A H-1-NMR STUDY OF BILIRUBIN IX-ALPHA SOLUBILIZATION BY CHOLATE MICELLES - APPLICATION OF NUCLEAR OVERHAUSER EFFECTS

The solubilization of bilirubin IX-Alpha in aqueous solution by sodium cholate micelles has been examined by 270 MHz 1H-NMR spectroscopy. Incorporation of bilirubin into the micelles is accompanied by specific shifts of bilirubin vinyl and bridgehead protons and the C18 and C19 methyl groups of the steroid. The observed chemical shifts show a monotonic concentration dependence suggesting that changes in aggregation size are continuous. Nuclear Overhauser effects (NOE) have been shown to be a useful probe or micellization. A 4:1 cholate/bilirubin mixture has been investigated by difference NOE spectroscopy. The observation of intermolecular nuclear Overhauser effects between peripheral protons of bilirubin and cholate are diagnostic of spatially proximate groups. Inter-cholate nuclear Overhauser effects increase in magnitude upon bilirubin incorporation suggesting closer packing of steroid molecules on solubilization of the pigment. Intramolecular nuclear Overhauser effects observed for solubilized bilirubin are consistent with a compact intramolecularly hydrogen-bonded conformation resembling that determined for bilirubin in the solid state.

The performance of irrigated mixtures of tall fescue, ryegrass and white clover in subtropical Australia. 2. The effects on yield and botanical composition of managing for quality.

The effects on yield, botanical composition and persistence, of using a variable defoliation schedule as a means of optimising the quality of the tall fescue component of simple and complex temperate pasture mixtures in a subtropical environment was studied in a small plot cutting experiment at Gatton Research Station in south-east Queensland. A management schedule of 2-, 3- and 4-weekly defoliations in summer, autumn and spring and winter, respectively, was imposed on 5 temperate pasture mixtures: 2 simple mixtures including tall fescue (Festuca arundinacea) and white clover (Trifolium repens); 2 mixtures including perennial ryegrass (Lolium perenne), tall fescue and white clover; and a complex mixture, which included perennial ryegrass, tall fescue, white, red (T. pratense) and Persian (T. resupinatum) clovers and chicory (Cichorium intybus). Yield from the variable cutting schedule was 9% less than with a standard 4-weekly defoliation. This loss resulted from reductions in both the clover component (13%) and cumulative grass yield (6%). There was no interaction between cutting schedule and sowing mixture, with simple and complex sowing mixtures reacting in a similar manner to both cutting schedules. The experiment also demonstrated that, in complex mixtures, the cutting schedules used failed to give balanced production from all sown components. This was especially true of the grass and white clover components of the complex mixture, as chicory and Persian clover components dominated the mixtures, particularly in the first year. Quality measurements (made only in the final summer) suggested that variable management had achieved a quality improvement with increases in yields of digestible crude protein (19%) and digestible dry matter (9%) of the total forage produced in early summer. The improvements in the yields of digestible crude protein and digestible dry matter of the tall fescue component in late summer were even greater (28 and 19%, respectively). While advantages at other times of the year were expected to be smaller, the data suggested that the small loss in total yield was likely to be offset by increases in digestibility of available forage for grazing stock, especially in the critical summer period.

Undersowing in a northern climate: effects on spring cereal yield and risk of nitrate leaching

Disadvantages of invariable cereal cropping, concern of nutrient leaching and prices of nitrogen (N) fertilizer have all increased during last decades. An undersown crop, which grows together with a main crop and after harvest, could mitigate all those questions. The aim of this study was to develop undersowing in Finnish conditions, so that it suits for spring cereal farming as well as possible and enhances taking care of soil and environment, especially when control of N is concerned. In total, 17 plant species were undersown in spring cereals during the field experiments between 1991-1999 at four sites in South and Central Finland, but after selection, eight of them were studied more thoroughly. Two legumes, one grass species and one mixture of them were included in long-term trials in order to study annually repeated undersowing. Further, simultaneous broadcasting of seeds instead of separate undersowing was studied. Grain yield response and the capacity of the undersown crop to absorb soil N or fix N from atmosphere, and the release of N were of greatest interest. Seeding rates of undersown crops and N fertilization rates during annually repeated undersowing were also studied. Italian ryegrass (Lolium multiflorum Lam., IR) absorbed soil nitrate N (NO3-N) most efficiently in autumn and timothy (Phleum pratense L.) in spring. The capacity of other grass species to absorb N was low, or it was insufficient considering the negative effect on grain yield. Red clover (Trifolium pratense L.) and white clover (Trifolium repens L.) suited well in annually repeated undersowing, supplying fixed N for cereals without markedly increased risk of N leaching. Autumn oriented growth rhythm of the studied legumes was optimal for undersowing, whereas the growth rhythm of grasses was less suited but varied between species. A model of adaptive undersowing system was outlined in order to emphasize allocation of measures according needs. After defining the goal of undersowing, many decisions are to be done. When diminishing N leaching is primarily sought, a mixture of IR and timothy is advantageous. Clovers suit for replacing N fertilization, as the positive residual effect is greater than the negative effect caused by competition. A mixture of legume and non legume is a good choice when increased diversity is the main target. Seeding rate is an efficient means for adjusting competition and N effects. Broadcasting with soil covering equipment can be used to establish an undersown crop. In addition, timing and method of cover crop termination have an important role in the outcome. Continuous observing of the system is needed as for instance conditions significantly affect growth of undersown crop and on the other hand N release from crop residues may increase in long run.

Solvent effects on the structure of N-methylpyrrole as studied by nmr in nematic solvents

The proton NMR spectra of N-methylpyrrole oriented in the nematic phases of liquid crystals with positive and negative diamagnetic anisotropies and their mixtures are reported. Geometrical parameters derived from the spectra at the critical point in the mixture of liquid crystals with positive and negative diamagnetic anisotropies, where macroscopic diamagnetic anisotropy vanishes, are similar to those obtained in the solvent with negative diamagnetic anisotropy. However, significant distortions in the molecular structure attributed to solvent effects have been observed in liquid crystals with positive diamagnetic anisotropy. The minimum energy conformation has one C---H of the methyl perpendicular to the ring.

Reactive state selectivity in photodimerization through micellar counter-ion effects: photodimerization of acenaphthylenes

Photodimerization of acenaphthylene and 5,6-dichloroacenaphthylene solubilized in sodium dodecylsulphate (SDS), cetyltrimethylammonium chloride (CTAC), dodecyltrimethylammonium chloride (DTAC), cetyltrimethylammonium bromide (CTAB) and Triton X-100 micelles gives a mixture of cis and trans dimers. The magnitude of the cis:trans ratio is sensitive to the type of micelle used. In CTAB micelles the heavy atom effect of the bromide counter-ions leads to an increased triplet-derived trans dimer yield, whereas in micelles with light atom counter-ions (CTAC, DTAC and SDS) the singlet-derived cis dimer predominates.

Effects of environmental variation on ecological and evolutionary dynamics

Environmental variation is a fact of life for all the species on earth: for any population of any particular species, the local environmental conditions are liable to vary in both time and space. In today's world, anthropogenic activity is causing habitat loss and fragmentation for many species, which may profoundly alter the characteristics of environmental variation in remaining habitat. Previous research indicates that, as habitat is lost, the spatial configuration of remaining habitat will increasingly affect the dynamics by which populations are governed. Through the use of mathematical models, this thesis asks how environmental variation interacts with species properties to influence population dynamics, local adaptation, and dispersal evolution. More specifically, we couple continuous-time continuous-space stochastic population dynamic models to landscape models. We manipulate environmental variation via parameters such as mean patch size, patch density, and patch longevity. Among other findings, we show that a mixture of high and low quality habitat is commonly better for a population than uniformly mediocre habitat. This conclusion is justified by purely ecological arguments, yet the positive effects of landscape heterogeneity may be enhanced further by local adaptation, and by the evolution of short-ranged dispersal. The predicted evolutionary responses to environmental variation are complex, however, since they involve numerous conflicting factors. We discuss why the species that have high levels of local adaptation within their ranges may not be the same species that benefit from local adaptation during range expansion. We show how habitat loss can lead to either increased or decreased selection for dispersal depending on the type of habitat and the manner in which it is lost. To study the models, we develop a recent analytical method, Perturbation expansion, to enable the incorporation of environmental variation. Within this context, we use two methods to address evolutionary dynamics: Adaptive dynamics, which assumes mutations occur infrequently so that the ecological and evolutionary timescales can be separated, and via Genotype distributions, which assume mutations are more frequent. The two approaches generally lead to similar predictions yet, exceptionally, we show how the evolutionary response of dispersal behaviour to habitat turnover may qualitatively depend on the mutation rate.

Modeling transport through an environment crowded by a mixture of obstacles of different shapes and sizes

Many biological environments are crowded by macromolecules, organelles and cells which can impede the transport of other cells and molecules. Previous studies have sought to describe these effects using either random walk models or fractional order diffusion equations. Here we examine the transport of both a single agent and a population of agents through an environment containing obstacles of varying size and shape, whose relative densities are drawn from a specified distribution. Our simulation results for a single agent indicate that smaller obstacles are more effective at retarding transport than larger obstacles; these findings are consistent with our simulations of the collective motion of populations of agents. In an attempt to explore whether these kinds of stochastic random walk simulations can be described using a fractional order diffusion equation framework, we calibrate the solution of such a differential equation to our averaged agent density information. Our approach suggests that these kinds of commonly used differential equation models ought to be used with care since we are unable to match the solution of a fractional order diffusion equation to our data in a consistent fashion over a finite time period.

Immunological Effects of Probiotic Bacteria in Prevention and Treatment of Allergic Diseases in Children

Epidemiological and experimental studies suggest that changes in gut microbial balance are associated with increases in the prevalence of allergic diseases. Probiotics are proposed to provide beneficial immunoregulatory signals which aid in oral tolerance achievement and alleviation of symptoms of allergic diseases. The present study evaluates both the immunological mechanisms of probiotics in infants with allergic diseases and their preventive aspect among infants prone to allergy. Furthermore, the purpose of the study was to characterise the immunological features of cord blood mononuclear cells (CBMCs) in infants at high genetic risk for allergy. GATA-3 expression (p = 0.03), interleukin (IL) -2(p = 0.026), and IL-5 (p = 0.013) secretion of stimulated CBMCs were higher in IgE-sensitized infants at age 2 than in non-allergic, non-sensitized infants. Lactobacillus GG (LGG) treatment increased secretion of IFN-γ by PBMCs in vitro in infants with cow s milk allergy (CMA) (p = 0.006) and in infants with IgE-associated eczema (p = 0.017), when compared to levels in the placebo group. A probiotic mixture, increased secretion of IL-4 by PBMCs in vitro in infants with CMA (p = 0.028), when compared with placebo-group levels. The LGG treatment induced higher plasma C-reactive protein (CRP) (p = 0.021) and IL-6 (p = 0.036) levels in infants with IgE-associated eczema than in the placebo group. The probiotic mixture induced higher plasma IL-10 levels in infants with eczema (p = 0.016). In the prevention study of allergic dis-eases, the infants receiving the probiotic mixture had higher plasma levels of CRP (p = 0.008), total IgA (p = 0.016), total IgE (p = 0.047), and IL-10 (p = 0.002) than did infants in the placebo group. Increased CRP level at age 6 months was associated with a decreased risk for eczema at age 2 not only in the infants who received probiotics but also in the placebo group (p = 0.034). In conclusion, the priming of the GATA-3 and IL-5 pathway can occur in utero, and a primary feature of T-cells predisposing to IgE-sensitization seems to directly favour Th2 deviation. LGG treatment induced increased plasma levels of CRP and IL-6 in infants with IgE-associated eczema, suggesting an activation of innate immu-nity. The probiotic mixture, when given to allergy-prone infants, induced inflammation, detected as increased plasma CRP levels, which at age 6 months was associated with decreased risk for eczema at age 2.The probiotic-induced response in allergy prone infants was characterized by their higher plasma IL-10, total IgE, and CRP levels, without induction of an allergen-specific IgE response. In this respect, the probiotics in infancy appear to induce protective immune profiles that are characteristic for chronic low-grade inflammation, a response resembling that of helminth-like infections.

Defoliation and patchy nutrient return drive grazing effects on plant and soil properties in a dairy cow pasture

Large herbivores can influence plant and soil properties in grassland ecosystems, but especially for belowground biota and processes, the mechanisms that explain these effects are not fully understood. Here, we examine the capability of three grazing mechanisms-plant defoliation, dung and urine return, and physical presence of animals (causing trampling and excreta return in patches)-to explain grazing effects in Phleum pratense-Festuca pratensis dairy cow pasture in Finland. Comparison of control plots and plots grazed by cows showed that grazing maintained original plant-community structure, decreased shoot mass and root N and P concentrations, increased shoot N and P concentrations, and had an inconsistent effect on root mass. Among soil fauna, grazing increased the abundance of fungivorous nematodes and Aporrectodea earthworms and decreased the abundance of detritivorous enchytraeids and Lumbricus earthworms. Grazing also increased soil density and pH but did not affect average soil inorganic-N concentration. To reveal the mechanisms behind these effects, we analyzed results from mowed plots and plots that were both mowed and treated with a dung and urine mixture. This comparison revealed that grazing effects on plant attributes were almost entirely explained by defoliation, with only one partly explained by excreta return. Among belowground attributes, however, the mechanisms were more mixed, with effects explained by defoliation, patchy excreta return, and cow trampling. Average soil inorganic-N concentration was not affected by grazing because it was simultaneously decreased by defoliation and increased by cow presence. Presence of cows created great spatial heterogeneity in soil N availability and abundance of fungivorous nematodes. A greenhouse trial revealed a grazing-induced soil feedback on plant growth, which was explained by patchiness in N availability rather than changes in soil biota. Our results show that grazing effects on plant attributes can be satisfactorily predicted using the effects of defoliation, whereas those on soil fauna and soil N availability need understanding of other mechanisms as well. The results indicate that defoliation-induced changes in plant ecophysiology and the great spatial variation in N availability created by grazers are the two key mechanisms through which large herbivores can control grassland ecosystems.

Effects of capillary waves on the thickness of wetting layers

The free energy contribution of capillary waves is calculated to show its significant dependence on the thickness of the liquid layer, when the thickness is very small. It is shown that these oscillations can play an important role in determining the thermodynamic stability of a wetting layer, close to the critical point of a binary liquid mixture in the case of both short range and long range forces. In particular, the thickness of the wetting layer goes to zero as the temperature T approaches Tc.

Impurity effects on the critical behaviour of the electrical resistance of binary liquid mixtures

The electrical resistance of the binary liquid system cyclohexane + acetic anhydride is measured, in the critical region, both in the pure mixture and when the mixture is doped with small amounts (≈ 100 ppm) of H2O/D2O impurities.T c was approached to aboutt=3×10−6 wheret=(T −T c )/T c . The critical exponentb ≈ 0.35 in the fit of the resistance data to the equationdR/dT ∼t −b does not seem to be affected appreciably by the impurities. There is a sign reversal ofdR/dt in the non-critical region. Binary liquid systems seem to violate the universality of the critical resistivity.

Inhibitory effects of wood extracts on the spoilage flora of marinated poultry meat

Polyphenolic compounds occurring naturally in knotwood of plants are known to have antimicrobial effects. The knots (i.e. the branch bases inside tree stems) and outer branches in pine trees contain a remarkably high concentration of phenolic stilbenes, while lignans are the major phenolic constituents of spruce knots. Large amount of these phenolic compounds can be extracted from wood knots at pulp and paper mills where their presence is undesirable. In Finland, marinating of broiler meat is done not only to increase or add value to the meat, but also to enhance the safety and shelf-life. These products are usually packed under a modified atmosphere for further protection against spoilage microorganisms. However, studies have revealed that addition of marinades to poultry products do not have an inhibitory effect on either some psychrotrophic anaerobic bacteria, such as Brochothrix thermosphacta or lactic acid bacteria associated with spoilage. Also, the activity of pathogenic Campylobacter jejuni is not affected by marinating. The objective of this study was to investigate the inhibitory and lethal activities of extracts from spruce (Picea spp.) and pine (Pinus spp.) knotwood and outer branches that are dissolved in ethanol against the spoilage microorganisms in modified atmosphere packaged marinated broiler products. Modified atmosphere packaged broiler products were separately inoculated with ‘normal’ marinades, marinades with 70% ethanol, marinades with a mixture of spruce and pine extracts dissolved in 70% ethanol or mixture of spruce and pine extracts in powder form. The bacterial colony forming units per gram obtained from each of the samples were analysed on de Man Rogosa and Sharpe agar at days 1, 6, 12 and 15. The results showed that there were significant differences in bacterial colony forming units per gram (P <0.05) between packages with ‘normal’ marinades and packages with extracts added to their marinades on the 12th and 15th day. It can be concluded that the addition of extracts from spruce and pine knotwood to marinades significantly retarded growth of spoilage microorganisms during the 15 day test period. However further research is warranted to characterise and establish the safety and suitability of the compound(s) in spruce and pine knotwood extracts that are responsible for inhibitory or lethal activity against the microbes that may be present in marinated poultry meat.

Phase nonequilibrium effects on the gain of a two-phase flow gasdynamic laser

Analysis of gas-particle nozzle flow is carried out with attention to the effect of dust particles on the vibrational relaxation phenomena and consequent effects on the gain of a gasdynamic laser. The phase nonequilibrium between the gas mixture and the particles during the nozzle expansion process is taken into account simultaneously. The governing equations of the two-phase nozzle flow have been transformed into similar form, and general correlating parameters have been obtained. It is shown from the present analysis that the particles present in the mixture affect the optimum gain obtainable from a gasdynamic laser adversely, and the effect depends on the size and loading of the particles in the mixture.

The effects of charge density and concentration on the composition of polyelectrolyte complexes

Polyelectrolyte complex formation involving carboxymethylcellulose and quaternized poly(vinylpyridine) as the polyions has been studied using viscosity and u.v. spectroscopic methods. The influence of charge density and molecular weight of two polycations on the composition of the complex has been investigated at two different concentrations. The charge density of the polycation is found to have different influences on the composition at different concentrations. The molecular weight of the polycation and the location of the ionic site on the polycation do not show any effect on the composition. A drastic increase in the viscosity of the polyion mixture containing quaternized poly(2-vinylpyridine) in the non-stoichiometric ratio shows evidence for the existence of the soluble polyelectrolyte complex. The results are analysed on the basis of the relative extension of the polyelectrolyte chains.

Autoignition in a non-premixed medium: DNS studies on the effects of three-dimensional turbulence

Direct numerical simulation (DNS) results of autoignition in anon-premixed medium under an isotropic, homogeneous, and decaying turbulence are presented. The initial mixture consists of segregated fuel parcels randomly distributed within warm air, and the entire medium is subjected to a three-dimensional turbulence. Chemical kinetics is modeled by a four-step reduced reaction mechanism for autoignition of n-heptane/air mixture. Thus, this work overcomes the principal limitations of a previous contribution of the authors on two-dimensional DNS of autoignition with a one-step reaction model. Specific attention is focused on the differences in the effects of two- and three-dimensional turbulence on autoignition characteristics. The three-dimensional results show that ignition spots are most likely to originate at locations jointly corresponding to the most reactive mixture fraction and low scalar dissipation rate. Further, these ignition spots are found to originate at locations corresponding to the core of local vortical structures, and after ignition, the burning gases move toward the vortex periphery Such a movement is explained as caused by the cyclostrophic imbalance developed when the local gas density is variable. These results lead to the conclusion that the local ignition-zone structure does not conform to the classical stretched flamelet description. Parametric studies show that the ignition delay time decreases with an increase in turbulence intensity. Hence, these three-dimensional simulation results resolve the discrepancy between trends in experimental data and predictions from DNSs of two-dimensional turbulence. This qualitative difference between DNS results from three- and two-dimensional simulations is discussed and attributed to the effect of vortex stretching that is present in the former, but not in the latter.