CHEMICAL AND BIOCHEMICAL PROPERTIES OF ARAUCARIA ANGUSTIFOLIA (BERT.) KTZE. FOREST SOILS IN THE STATE OF SAO PAULO

Araucaria angustifolia, commonly named Araucaria, is a Brazilian native species that is intensively exploited due to its timber quality. Therefore, Araucaria is on the list of species threatened by extinction. Despite the importance of soil for forest production, little is known about the soil properties of the highly fragmented Araucaria forests. This study was designed to investigate the use of chemical and biological properties as indicators of conservation and anthropogenic disturbance of Araucaria forests in different sampling periods. The research was carried out in two State parks of Sao Paulo: Parque Estadual Turistico do Alto do Ribeira and Parque Estadual de Campos de Jordao. The biochemical properties carbon and nitrogen in microbial biomass (MB-C and MB-N), basal respiration (BR), the metabolic quotient (qCO(2)) and the following enzyme activities: beta-glucosidase, urease, and fluorescein diacetate hydrolysis (FDA) were evaluated. The sampling period (dry or rainy season) influenced the results of mainly MB-C, MB-N, BR, and qCO(2). The chemical and biochemical properties, except K content, were sensitive indicators of differences in the conservation and anthropogenic disturbance stages of Araucaria forests. Although these forests differ in biochemical and chemical properties, they are efficient in energy use and conservation, which is shown by their low qCO(2), suggesting an advanced stage of succession.

Chemical and biochemical properties of Araucaria angustifolia (Bert.) Ktze. forest soils in the state of São Paulo

Araucaria angustifolia, commonly named Araucaria, is a Brazilian native species that is intensively exploited due to its timber quality. Therefore, Araucaria is on the list of species threatened by extinction. Despite the importance of soil for forest production, little is known about the soil properties of the highly fragmented Araucaria forests. This study was designed to investigate the use of chemical and biological properties as indicators of conservation and anthropogenic disturbance of Araucaria forests in different sampling periods. The research was carried out in two State parks of São Paulo: Parque Estadual Turístico do Alto do Ribeira and Parque Estadual de Campos de Jordão. The biochemical properties carbon and nitrogen in microbial biomass (MB-C and MB-N), basal respiration (BR), the metabolic quotient (qCO2) and the following enzyme activities: β-glucosidase, urease, and fluorescein diacetate hydrolysis (FDA) were evaluated. The sampling period (dry or rainy season) influenced the results of mainly MB-C, MB-N, BR, and qCO2. The chemical and biochemical properties, except K content, were sensitive indicators of differences in the conservation and anthropogenic disturbance stages of Araucaria forests. Although these forests differ in biochemical and chemical properties, they are efficient in energy use and conservation, which is shown by their low qCO2, suggesting an advanced stage of succession.

Physico-chemical and microstructural properties of food dispersions

The macroscopic properties of oily food dispersions, such as rheology, mechanical strength, sensory attributes (e.g. mouth feel, texture and even flavour release) and as well as engineering properties are strongly determined by their microstructure, that is considered a key parameter in the understanding of the foods behaviour . In particular the rheological properties of these matrices are largely influenced by their processing techniques, particle size distribution and composition of ingredients. During chocolate manufacturing, mixtures of sugar, cocoa and fat are heated, cooled, pressurized and refined. These steps not only affect particle size reduction, but also break agglomerates and distribute lipid and lecithin-coated particles through the continuous phase, this considerably modify the microstructure of final chocolate. The interactions between the suspended particles and the continuous phase provide information about the existing network and consequently can be associated to the properties and characteristics of the final dispersions. Moreover since the macroscopic properties of food materials, are strongly determined by their microstructure, the evaluation and study of the microstructural characteristics, can be very important for a through understanding of the food matrices characteristics and to get detailed information on their complexity. The aim of this study was investigate the influence of formulation and each process step on the microstructural properties of: chocolate type model systems, dark milk and white chocolate types, and cocoa creams. At the same time the relationships between microstructural changes and the resulting physico-chemical properties of: chocolate type dispersions model systems dark milk and white chocolate were investigated.

Ab initio quantum mechanical investigation of structural and chemical-physical properties of selected minerals for minero-petrological, structural ceramic and biomaterial applications

The purpose of this thesis is the atomic-scale simulation of the crystal-chemical and physical (phonon, energetic) properties of some strategically important minerals for structural ceramics, biomedical and petrological applications. These properties affect the thermodynamic stability and rule the mineral-environment interface phenomena, with important economical, (bio)technological, petrological and environmental implications. The minerals of interest belong to the family of phyllosilicates (talc, pyrophyllite and muscovite) and apatite (OHAp), chosen for their importance in industrial and biomedical applications (structural ceramics) and petrophysics. In this thesis work we have applicated quantum mechanics methods, formulas and knowledge to the resolution of mineralogical problems ("Quantum Mineralogy”). The chosen theoretical approach is the Density Functional Theory (DFT), along with periodic boundary conditions to limit the portion of the mineral in analysis to the crystallographic cell and the hybrid functional B3LYP. The crystalline orbitals were simulated by linear combination of Gaussian functions (GTO). The dispersive forces, which are important for the structural determination of phyllosilicates and not properly con-sidered in pure DFT method, have been included by means of a semi-empirical correction. The phonon and the mechanical properties were also calculated. The equation of state, both in athermal conditions and in a wide temperature range, has been obtained by means of variations in the volume of the cell and quasi-harmonic approximation. Some thermo-chemical properties of the minerals (isochoric and isobaric thermal capacity) were calculated, because of their considerable applicative importance. For the first time three-dimensional charts related to these properties at different pressures and temperatures were provided. The hydroxylapatite has been studied from the standpoint of structural and phonon properties for its biotechnological role. In fact, biological apatite represents the inorganic phase of vertebrate hard tissues. Numerous carbonated (hydroxyl)apatite structures were modelled by QM to cover the broadest spectrum of possible biological structural variations to fulfil bioceramics applications.

Analysis of factors influencing the physical, chemical and sensorial properties of Serra da Estrela cheeses

The objective of this study was to evaluate the chemical, color, textural, and sensorial characteristics of Serra da Estrela cheese and also to identity the factors affecting these properties, namely thistle ecotype, place of production, dairy and maturation. The results demon- strated that the cheeses lost weight mostly during the first stage of maturation, which was negatively correlated with moisture content, being this also observed for fat and protein contents. During maturation the cheeses became darker and with a yellowish coloration. A strong corre- lation was found between ash and chlorides contents, being the last directly related to the added salt in the manufacturing process. The flesh firmness showed a strong positive correlation with the rind harness and the firmness of inner paste. Stickiness was strongly related with all the other textural properties being indicative of the creamy nature of the paste. Adhesiveness was posi- tively correlated with moisture content and negatively correlated with maturation time. The trained panelists liked the cheeses, giving high overall assessment scores, but these were not significantly correlated with the physicochemical properties. The salt differences between cheeses were not evident for the panelists, which was corroborated by the absence of correlation between the perception of saltiness and the analyzed chlorides con- tents. The Factorial Analysis of the chemical and physical properties evidenced that they could be explained by two factors, one associated to the texture and the color and the other associated with the chemical properties. Finally, there was a clear influence of the thistle ecotype, place of production and dairy factors in the analyzed properties.

Effect of drying on the physical, chemical and sensorial properties of kiwi

Kiwi fruit is a highly nutritional fruit due to the high level of vitamin C and its strong antioxidant capacity due to a wide number of phytonutrients including carotenoids, lutein, phenolics, flavonoids and chlorophyll [1]. Drying consists of a complex process in which simultaneous heat and mass transfer occur. Several alterations occur during the drying of foods at many levels (physical, chemical, nutritional or sensorial) which are influenced by a number of factors, including processing conditions [2]. Temperature is particularly important because of the effects it produces at the chemical and also at the physical level, particularly colour and texture [3]. In the present work were evaluated the changes in sliced kiwi when exposed to air drying at different temperatures (50, 60, 70, 80 ºC), namely in terms of some chemical properties like ascorbic acid or phenolic compounds, physical characteristics like colour and texture and also at the sensorial level. All experiments followed standard established procedures and several replicates were done to assess each property. The results obtained indicated that moisture was reduced with drying by 74 to 87%, depending on the temperature. Also ascorbic acid decreased with drying, being 7% for 50 ºC and increasing up to 28% for the highest temperature (80 ºC). The phenolic compounds and antioxidant activity were also very much affected by the drying temperature. The water activity of the dried samples varied from 0.658 to 0.753, being compatible with a good preservation. Regarding colour, the total colour difference between the dried samples and the fresh sample was found to vary in the range 9.45 – 17.17. The textural parameters were also much affected by drying, namely hardness which decreased by 45 to 72 %, and all other parameters increased: cohesiveness (approximately doubled), springiness (increased 2 to 3 times) and chewiness which increased up to 2.5 times that off the fresh sample. Adhesiveness, which was observed for the fresh samples (-4.02 N.s) disappeared in all the dried samples. The sensorial analysis made to the dried samples allowed establishing the sensorial profiles as shown in Figure 1.

A physico-chemical characterisation of particulate emissions from a compression ignition engine : the influence of biodiesel feedstock

This study undertook a physico-chemical characterisation of particle emissions from a single compression ignition engine operated at one test mode with 3 biodiesel fuels made from 3 different feedstocks (i.e. soy, tallow and canola) at 4 different blend percentages (20%, 40%, 60% and 80%) to gain insights into their particle-related health effects. Particle physical properties were inferred by measuring particle number size distributions both with and without heating within a thermodenuder (TD) and also by measuring particulate matter (PM) emission factors with an aerodynamic diameter less than 10 μm (PM10). The chemical properties of particulates were investigated by measuring particle and vapour phase Polycyclic Aromatic Hydrocarbons (PAHs) and also Reactive Oxygen Species (ROS) concentrations. The particle number size distributions showed strong dependency on feedstock and blend percentage with some fuel types showing increased particle number emissions, whilst others showed particle number reductions. In addition, the median particle diameter decreased as the blend percentage was increased. Particle and vapour phase PAHs were generally reduced with biodiesel, with the results being relatively independent of the blend percentage. The ROS concentrations increased monotonically with biodiesel blend percentage, but did not exhibit strong feedstock variability. Furthermore, the ROS concentrations correlated quite well with the organic volume percentage of particles – a quantity which increased with increasing blend percentage. At higher blend percentages, the particle surface area was significantly reduced, but the particles were internally mixed with a greater organic volume percentage (containing ROS) which has implications for using surface area as a regulatory metric for diesel particulate matter (DPM) emissions.

Influence of fatty acid structure on fuel properties of algae derived biodiesel

Physical and chemical properties of biofuel are influenced by structural features of fatty acid such as chain length, degree of unsaturation and branching of the chain. A simple and reliable calculation method to estimate fuel property is therefore needed to avoid experimental testing which is difficult, costly and time consuming. Typically in commercial biodiesel production such testing is done for every batch of fuel produced. In this study 9 different algae species were selected that were likely to be suitable for subtropical climates. The fatty acid methyl esters (FAMEs) of all algae species were analysed and the fuel properties like cetane number (CN), cold filter plugging point (CFPP), kinematic viscosity (KV), density and higher heating value (HHV) were determined. The relation of each fatty acid with particular fuel property is analysed using multivariate and multi-criteria decision method (MCDM) software. They showed that some fatty acids have major influences on the fuel properties whereas others have minimal influence. Based on the fuel properties and amounts of lipid content rank order is drawn by PROMETHEE-GAIA which helped to select the best algae species for biodiesel production in subtropical climates. Three species had fatty acid profiles that gave the best fuel properties although only one of these (Nannochloropsis oculata) is considered the best choice because of its higher lipid content.

Microalgal species selection for biodiesel production based on fuel properties derived from fatty acid profiles

Physical and chemical properties of biodiesel are influenced by structural features of the fatty acids, such as chain length, degree of unsaturation and branching of the carbon chain. This study investigated if microalgal fatty acid profiles are suitable for biodiesel characterization and species selection through Preference Ranking Organisation Method for Enrichment Evaluation (PROMETHEE) and Graphical Analysis for Interactive Assistance (GAIA) analysis. Fatty acid methyl ester (FAME) profiles were used to calculate the likely key chemical and physical properties of the biodiesel [cetane number (CN), iodine value (IV), cold filter plugging point, density, kinematic viscosity, higher heating value] of nine microalgal species (this study) and twelve species from the literature, selected for their suitability for cultivation in subtropical climates. An equal-parameter weighted (PROMETHEE-GAIA) ranked Nannochloropsis oculata, Extubocellulus sp. and Biddulphia sp. highest; the only species meeting the EN14214 and ASTM D6751-02 biodiesel standards, except for the double bond limit in the EN14214. Chlorella vulgaris outranked N. oculata when the twelve microalgae were included. Culture growth phase (stationary) and, to a lesser extent, nutrient provision affected CN and IV values of N. oculata due to lower eicosapentaenoic acid (EPA) contents. Application of a polyunsaturated fatty acid (PUFA) weighting to saturation led to a lower ranking of species exceeding the double bond EN14214 thresholds. In summary, CN, IV, C18:3 and double bond limits were the strongest drivers in equal biodiesel parameter-weighted PROMETHEE analysis.

Tensile properties of a boron/nitrogen-doped carbon nanotube–graphene hybrid structure

Doping is an effective approach that allows for the intrinsic modification of the electrical and chemical properties of nanomaterials. Recently, a graphene and carbon nanotube hybrid structure (GNHS) has been reported, which extends the excellent properties of carbon-based materials to three dimensions. In this paper, we carried out a first-time investigation on the tensile properties of the hybrid structures with different dopants. It is found that with the presence of dopants, the hybrid structures usually exhibit lower yield strength, Young’s modulus, and earlier yielding compared to that of a pristine hybrid structure. For dopant concentrations below 2.5% no significant reduction of Young’s modulus or yield strength could be observed. For all considered samples, the failure is found to initiate at the region where the nanotubes and graphene sheets are connected. After failure, monatomic chains are normally observed around the failure region. Dangling graphene layers without the separation of a residual CNT wall are found to adhere to each other after failure with a distance of about 3.4 Å. This study provides a fundamental understanding of the tensile properties of the doped graphene–nanotube hybrid structures, which will benefit the design and also the applications of graphene-based hybrid materials.

A review of hydrothermal liquefaction bio-crude properties and prospects for upgrading to transportation fuels

Hydrothermal liquefaction (HTL) presents a viable route for converting a vast range of materials into liquid fuel, without the need for pre-drying. Currently, HTL studies produce bio-crude with properties that fall short of diesel or biodiesel standards. Upgrading bio-crude improves the physical and chemical properties to produce a fuel corresponding to diesel or biodiesel. Properties such as viscosity, density, heating value, oxygen, nitrogen and sulphur content, and chemical composition can be modified towards meeting fuel standards using strategies such as solvent extraction, distillation, hydrodeoxygenation and catalytic cracking. This article presents a review of the upgrading technologies available, and how they might be used to make HTL bio-crude into a transportation fuel that meets current fuel property standards.

Investigating physical properties of solid dosage forms during pharmaceutical processing : Process analytical applications of vibrational spectroscopy

In order to improve and continuously develop the quality of pharmaceutical products, the process analytical technology (PAT) framework has been adopted by the US Food and Drug Administration. One of the aims of PAT is to identify critical process parameters and their effect on the quality of the final product. Real time analysis of the process data enables better control of the processes to obtain a high quality product. The main purpose of this work was to monitor crucial pharmaceutical unit operations (from blending to coating) and to examine the effect of processing on solid-state transformations and physical properties. The tools used were near-infrared (NIR) and Raman spectroscopy combined with multivariate data analysis, as well as X-ray powder diffraction (XRPD) and terahertz pulsed imaging (TPI). To detect process-induced transformations in active pharmaceutical ingredients (APIs), samples were taken after blending, granulation, extrusion, spheronisation, and drying. These samples were monitored by XRPD, Raman, and NIR spectroscopy showing hydrate formation in the case of theophylline and nitrofurantoin. For erythromycin dihydrate formation of the isomorphic dehydrate was critical. Thus, the main focus was on the drying process. NIR spectroscopy was applied in-line during a fluid-bed drying process. Multivariate data analysis (principal component analysis) enabled detection of the dehydrate formation at temperatures above 45°C. Furthermore, a small-scale rotating plate device was tested to provide an insight into film coating. The process was monitored using NIR spectroscopy. A calibration model, using partial least squares regression, was set up and applied to data obtained by in-line NIR measurements of a coating drum process. The predicted coating thickness agreed with the measured coating thickness. For investigating the quality of film coatings TPI was used to create a 3-D image of a coated tablet. With this technique it was possible to determine coating layer thickness, distribution, reproducibility, and uniformity. In addition, it was possible to localise defects of either the coating or the tablet. It can be concluded from this work that the applied techniques increased the understanding of physico-chemical properties of drugs and drug products during and after processing. They additionally provided useful information to improve and verify the quality of pharmaceutical dosage forms

Soil properties and crop yields in a dryland Vertisol sown with cotton-based crop rotations

Information on the effects of growing cotton (Gossypium hirsutum L.)-based crop rotations on soil quality of dryland Vertisols is sparse. The objective of this study was to quantify the effects of growing cereal and leguminous crops in rotation with dryland cotton on physical and chemical properties of a grey Vertisol near Warra, SE Queensland, Australia. The experimental treatments, selected after consultations with local cotton growers, were continuous cotton (T1), cotton-sorghum (Sorghum bicolor (L.) Moench.) (T2), cotton-wheat (Triticum aestivum L.) double cropped (T3), cotton-chickpea (Cicer arietinum L.) double cropped followed by wheat (T4) and cotton-wheat (T5). From 1993 to 1996 land preparation was by chisel ploughing to about 0.2 m followed by two to four cultivations with a Gyral tyne cultivator. Thereafter all crops were sown with zero tillage except for cultivation with a chisel plough to about 0.07-0.1 m after cotton picking to control heliothis moth pupae. Soil was sampled from 1996 to 2004 and physical (air-filled porosity of oven-dried soil, an indicator of soil compaction; plastic limit; linear shrinkage; dispersion index) and chemical (pH in 0.01 M CaCl2, organic carbon, exchangeable Ca, Mg, K and Na contents) properties measured. Crop rotation affected soil properties only with respect to exchangeable Na content and air-filled porosity. In the surface 0.15 m during 2000 and 2001 lowest air-filled porosity occurred with T1 (average of 34.6 m3/100 m3) and the highest with T3 (average of 38.9 m3/100 m3). Air-filled porosity decreased in the same depth between 1997 and 1998 from 45.0 to 36.1 m3/100 m3, presumably due to smearing and compaction caused by shallow cultivation in wet soil. In the subsoil, T1 and T2 frequently had lower air-filled porosity values in comparison with T3, T4 and T5, particularly during the early stages of the experiment, although values under T1 increased subsequently. In general, compaction was less under rotations which included a wheat crop (T3, T4, T5). For example, average air-filled porosity (in m3/100 m3) in the 0.15-0.30 m depth from 1996 to 1999 was 19.8 with both T1 and T2, and 21.2 with T3, 21.1 with T4 and 21.5 with T5. From 2000 to 2004, average air-filled porosity (in m3/100 m3) in the same depth was 21.3 with T1, 19.0 with T2, 19.8 with T3, 20.0 with T4 and 20.5 with T5. The rotation which included chickpea (T4) resulted in the lowest exchangeable Na content, although differences among rotations were small. Where only a cereal crop with a fibrous root system was sown in rotation with cotton (T2, T3, T5) linear shrinkage in the 0.45-0.60 m depth was lower than in rotations, which included tap-rooted crops such as chickpea (T4) or continuous cotton (T1). Dispersion index and organic carbon decreased, and plastic limit increased with time. Soil organic carbon stocks decreased at a rate of 1.2 Mg/ha/year. Lowest average cotton lint yield occurred with T2 (0.54 Mg/ha) and highest wheat yield with T3 (2.8 Mg/ha). Rotations which include a wheat crop are more likely to result in better soil structure and cotton lint yield than cotton-sorghum or continuous cotton.

Sap properties and alk(en)ylresorcinol concentrations in Australian-grown mangoes.

Physical and chemical properties of sap and sap concentrations of constitutive alk(en)ylresorcinols were determined in several varieties of mango grown in different locations in Queensland, Australia, over two consecutive cropping seasons. Sap weight from individual fruit, sap pH, percentage of non-aqueous sap and concentrations of constitutive alk(en)ylresorcinols (5-n-heptadecenylresorcinol and 5-n-pentadecylresorcinol) in sap varied significantly among the varieties. 'Calypso', 'Keitt', 'Kensington Pride' and 'Celebration' had the greatest proportion of non-aqueous sap, whereas 'Nam Doc Mai' had the least. The highest concentrations of 5-n-heptadecenylresorcinol were found in the sap of 'Kensington Pride', and the lowest in 'Honey Gold' and 'Nam Doc Mai'. Highest concentrations of 5-n-pentadecylresorcinol were found in sap of 'Calypso' and 'Celebration', and the lowest levels were in 'Honey Gold' and 'Nam Doc Mai'. There was a direct relationship between the percentage of non-aqueous sap and the concentrations of alk(en)ylresorcinols (r(2) = 0.77 for 5-n-heptadecenylresorcinol, and r(2) = 0.87 for 5-n-pentadecylresorcinol). The alk(en)ylresorcinols were distributed mainly in the upper non-aqueous phase of 'Kensington Pride' sap. Growing location also had significant effects on the composition of mango sap but the effects appeared to be related to differences in maturity. Sap removal is necessary to prevent sapburn, but considerable quantities of alk(en)ylresorcinols that assist in protecting the harvested fruit from anthracnose disease are also removed.

Physio-chemical assessment of beauty leaf (Calophyllum inophyllum) as second-generation biodiesel feedstock

Recently, second-generation (non-vegetable oil) feedstocks for biodiesel production are receiving significant attention due to the cost and social effects connected with utilising food products for the production of energy products. The Beauty leaf tree (Calophyllum inophyllum) is a potential source of non-edible oil for producing second-generation biodiesel because of its suitability for production in an extensive variety of atmospheric condition, easy cultivation, high fruit production rate, and the high oil content in the seed. In this study, oil was extracted from Beauty leaf tree seeds through three different oil extraction methods. The important physical and chemical properties of these extracted Beauty leaf oils were experimentally analysed and compared with other commercially available vegetable oils. Biodiesel was produced using a two-stage esterification process combining of an acid catalysed pre-esterification process and an alkali catalysed transesterification process. Fatty acid methyl ester (FAME) profiles and important physicochemical properties were experimentally measured and estimated using equations based on the FAME analysis. The quality of Beauty leaf biodiesels was assessed and compared with commercially available biodiesels through multivariate data analysis using PROMETHEE-GAIA software. The results show that mechanical extraction using a screw press produces oil at a low cost, however, results in low oil yields compared with chemical oil extraction. High pressure and temperature in the extraction process increase oil extraction performance. On the contrary, this process increases the free fatty acid content in the oil. A clear difference was found in the physical properties of Beauty leaf oils, which eventually affected the oil to biodiesel conversion process. However, Beauty leaf oils methyl esters (biodiesel) were very consistent physicochemical properties and able to meet almost all indicators of biodiesel standards. Overall this study found that Beauty leaf is a suitable feedstock for producing second-generation biodiesel in commercial scale. Therefore, the findings of this study are expected to serve as the basis for further development of Beauty leaf as a feedstock for industrial scale second-generation biodiesel production.