Impact of land-use on soil organic matter quality in south-western Australia - characterization with C-13 CP/MAS NMR spectroscopy

The influence of change in land-use from native vegetation to pasture (20-71 yr after conversion), and subsequent change from pasture to eucalypt plantation (7-10 yr after conversion) on soil organic matter quality was investigated using C-13 CP/MAS NMR spectroscopy. We studied surface soil (0-10 cm) from six sites representing a range of soil, and climate types from south-western Australia. Total C in the samples ranged from 1.6 to 5.5%, but the relative proportions of the four primary spectral regions (alkyl, O-alkyl, aromatic and carboxylic) were similar across the sites, and changes due to land-use at each site were relatively minor. Main impacts of changed land-use were higher O-alkyl (carbohydrate) material under pasture than under native vegetation and plantation (P = 0.048), and lower aromatic C under pasture than under native vegetation (P = 0.027). The decrease in aromatic C in pasture soils was related to time since clearing. (C) 2002 Elsevier Science Ltd. All rights reserved.

Enhancing the immunogenicity and modulating the fine epitope recognition of antisera to a helical group A streptococcal peptide vaccine candidate from the M protein using lipid-core peptide technology

A conserved helical peptide vaccine candidate from the M protein of group A streptococci, p145, has been described. Minimal epitopes within p145 have been defined and an epitope recognized by protective antibodies, but not by autoreactive T cells, has been identified. When administered to mice, p145 has low immunogenicity. Many boosts of peptide are required to achieve a high antibody titre (> 12 800). To attempt to overcome this low immunogenicity, lipid-core peptide technology was employed. Lipid-core peptides (LCP) consist of an oligomeric polylysine core, with multiple copies of the peptide of choice, conjugated to a series of lipoamino acids, which acts as an anchor for the antigen. Seven different LCP constructs based on the p145 peptide sequence were synthesized (LCP1-->LCP7) and the immunogenicity of the compounds examined. The most immunogenic constructs contained the longest alkyl side-chains. The number of lipoamino acids in the constructs affected the immunogenicity and spacing between the alkyl side-chains increased immunogenicity. An increase in immunogenicity (enzyme-linked immunosorbent assay (ELISA) titres) of up to 100-fold was demonstrated using this technology and some constructs without adjuvant were more immunogenic than p145 administered with complete Freund's adjuvant (CFA). The fine specificity of the induced antibody response differed for the different constructs but one construct, LCP4, induced antibodies of identical fine specificity to those found in endemic human serum. Opsonic activity of LCP4 antisera was more than double that of p145 antisera. These data show the potential for LCP technology to both enhance immunogenicity of complex peptides and to focus the immune response towards or away from critical epitopes.

Composition and quality of harvest residues and soil organic matter under windrow residue management in young hoop pine plantations as revealed by solid-state C-13 NMR spectroscopy

Solid-state C-13 nuclear magnetic resonance (NMR) with cross-polarisation (CP) and magic-angle-spinning (MAS) was used to: (a) examine the changes in carbon (C) composition of windrowed harvest residues during the first 3 years of hoop pine plantations in subtropical Australia; (b) assess the impacts of windrowed harvest residues on soil organic matter (SOM) composition and quality in the 0-10 cm soil layer. Harvest residues were collected from 0-, 1-, 2- and 3-year-old windrows of ca. 2.5 m width (15 m apart for 0-, 1- and 2-year-old sites and 10 m apart for 3-year-old site). Soils from the 0 to 10 cm soil layer were collected from the 1-, 2- and 3-year-old sites. The 13C NMR spectra of the harvest residues indicated the presence of lignin in the hoop pine wood, foliage and newly incorporated organic matter (NIOM). Condensed tannin structures were found in the decay-resistant bark, small wood and foliage, but were absent in other residue components and SOM. The NMR spectra of small wood samples contained condensed tannin structures because the outer layer of bark was not removed. NIOM showed a shift from foliage-like structures (celluloses) to lignin-type structures, indicating an incorporation of woody residues from the decomposing harvest residues. Suberins were also present in the small wood, foliage and bark. The 13C CP NMR spectra of SOM indicated that in areas where windrows were present, SOM did not show compositional changes. However, an increase in SOM quality under the windrows in the second year after their formation as characterised by the alkyl C/O-alkyl C (A/O-A) ratio was mainly due to inputs from the decomposition of the labile, readily available components of the windrowed harvest residues. (C) 2002 Published by Elsevier Science B.V.

How does residue management impact soil organic matter composition and quality under Eucalyptus globulus plantations in southwestern Australia?

This study investigated the influence of harvest residue management practices on soil organic matter (SOM) composition and quality from two second-rotation Eucalyptus globulus plantations in southwestern Australia, using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy with cross-polarisation and magic-angle-spinning (CPMAS). Soil samples (0–5 cm) were collected every 12 months for 5 years from two sites that had contrasting soil types and fertility. Harvest residue management treatments established at both sites were (a) no harvest residues; and (b) double harvest residues. The use of 13C CPMAS and DD NMR spectroscopy enabled the successful non-destructive detection of SOM quality changes in the two E. globulus plantations. Relative intensities of 13C CPMAS NMR spectral regions were similar at both sites, and for both harvest residue treatments, indicating that SOM composition was also similar. Dipolar dephasing (DD) NMR spectra revealed resonances in SOM assigned to lignin and tannin structures, with larger resonances in the carbonyl and alkyl C regions that were indicative of cuticular material, enabling detection of changes in SOM quality. Retention of double harvest residues on the soil surface increased the soil quality compared with removal of all harvest residues at both sites as indicated by the NMR aromaticities, but this was most noticeable at Manjimup, which had greater initial soil fertility.

New heterogeneous catalysts for trans-esterification of triglycerides

This paper describes preliminary work done towards the development of new metallic heterogeneous catalysts to be used in the transesterification reaction of triglycerides, which is of considerable interest in the production of biodiesel. Biodiesel, is a mixture of mono-alkyl esters of fatty acids, and is currently manufactured by transesterification of triglycerides with methanol using NaOH or KOH as liquid base catalyst. Catalysts as such are corrosive to the equipment, and as these catalysts are in liquid phase must be neutralized after the completion of the reaction, typically using HCl, thus producing salt streams. Moreover, due to the presence of free fatty acids it reacts to form soaps as unwanted by-products, hence requiring more expensive separation processes. Therefore, there is a great need on the development of industrial processes for biodiesel production using solid acid catalysts. The key benefit of using solid acid catalysts is that no polluting by-products are formed and the catalysts do not have to be removed since they do not mix with the biodiesel product.

Efficient cyclohexane oxidation with hydrogen peroxide catalysed by a C-scorpionate iron(II) complex immobilized on desilicated MOR zeolite

The hydrotris(pyrazol-1-yl)methane iron(II) complex [FeCl2{eta(3)-HC(pz)(3)}] (Fe, pz = pyrazol-1-yl) immobilized on commercial (MOR) or desilicated (MOR-D) zeolite, catalyses the oxidation of cyclohexane with hydrogen peroxide to cyclohexanol and cyclohexanone, under mild conditions. MOR-D/Fe (desilicated zeolite supported [FeCl2{eta(3)-HC(pz)(3)}] complex) provides an outstanding catalytic activity (TON up to 2.90 x 10(3)) with the concomitant overall yield of 38%, and can be easy recovered and reused. The MOR or MOR-D supported hydrotris(pyrazol-1-yl)methane iron(II) complex (MOR/Fe and MOR-D/Fe, respectively) was characterized by X-ray powder diffraction, ICP-AES, and TEM studies as well as by IR spectroscopy and N-2 adsorption at -196 degrees C. The catalytic operational conditions (e.g., reaction time, type and amount of oxidant, presence of acid and type of solvent) were optimized. (C) 2013 Elsevier B.V. All rights reserved.

Eficiência de antioxidantes em biodiesel

Mestrado em Engenharia Química.Ramo optimização energética na indústria química

Avaliação da influência de antioxidantes na estabilização de biodiesel

O biodiesel é uma fonte de energia renovável, que se pode obter pela transformação dos resíduos domésticos, e é ambientalmente inócuo, e fácil de transportar, pois tem um ponto de fulgor elevado. Atualmente tem-se focado a atenção nos efeitos da oxidação do biodiesel causados pelo contato com o ar ambiente durante o seu armazenamento. Os produtores, fornecedores e consumidores, pretendem garantir que a qualidade do biodiesel e das suas misturas com combustíveis destilados do petróleo, mantém-se durante longos períodos de armazenamento. A maioria dos óleos vegetais e das gorduras animais, usados como matéria – prima, são triacilgliceróis com grupos ácido gordos de cadeia longa (C16 – C18) ligados por ligações éster a uma estrutura de glicerol. O objetivo deste estudo foi avaliar a eficiência do ácido gálhico e seus derivados alquilo ésteres aumentando a resistência relativa à oxidação do ácido linoléico, inibindo a peroxidação ácido gordos de cadeia longa insaturados. Outro objetivo foi estudar a taxa de inibição da auto-oxidação do ácido linoleico. Foi, ainda estudado o efeito que a concentração do antioxidante, tinha na estabilidade do ácido linoleico. No caso do ácido gálhico verificou-se que o aumento para o dobro da concentração do antioxidante utilizada, obtinha-se quase o dobro da taxa de inibição da oxidação do ácido linoleico. A auto-oxidação de ácido linoleico é acompanhada pela formação do seu dieno conjugado, o qual foi medido sua absorvância, durante 7 dias, por espetrofotometria de absorção UV a 234 nm. Uma diminuição da taxa de formação de dieno conjugado, indica o aumento da atividade antioxidante do composto adicionado à micela de ácido linoleico. Os resultados obtidos permitem concluir que de todos os antioxidantes testados o galhato de butilo é o que possibilita uma maior inibição da oxidação do ácido linoleico para as duas concentrações de antioxidantes testadas (0,1 mM e 1mM), obteve-se uma percentagem de inibição do ácido linoleico de 54,0% e 63,6%, respetivamente. O estudo comparativo da estabilização do ácido linoleico com o antioxidante de referência, o butil -hidroxitolueno, mostrou que este composto tem um poder de estabilização inferior a qualquer dos antioxidantes estudados. Os resultados deste estudo demonstraram que a utilização de compostos fenólicos, em especial o galhato de butilo, constitui uma boa alternativa para a estabilização de matrizes lipídicas, nomeadamente de combustíveis como o biodiesel.

Trits(Pyrazol-1-YL)methane metal complexes for catalytic mild oxidative functionalizations of alkanes, alkanes and ketones

This work concerns recent advances (since 2005) in the oxidative functionalization of alkanes, alkenes and ketones, under mild conditions, catalyzed by homoscorpionate tris(pyrazol-1-yl)methane metal complexes. The main types of such homogeneous or supported catalysts are classified, and the critical analysis of the most efficient catalytic systems in the different reactions is presented. These reactions include the mild oxidation of alkanes (typically cyclohexane as a model substrate) with hydrogen peroxide (into alkyl hydroperoxides, alcohols, and ketones), the hydrocarboxylation of gaseous alkanes (with carbon monoxide and potassium peroxodisulfate) into the corresponding Cn+1 carboxylic acids, as well as the epoxidation of alkenes and the Baeyer-Villiger oxidation of linear and cyclic ketones with hydrogen peroxide into the corresponding esters and lactones. Effects of various reaction parameters are highlighted and the preferable requirements for a prospective homogeneous or supported C-scorpionate-M-based catalyst in oxidative transformations of those substrates are identified. (C) 2014 Elsevier B.V. All rights reserved.

Redox-active cytotoxic diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes: Reduction behaviour and theoretical interpretation

Two series of new diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl), formulated as the mononuclear [R2Sn(HL)(2)] (1:2) (a, R=Bu-n and Ph) and the polymeric [R2SnL](n) (1:1) (b, R=Bu-n) compounds, were prepared and fully characterized. Single crystal X-ray diffraction for [(Bu2Sn)-Bu-n{C5H9C(O)NHO}(2)] (3a) discloses the cis geometry and strong intermolecular NH center dot center dot center dot O interactions. The in vitro cytotoxic activities of the complexes were evaluated against HL-60, Bel-7402, BGC-823 and KB human tumour cell lines, the greater activity concerning [(Bu2Sn)-Bu-n(HL)(2)] [HL=C3H5C(O)NHO (1a), C6H11C(O)NHO (4a)] towards BGC-823. The complexes undergo, by cyclic voltammetry and controlled-potential electrolysis, one irreversible overall two-electron cathodic process at a reduction potential that does not appear to correlate with the antitumour activity. The electrochemical behaviour of [R2Sn(C5H9C(O)NHO)(2)] [R=Bu-n (3a), Ph (7a)] was also investigated using density functional theory (DFT) methods, showing that the ultimate complex structure and the mechanism of its formation are R dependent: for the aromatic (R = Ph) complex, the initial reduction step is centred on the phenyl ligands and at the metal, being followed by a second reduction with Sn-O and Sn-C ruptures, whereas for the alkyl (R=Bu-n) complex the first reduction step is centred on one of the hydroxamate ligands and is followed by a second reduction with Sn-O bond cleavages and preservation of the alkyl ligands. In both cases, the final complexes are highly coordinative unsaturated Sn-II species with the cis geometry, features that can be of biological significance.

Electrorheology study of a series of LC cyanobiphenyls: Experimental and theoretical treatment

In this work we study the electro-rheological behaviour of a series of four liquid crystal (LC) cyanobiphenyls with a number of carbon atoms in the alkyl group, ranging from five to eight (5CB–8CB). We present the flow curves for different temperatures and under the influence of an external electric field, ranging from 0 to 3 kV/mm, and the viscosity as a function of the temperature, for the same values of electric field, obtained for different shear rates. Theoretical interpretation of the observed behaviours is proposed in the framework of the continuum theory of Leslie–Ericksen for low molecular weight nematic LCs. In our analysis, the director alignment angle is only a function of the ratio between the shear rate and the square of the electric field – boundary conditions are neglected. By fitting the theoretical model to the experimental data, we are able to determine some viscosity coefficients and the dielectric anisotropy as a function of temperature. To interpret the behaviour of the flow curves near the nematic–isotropic transitions, we apply the continuum theory of Olmsted–Goldbart, which extends the theory of Leslie–Ericksen to the case where the degree of alignment of the LC molecules can also vary.

Molecular details of INH-C-10 binding to wt KatG and Its S315T mutant

Isoniazid (INH) is still one of the two most effective antitubercular drugs and is included in all recommended multitherapeutic regimens. Because of the increasing resistance of Mycobacterium tuberculosis to INH, mainly associated with mutations in the katG gene, new INH-based compounds have been proposed to circumvent this problem. In this work, we present a detailed comparative study of the molecular determinants of the interactions between wt KatG or its S315T mutant form and either INH or INH-C10, a new acylated INH derivative. MD simulations were used to explore the conformational space of both proteins, and results indicate that the S315T mutation did not have a significant impact on the average size of the access tunnel in the vicinity of these residues. Our simulations also indicate that the steric hindrance role assigned to Asp137 is transient and that electrostatic changes can be important in understanding the enzyme activity data of mutations in KatG. Additionally, molecular docking studies were used to determine the preferred modes of binding of the two substrates. Upon mutation, the apparently less favored docking solution for reaction became the most abundant, suggesting that S315T mutation favors less optimal binding modes. Moreover, the aliphatic tail in INH-C10 seems to bring the hydrazine group closer to the heme, thus favoring the apparent most reactive binding mode, regardless of the enzyme form. The ITC data is in agreement with our interpretation of the C10 alkyl chain role and helped to rationalize the significantly lower experimental MIC value observed for INH-C10. This compound seems to be able to counterbalance most of the conformational restrictions introduced by the mutation, which are thought to be responsible for the decrease in INH activity in the mutated strain. Therefore, INH-C10 appears to be a very promising lead compound for drug development.

Phase behaviour of alternative solvents

Dissertation presented to obtain the Ph.D. degree in Chemistry (Physical Chemistry) at the Instituto de Tecnologia Química e Biológica da Universidade Nova de Lisboa

Eficiência de antioxidantes na estabilização do Biodiesel

O Biodiesel é uma fonte de energia renovável que actualmente se encontra em expansão. O Biodiesel é constituído por uma mistura de ésteres alquílicos de ácidos gordos. A existência de ácidos gordos insaturados torna o Biodiesel quimicamente menos estável, podendo ocorrer oxidação, degradação e polimerização do combustível, se este for inadequadamente armazenado ou transportado. O objectivo deste trabalho consistiu em avaliar a eficiência da utilização de antioxidantes fenólicos (ácido protocatecuico, ácido gálico, ácido 3,4 di-hidroxifenilacético, ácido cafeico, ácido hidrocafeico, ácido 3,4,5-tri-hidroxicinâmico, ácido m-coumárico e ácido p-coumárico), na estabilização do Biodiesel. O estudo envolveu a análise da influência do uso de cada um dos antioxidantes na inibição da peroxidação lipídica do ácido linoleico um dos principais ácidos gordos insaturados presentes na matéria-prima utilizada na produção de Biodiesel. A avaliação do efeito de inibição dos antioxidantes na peroxidação do ácido linoleico foi efetuada usando o método do tiocianato de ferro (III). Os resultados obtidos demonstraram, que todos os ácidos fenólicos estudados, apresentam uma elevada capacidade para inibir a peroxidação lipídica do ácido linoleico. As percentagens de inibição da peroxidação do ácido linoleico variaram entre os 72%, observada para o ácido p-coumárico, e os 82 %, verificada para o ácido protocatecuico. A eficiência de inibição da peroxidação por parte dos antioxidantes fenólicos em estudo foi comparada com a obtida utilizando um antioxidante de referência, o trolox. A eficiência de inibição obtida para todos os antioxidantes fenólicos estudados foi muito superior à observada para o trolox. Os resultados obtidos nesta dissertação permitem concluir que a utilização de ácidos fenólicos constitui uma boa alternativa para a estabilização de matrizes lipídicas, particularmente em combustíveis como o Biodiesel.

Protein adducts from the anti-HIV drug abacavir – possible biomarkers of drug toxicity

Dissertação para obtenção do Grau de Mestre em Genética Molecular e Biomedicina