Vibrational spectroscopic characterization of the phosphate mineral anapaite Ca2Fe2+(PO4)2 · 4(H2O)

We have characterized anapaite Ca2Fe2+(PO4)2·4(H2O), a rare Ca and Fe phosphate, using a combination of electron microscopy and vibrational spectroscopy. The mineral occurs in soils and lacustrine sediments and is usually related to the diagenetic process in phosphorous rich sediments. The phosphate anion is characterized by its Raman spectrum with an intense sharp band at 943 cm-1, attributed to the ν1 PO4 3- symmetric stretching mode. Three bands at 992, 1039 and 1071 cm-1 are attributed to ν3 PO4 3-antisymmetric stretching modes. The infrared spectrum of anapaite shows complexity with a series of overlapping bands. Water in the structure of anapaite is observed by OH stretching vibrations at 2777, 3022 and 3176 cm-1 (Raman) and 2744, 3014 and 3096 cm-1 (infrared). The position of these bands provides evidence for the strong hydrogen bonding of water in the anapaite structure and contributes to the stability of the mineral.

Modified alumina nanofiber membranes for protein separation

Large-scale purification/separation of bio-substances is a key technology required for rapid production of biological substances in bioengineering. Membrane filtration is a new separation process and has potential to be used for concentration (removal of solvent), desalting (removal of low molecular weight compounds), clarification (removal of particles), and fractionation (protein-protein separation). In this study, we developed an efficient membrane for protein separation based on ceramic nanofibers. Alumina nanofibers were prepared on a porous support and formed large flow passages. The radical changes in membrane structure provided new ceramic membranes with a large porosity (more than 70%) due to the replacement of bulk particles with fine fibers as building components. The pore size had an average of 11 nm and pure water flux was approximately 360 L•h-1•m-2•bar-1. Further surface modification with a self-assembled monolayer of (3-aminopropyl) triethoxysilane enhanced the membrane filtration properties. Characterization with SEM, FTIR, contact angle, and proteins separation tests indicated that the fibril layers uniformly spread on the surface of the porous support. Moreover, the membrane surface was changed from hydrophilic to hydrophobic after silane groups were grafted. It demonstrated that the silane-grafted alumina fiber membrane can reject 100% BSA protein and 92% cellulase protein. It was also able to retain 75% trypsin protein while maintaining a permeation flux of 48 L•h-1•m-2•bar-1.

Soil moisture monitoring at the field scale using neutron probe

Measurement of the moisture variation in soils is required for geotechnical design and research because soil properties and behavior can vary as moisture content changes. The neutron probe, which was developed more than 40 years ago, is commonly used to monitor soil moisture variation in the field. This study reports a full-scale field monitoring of soil moisture using a neutron moisture probe for a period of more than 2 years in the Melbourne (Australia) region. On the basis of soil types available in the Melbourne region, 23 sites were chosen for moisture monitoring down to a depth of 1500 mm. The field calibration method was used to develop correlations relating the volumetric moisture content and neutron counts. Observed results showed that the deepest “wetting front” during the wet season was limited to the top 800 to 1000 mm of soil whilst the top soil layer down to about 550mmresponded almost immediately to the rainfall events. At greater depths (550 to 800mmand below 800 mm), the moisture variations were relatively low and displayed predominantly periodic fluctuations. This periodic nature was captured with Fourier analysis to develop a cyclic moisture model on the basis of an analytical solution of a one-dimensional moisture flow equation for homogeneous soils. It is argued that the model developed can be used to predict the soil moisture variations as applicable to buried structures such as pipes.

Effect of soil properties on the response of pile to underground explosion

This paper develops and presents a fully coupled non-linear finite element procedure to treat the response of piles to ground shocks induced by underground explosions. The Arbitrary Lagrange Euler coupling formulation with proper state material parameters and equations are used in the study. Pile responses in four different soil types, viz, saturated soil, partially saturated soil and loose and dense dry soils are investigated and the results compared. Numerical results are validated by comparing with those from a standard design manual. Blast wave propagation in soils, horizontal pile deformations and damages in the pile are presented. The pile damage presented through plastic strain diagrams will enable the vulnerability assessment of the piles under the blast scenarios considered. The numerical results indicate that the blast performance of the piles embedded in saturated soil and loose dry soil are more severe than those in piles embedded in partially saturated soil and dense dry soil. Present findings should serve as a benchmark reference for future analysis and design.

A model to explain specific cellular communications and cellular harmony: - a hypothesis of coupled cells and interactive coupling molecules

Background The various cell types and their relative numbers in multicellular organisms are controlled by growth factors and related extracellular molecules which affect genetic expression pathways. However, these substances may have both/either inhibitory and/or stimulatory effects on cell division and cell differentiation depending on the cellular environment. It is not known how cells respond to these substances in such an ambiguous way. Many cellular effects have been investigated and reported using cell culture from cancer cell lines in an effort to define normal cellular behaviour using these abnormal cells. A model is offered to explain the harmony of cellular life in multicellular organisms involving interacting extracellular substances. Methods A basic model was proposed based on asymmetric cell division and evidence to support the hypothetical model was accumulated from the literature. In particular, relevant evidence was selected for the Insulin-Like Growth Factor system from the published data, especially from certain cell lines, to support the model. The evidence has been selective in an attempt to provide a picture of normal cellular responses, derived from the cell lines. Results The formation of a pair of coupled cells by asymmetric cell division is an integral part of the model as is the interaction of couplet molecules derived from these cells. Each couplet cell will have a receptor to measure the amount of the couplet molecule produced by the other cell; each cell will be receptor-positive or receptor-negative for the respective receptors. The couplet molecules will form a binary complex whose level is also measured by the cell. The hypothesis is heavily supported by selective collection of circumstantial evidence and by some direct evidence. The basic model can be expanded to other cellular interactions. Conclusions These couplet cells and interacting couplet molecules can be viewed as a mechanism that provides a controlled and balanced division-of-labour between the two progeny cells, and, in turn, their progeny. The presence or absence of a particular receptor for a couplet molecule will define a cell type and the presence or absence of many such receptors will define the cell types of the progeny within cell lineages.

Thin-Layer Chromatography with Ultraviolet and Mass Spectrometric Detection: From Preparative-Layer to Miniaturized Ultra-Thin-Layer Technique

The present challenge in drug discovery is to synthesize new compounds efficiently in minimal time. The trend is towards carefully designed and well-characterized compound libraries because fast and effective synthesis methods easily produce thousands of new compounds. The need for rapid and reliable analysis methods is increased at the same time. Quality assessment, including the identification and purity tests, is highly important since false (negative or positive) results, for instance in tests of biological activity or determination of early-ADME parameters in vitro (the pharmacokinetic study of drug absorption, distribution, metabolism, and excretion), must be avoided. This thesis summarizes the principles of classical planar chromatographic separation combined with ultraviolet (UV) and mass spectrometric (MS) detection, and introduces powerful, rapid, easy, low-cost, and alternative tools and techniques for qualitative and quantitative analysis of small drug or drug-like molecules. High performance thin-layer chromatography (HPTLC) was introduced and evaluated for fast semi-quantitative assessment of the purity of synthesis target compounds. HPTLC methods were compared with the liquid chromatography (LC) methods. Electrospray ionization mass spectrometry (ESI MS) and atmospheric pressure matrix-assisted laser desorption/ionization MS (AP MALDI MS) were used to identify and confirm the product zones on the plate. AP MALDI MS was rapid, and easy to carry out directly on the plate without scraping. The PLC method was used to isolate target compounds from crude synthesized products and purify them for bioactivity and preliminary ADME tests. Ultra-thin-layer chromatography (UTLC) with AP MALDI MS and desorption electrospray ionization mass spectrometry (DESI MS) was introduced and studied for the first time. Because of the thinner adsorbent layer, the monolithic UTLC plate provided 10 100 times better sensitivity in MALDI analysis than did HPTLC plates. The limits of detection (LODs) down to low picomole range were demonstrated for UTLC AP MALDI and UTLC DESI MS. In a comparison of AP and vacuum MALDI MS detection for UTLC plates, desorption from the irregular surface of the plates with the combination of an external AP MALDI ion source and an ion trap instrument provided clearly less variation in mass accuracy than the vacuum MALDI time-of-flight (TOF) instrument. The performance of the two-dimensional (2D) UTLC separation with AP MALDI MS method was studied for the first time. The influence of the urine matrix on the separation and the repeatability was evaluated with benzodiazepines as model substances in human urine. The applicability of 2D UTLC AP MALDI MS was demonstrated in the detection of metabolites in an authentic urine sample.

Characterisation and processing of amorphous binary mixtures with low glass transition temperature

The number of drug substances in formulation development in the pharmaceutical industry is increasing. Some of these are amorphous drugs and have glass transition below ambient temperature, and thus they are usually difficult to formulate and handle. One reason for this is the reduced viscosity, related to the stickiness of the drug, that makes them complicated to handle in unit operations. Thus, the aim in this thesis was to develop a new processing method for a sticky amorphous model material. Furthermore, model materials were characterised before and after formulation, using several characterisation methods, to understand more precisely the prerequisites for physical stability of amorphous state against crystallisation. The model materials used were monoclinic paracetamol and citric acid anhydrate. Amorphous materials were prepared by melt quenching or by ethanol evaporation methods. The melt blends were found to have slightly higher viscosity than the ethanol evaporated materials. However, melt produced materials crystallised more easily upon consecutive shearing than ethanol evaporated materials. The only material that did not crystallise during shearing was a 50/50 (w/w, %) blend regardless of the preparation method and it was physically stable at least two years in dry conditions. Shearing at varying temperatures was established to measure the physical stability of amorphous materials in processing and storage conditions. The actual physical stability of the blends was better than the pure amorphous materials at ambient temperature. Molecular mobility was not related to the physical stability of the amorphous blends, observed as crystallisation. Molecular mobility of the 50/50 blend derived from a spectral linewidth as a function of temperature using solid state NMR correlated better with the molecular mobility derived from a rheometer than that of differential scanning calorimetry data. Based on the results obtained, the effect of molecular interactions, thermodynamic driving force and miscibility of the blends are discussed as the key factors to stabilise the blends. The stickiness was found to be affected glass transition and viscosity. Ultrasound extrusion and cutting were successfully tested to increase the processability of sticky material. Furthermore, it was found to be possible to process the physically stable 50/50 blend in a supercooled liquid state instead of a glassy state. The method was not found to accelerate the crystallisation. This may open up new possibilities to process amorphous materials that are otherwise impossible to manufacture into solid dosage forms.

Microbial transformation of a fungicide-derived amine, dimethyl-p-phenylene diamine by Alcaligenes DM4

Abstract Microbial transformation of N, N-dimethyl-p-phenylene diamine (DMPDA), a microbial product formed from the fungicide fenaminosulf (p-dimethylaminobenzenediazo sodium sulfonate) was studied by enriching microbes in soils treated with the amine. Microorganisms isolated from DMPDA-treated soil belonged to the genera of Micrococcus, Alcaligenes, and Corynebacterium. Of the various isolates, Alcaligenes DM4 showed maximal growth on DMPDA utilizing it as sources of carbon and nitrogen. When grown in mineral salts basal medium containing 0.05% DMPDA to serve as carbon and nitrogen sources, Alcaligenes DM4 grew exponentially up to 18 h. Even though the characterization of the complete pathway of microbial degradation of DMPDA could not be carried out due to the auto-oxidation of the compound, the initial transformation product of DMPDA by Alcaligenes DM4 has been identified as a dimer. The dimer is generated into the culture medium presumably by the extra-cellular oxidase of Alcaligenes DM4. It is suggested that the risk-benefit evaluation on the use of fenaminosulf is to be made taking into consideration the microbial transformations of the fungicide.

Phosphorus nutrition and tolerance of cotton to water stress: II. Water relations, free and bound water and leaf expansion rate

In previous experiments, increased leaf-Phosphorus (P) content with increasing P supply enhanced the individual leaf expansion and water content of fresh cotton leaves in a severely drying soil. In this paper, we report on the bulk water content of leaves and its components, free and bound water, along with other measures of plant water status, in expanding cotton leaves of various ages in a drying soil with different P concentrations. The bound water in living tissue is more likely to play a major role in tolerance to abiotic stresses by maintaining the structural integrity and/or cell wall extensibility of the leaves, whilst an increased amount of free water might be able to enhance solute accumulation, leading to better osmotic adjustment and tolerance to water stress, and maintenance of the volumes of sub-cellular compartments for expansive leaf growth. There were strong correlations between leaf-P%, leaf water (total, free and bound water) and leaf expansion rate (LER) under water stress conditions in a severely drying soil. Increased soil-P enhanced the uptake of P from a drying soil, leading to increased supply of osmotically active inorganic solutes to the cells in growing leaves. This appears to have led to the accumulation of free water and more bound water, ultimately leading to increased leaf expansion rates as compared to plants in low P soil under similar water stress conditions. The greater amount of bound and free water in the high-P plants was not necessarily associated with changes in cell turgor, and appears to have maintained the cell-wall properties and extensibility under water stressed conditions in soils that are nutritionally P-deficient.

Rootzone amendments to improve soil moisture relations under newly-laid sod

Three experiments were conducted on the use of water retaining amendments under newly-laid turf mats. The work focused on the first 12 weeks of establishment. In soils that already possessed a good water-holding capacity, water retaining amendments did not provide any benefit. On a sand-based profile, a rooting depth of 200 mm was achieved with soil amendment products within three weeks of laying turf. Most products differed in their performance relative to each other at each three weekly measurement interval. Polyacrylamide gels gave superior results when the crystals were incorporated into the soil profile. They were not suitable for broadcasting at the soil/sod interface. Finer grades of crystals were less likely to be subject to excessive expansion than medium grade crystals after heavy rainfall. Turf establishment was more responsive to products at higher application rates, however these higher rates may result in surface stability problems.

Lantana camara L. (Verbenaceae) invasion effects on soil physicochemical properties

Lantana camara is a recognized weed of worldwide significance due to its extensive distribution and its impacts on primary industries and nature conservation. However, quantitative data on the impact of the weed on soil ecosystem properties are scanty, especially in SE Australia, despite the pervasive presence of the weed along its coastal and inland regions. Consequently, mineral soils for physicochemical analyses were collected beneath and away from L. camara infestations in four sites west of Brisbane, SE Australia. These sites (hoop pine plantation, cattle farm, and two eucalyptus forests with occasional grazing and a fire regime, respectively) vary in landscape and land-use types. Significant site effect was more frequently observed than effect due to invasion status. Nonetheless, after controlling for site differences, ~50% of the 23 soil traits examined differed significantly between infested and non-infested soils. Moisture, pH, Ca, total and organic C, and total N (but not exchangeable N in form of NO3-) were significantly elevated, while sodium, chloride, copper, iron, sulfur, and manganese, many of which can be toxic to plant growth if present in excess levels, were present at lower levels in soils supporting L. camara compared to soils lacking the weed. These results indicate that L. camara can improve soil fertility and influence nutrient cycling, making the substratum ideal for its own growth and might explain the ability of the weed to outcompete other species, especially native ones.

Influence of soil organic amendments on suppression of the burrowing nematode, Radopholus similis, on the growth of bananas.

Radopholus similis is a major constraint to banana production in Australia and growers have relied on nematicides to manage production losses. The use of organic amendments is one method that may reduce the need for nematicides, but there is limited knowledge of the influence of organic amendments on endo-migratory nematodes, such as R. similis. Nine different amendments, namely, mill mud, mill ash, biosolids, municipal waste compost, banana residue, grass hay, legume hay, molasses and calcium silicate were applied to the three major soil types of the wet tropics region used for banana production. The nutrient content of the amendments was also determined. Banana plants were inoculated with R. similis and grown in the soil-amendment mix for 12-weeks in a glasshouse experiment. Assessments of plant growth, plant-parasitic nematodes and soil nematode community characteristics were made at the termination of the experiment. Significant suppression of plant-parasitic nematodes occurred in soils amended with legume hay, grass hay, banana residue and mill mud relative to untreated soil. These amendments were found to have the highest N and C content. The application of banana residue and mill mud significantly increased shoot dry weight at the termination of the experiment relative to untreated soil. Furthermore, the applications of banana residue, grass hay, mill mud and municipal waste compost increased the potential for suppression of plant-parasitic nematodes through antagonistic activity. The application of amendments that are high in C and N appeared to be able to induce suppression of plant-parasitic nematodes in bananas, by developing a more favourable environment for antagonistic organisms.

Bacterial extracellular polysaccharides

Extracellular polysaccharides are as structurally and functionally diverse as the bacteria that synthesise them. They can be present in many forms, including cell-bound capsular polysaccharides, unbound "slime", and as O-antigen component of lipopolysaccharide, with an equally wide range of biological functions. These include resistance to desiccation, protection against nonspecific and specific host immunity, and adherence. Unsurprisingly then, much effort has been made to catalogue the enormous structural complexity of the extracellular polysaccharides made possible by the wide assortment of available monosaccharide combinations, non-carbohydrate residues, and linkage types, and to elucidate their biosynthesis and export. In addition, the work is driven by the commercial potential of these microbial substances in food, pharmaceutics and biomedical industries. Most recently, bacteria-mediated environmental restoration and bioleaching have been attracting much attention owing to their potential to remediate environmental effluents produced by the mining and metallurgy industries. In spite of technological advances in chemistry, molecular biology and imaging techniques that allowed for considerable expansion of knowledge pertaining to the bacterial surface polysaccharides, current understanding of the mechanisms of synthesis and regulation of extracellular polysaccharides is yet to fully explain their structural intricacy and functional variability.

Cat's claw creeper vine, Macfadyena unguis-cati (Bignoniaceae), invasion impacts: comparative leaf nutrient content and effects on soil physicochemical properties

Macfadyena unguis-cati (L.) Gentry (Bignoniaceae) is a major environmental weed in coastal Queensland, Australia. There is a lack of quantitative data on its leaf chemistry and its impact on soil properties. Soils from infested vs uninfested areas, and leaves of M. unguis-cati and three co-occurring vine species (one exotic, two native) were collected at six sites (riparian and non-riparian) in south-eastern Queensland. Effects of invasion status, species, site and habitat type were examined using univariate and multivariate analyses. Habitat type had a greater effect on soil nutrients than on leaf chemistry. Invasion effect of M. unguis-cati on soil chemistry was more pronounced in non-riparian than in riparian habitat. Significantly higher values were obtained in M. unguis-cati infested (vs. uninfested) soils for ~50% of traits. Leaf ion concentrations differed significantly between exotic and native vines. Observed higher leaf-nutrient load (especially nitrogen, phosphorus and potassium) in exotic plants aligns with the preference of invasive plant species for disturbed habitats with higher nutrient input. Higher load of trace elements (aluminium, boron, cadmium and iron) in its leaves suggests that cycling of heavy-metal ions, many of which are potentially toxic at excess level, could be accelerated in soils of M. unguis-cati-invaded landscape. Although inferences from the present study are based on correlative data, the consistency of the patterns across many sites suggests that M. unguis-cati may improve soil fertility and influence nutrient cycling, perhaps through legacy effects of its own litter input.

Skogsbränslets elementära sammansättning med tanke på förbränningsprocessen och för näringsämnesförluster i ekosystemet

There are several reasons for increasing the usage of forest biomass for energy in Finland. Apart from the fact that forest biomass is a CO2 -neutral energy source, it is also a domestic resource distributed throughout the country. Usage of forest biomass in the form of logging residues decreases Finland’s dependence of energy import and increases both incomes and employment. Wood chips are mainly made from logging residues, which constitute 64 % of the raw material. A large-scale use of forest biomass requires heed also to the potential negative aspects. Forest bioenergy is used extensively, but its impacts on the forests soil nutrition and carbon balance has not been studied much. Nor have there been many studies on the heavy metal or chlorine content of logging residues. The goal of this study was to examine the content of carbon, macronutrients, heavy metals and other for the combustion harmful substances in Scots pine and Norway spruce wood chips, and to estimate the effect of harvesting of logging residues on the forests carbon and nutrient balance. Another goal was to examine the energy content of the clear cut remains. The Wood chips for this study were gathered from pine and spruce dominated clear cut sites in southern Finland, in the costal forests between Hankoo and Siuntio. The number of sample locations were 29, and the average area was 3,15 ha and the average timber volume 212,6 m3 ha -1. The average logged timber volume was for Scots pine timber 70 m3 ha -1 and for Norway spruce timber 124 m3 ha -1 and for deciduous timber (birch and alder) 18,5 m3 ha -1. The proportion of spruce in the logging residues and the stand-volume were relevant for how much nutrients were taken from the forest ecosystem when harvesting logging residues. In this study it was noted that the nutrient content of the logging residues clearly increased when the percentage of spruce in the timber volume increased. The S, K, Na and Cl -contents in the logging residues in this study increased with an increasing percentage of spruce, which is probably due to the fact that the spruce is an effective collector of atmospheric dry-deposition. The amounts of nutrients that were lost when harvesting logging residues were less than those referred to in the literature. Within a circulation period (100 years), the forest soil gets substantially more nutrients from atmospheric deposition, litter fall and weathering than is lost through harvesting of logging residues after a clear cut. Harvesting of the logging residues makes for a relatively modest increase of the quantity of carbon that is removed from the forest compared to traditional forestry. Due to the fact that the clear cut remains in my study showed a high content of chlorine, there is a risk of corrosion in connection to the incineration of the logging residues in power plants especially at coastal areas/forests. The risk of sulphur -related corrosion is probably rather small, because S concentrations are relatively low in woodchips. The clear cut remains showed rather high heavy metal contents. If the heavy metal contents in this study are representative for the clear cut remains in the coastal forests generally, there might be reason to exert some caution when using the ash for forest fertilizing purposes.