitz, 1990 in Parque Nacional da Serra da Canastra (PNSC) and Juiz de Fora (JF), southeastern Brazil. From November 1998 to September 2001 a total of 131 individuals were captured in wire-cage live-traps and 52 by pitfalls traps. They were all marked and released at the site. The largest abundances were registered during the dry season, and most of the captures occurred in open habitats. The mean body mass of the two populations was significantly different (18.1 g at PNSC versus 13.1 g at JF; H = 46.2678, g.l.=2, p<0.001). In PNSC, individuals were reproductively active from August to February, and juveniles were present from May to August. The results suggest that the changes in vegetation structure caused by deforestation and intensive agricultural activities could increase the predation rate, affecting the mean body mass of the population.

HLA photoaffinity labeling reveals overlapping binding of homologous melanoma-associated gene peptides by HLA-A1, HLA-A29, and HLA-B44.

Melanoma-associated genes (MAGEs) encode tumor-specific antigens that can be recognized by CD8+ cytotoxic T lymphocytes. To investigate the interaction of the HLA-A1-restricted MAGE-1 peptide 161-169 (EADPT-GHSY) with HLA class I molecules, photoreactive derivatives were prepared by single amino acid substitution with N beta-[iodo-4-azidosalicyloyl]-L-2,3-diaminopropionic acid. These derivatives were tested for their ability to bind to, and to photoaffinity-label, HLA-A1 on C1R.A1 cells. Only the derivatives containing the photoreactive amino acid in position 1 or 7 fulfilled both criteria. Testing the former derivative on 14 lymphoid cell lines expressing over 44 different HLA class I molecules indicated that it efficiently photoaffinity-labeled not only HLA-A1, but possibility also HLA-A29 and HLA-B44. MAGE peptide binding by HLA-A29 and HLA-B44 was confirmed by photoaffinity labeling with photoreactive MAGE-3 peptide derivatives on C1R.A29 and C1R.B44 cells, respectively. The different photoaffinity labeling systems were used to access the ability of the homologous peptides derived from MAGE-1, -2, -3, -4a, -4b, -6, and -12 to bind to HLA-A1, HLA-A29, and HLA-B44. All but the MAGE-2 and MAGE-12 nonapeptides efficiently inhibited photoaffinity labeling of HLA-A1, which is in agreement with the known HLA-A1 peptide-binding motif (acidic residue in P3 and C-terminal tyrosine). In contrast, photoaffinity labeling of HLA-A29 was efficiently inhibited by these as well as by the MAGE-3 and MAGE-6 nonapeptides. Finally, the HLA-B44 photoaffinity labeling, unlike the HLA-A1 and HLA-A29 labeling, was inhibited more efficiently by the corresponding MAGE decapeptides, which is consistent with the reported HLA-B44 peptide-binding motif (glutamic acid in P2, and C-terminal tyrosine or phenylalanine). The overlapping binding of homologous MAGE peptides by HLA-A1, A29, and B44 is based on different binding principles and may have implications for immunotherapy of MAGE-positive tumors.

Structural components in functional data

Analyzing functional data often leads to finding common factors, for which functional principal component analysis proves to be a useful tool to summarize and characterize the random variation in a function space. The representation in terms of eigenfunctions is optimal in the sense of L-2 approximation. However, the eigenfunctions are not always directed towards an interesting and interpretable direction in the context of functional data and thus could obscure the underlying structure. To overcome such difficulty, an alternative to functional principal component analysis is proposed that produces directed components which may be more informative and easier to interpret. These structural components are similar to principal components, but are adapted to situations in which the domain of the function may be decomposed into disjoint intervals such that there is effectively independence between intervals and positive correlation within intervals. The approach is demonstrated with synthetic examples as well as real data. Properties for special cases are also studied.

Catalytic and anticancer activities of sawhorse-type diruthenium tetracarbonyl complexes derived from fluorinated fatty acids

The reaction of fluorinated fatty acids, perfluorobutyric acid (C3F7CO2H), and perfluorododecanoic acid (C11F23CO2H), with dodecacarbonyltriruthenium (Ru-3(CO)(12)) under reflux in tetrahydrofuran, followed by addition of two-electron donors (L) such as pyridine, 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane, or triphenylphosphine, gives stable diruthenium complexes Ru-2(CO)(4)((2)-(2)-O2CC3F7)(2)(L)(2) (1a, L=C5H5N; 1b, L=PTA; 1c, L=PPh3) and Ru-2(CO)(4)((2)-(2)-O2CC11F23)(2)(L)(2) (2a, L=C5H5N; 2b, L=PTA; 2c, L=PPh3). The catalytic activity of the complexes for hydrogenation of styrene under supercritical carbon dioxide has been assessed and compared to the analogous triphenylphosphine complexes with non-fluorinated carboxylato groups Ru-2(CO)(4)((2)-(2)-O2CC3H7)(2)(PPh3)(2) (3) and Ru-2(CO)(4)((2)-(2)-O2CC11H23)(2)(PPh3)(2) (4). In addition, the cytotoxicities of the fluorinated complexes 1 were also evaluated on several human cancer cell lines (A2780, A549, Me300, HeLa). The complexes appear to be moderately cytotoxic, showing greater activity on the Me300 melanoma cells. Single-crystal X-ray structure analyses of 1a and 3 show the typical sawhorse-type arrangement of the diruthenium tetracarbonyl backbone with two bridging carboxylates and two terminal ligands occupying the axial positions.

Focused time-lapse inversion of radio and audio magnetotelluric data

Geoelectrical techniques are widely used to monitor groundwater processes, while surprisingly few studies have considered audio (AMT) and radio (RMT) magnetotellurics for such purposes. In this numerical investigation, we analyze to what extent inversion results based on AMT and RMT monitoring data can be improved by (1) time-lapse difference inversion; (2) incorporation of statistical information about the expected model update (i.e., the model regularization is based on a geostatistical model); (3) using alternative model norms to quantify temporal changes (i.e., approximations of l(1) and Cauchy norms using iteratively reweighted least-squares), (4) constraining model updates to predefined ranges (i.e., using Lagrange Multipliers to only allow either increases or decreases of electrical resistivity with respect to background conditions). To do so, we consider a simple illustrative model and a more realistic test case related to seawater intrusion. The results are encouraging and show significant improvements when using time-lapse difference inversion with non l(2) model norms. Artifacts that may arise when imposing compactness of regions with temporal changes can be suppressed through inequality constraints to yield models without oscillations outside the true region of temporal changes. Based on these results, we recommend approximate l(1)-norm solutions as they can resolve both sharp and smooth interfaces within the same model. (C) 2012 Elsevier B.V. All rights reserved.