Effects of dietary phosphorus and calcium-to-phosphorus ratio on calcium and bone metabolism in healthy 20- to 43-year-old Finnish women

Dietary habits have changed during the past decades towards an increasing consumption of processed foods, which has notably increased not only total dietary phosphorus (P) intake, but also intake of P from phosphate additives. While the intake of calcium (Ca) in many Western countries remains below recommended levels (800 mg/d), the usual daily P intake in a typical Western diet exceeds by 2- to 3-fold the dietary guidelines (600 mg/d). The effects of high P intake in healthy humans have been investigated seldom. In this thesis healthy 20- to 43-year-old women were studied. In the first controlled study (n = 14), we examined the effects of P doses, and in a cross-sectional study (n = 147) the associations of habitual P intakes with Ca and bone metabolism. In this same cross-sectional study, we also investigated whether differences exist between dietary P originating from natural P sources and phosphate additives. The second controlled study (n = 12) investigated whether by increasing the Ca intake, the effects of a high P intake could be reduced. The associations of habitual dietary calcium-to-phosphorus ratios (Ca:P ratio) with Ca and bone metabolism were determined in a cross-sectional study design (n = 147). In the controlled study, the oral intake of P doses (495, 745, 1245 and 1995 mg/d) with a low Ca intake (250 mg/d) increased serum parathyroid hormone (S-PTH) concentration in a dose-dependent manner. In addition, the highest P dose decreased serum ionized calcium (S-iCa) concentration and bone formation and increased bone resorption. In the second controlled study with a dietary P intake of 1850 mg/d, by increasing the Ca intake from 480 mg/d to 1080 mg/d and then to 1680 mg/d, the S-PTH concentration decreased, the S-iCa concentration increased and bone resorption decreased dose-dependently. However, not even the highest Ca intake could counteract the effect of high dietary P on bone formation, as indicated by unchanged bone formation activity. In the cross-sectional studies, a higher habitual dietary P intake (>1650 mg/d) was associated with lower S-iCa and higher S-PTH concentrations. The consumption of phosphate additive-containing foods was associated with a higher S-PTH concentration. Moreover, habitual low dietary Ca:P ratios (≤0.50, molar ratio) were associated with higher S-PTH concentrations and 24-h urinary Ca excretions, suggesting that low dietary Ca:P ratios may interfere with homeostasis of Ca metabolism and increase bone resorption. In summary, excessive dietary P intake in healthy Finnish women seems to be detrimental to Ca and bone metabolism, especially when dietary Ca intake is low. The results indicate that by increasing dietary Ca intake to the recommended level, the negative effects of high P intake could be diminished, but not totally prevented. These findings imply that phosphate additives may be more harmful than natural P. Thus, reduction of an excessively high dietary P intake is also beneficial for healthy individuals.

Albert and Elsa Einstein on board ship with captain and unidentified man and woman leaving Hamburg going to California Portraits; Groups

Digital Image

Portrait of Albert Einstein in the Southern California desert Portraits; Men

Verso: "Er sinnt in der Wueste"

Polymerization of Ethene and Branched α-olefins with Group IV Metal Complexes Bearing Nitrogen- and Oxygen-Based Ligands

The commodity plastics that are used in our everyday lives are based on polyolefin resins and they find wide variety of applications in several areas. Most of the production is carried out in catalyzed low pressure processes. As a consequence polymerization of ethene and α-olefins has been one of the focus areas for catalyst research both in industry and academia. Enormous amount of effort have been dedicated to fine tune the processes and to obtain better control of the polymerization and to produce tailored polymer structures The literature review of the thesis concentrates on the use of Group IV metal complexes as catalysts for polymerization of ethene and branched α-olefins. More precisely the review is focused on the use of complexes bearing [O,O] and [O,N] type ligands which have gained considerable interest. Effects of the ligand framework as well as mechanical and fluxional behaviour of the complexes are discussed. The experimental part consists mainly of development of new Group IV metal complexes bearing [O,O] and [O,N] ligands and their use as catalysts precursors in ethene polymerization. Part of the experimental work deals with usage of high-throughput techniques in tailoring properties of new polymer materials which are synthesized using Group IV complexes as catalysts. It is known that the by changing the steric and electronic properties of the ligand framework it is possible to fine tune the catalyst and to gain control over the polymerization reaction. This is why in this thesis the complex structures were designed so that the ligand frameworks could be fairly easily modified. All together 14 complexes were synthesised and used as catalysts in ethene polymerizations. It was found that the ligand framework did have an impact within the studied catalyst families. The activities of the catalysts were affected by the changes in complex structure and also effects on the produced polymers were observed: molecular weights and molecular weight distributions were depended on the used catalyst structure. Some catalysts also produced bi- or multi-modal polymers. During last decade high-throughput techniques developed in pharmaceutical industries have been adopted into polyolefin research in order to speed-up and optimize the catalyst candidates. These methods can now be regarded as established method suitable for both academia and industry alike. These high-throughput techniques were used in tailoring poly(4-methyl-1-pentene) polymers which were synthesized using Group IV metal complexes as catalysts. This work done in this thesis represents the first successful example where the high-throughput synthesis techniques are combined with high-throughput mechanical testing techniques to speed-up the discovery process for new polymer materials.

Late Transition Metal and Aluminum Complexes for the Polymerization of Ethene and Acrylates

Polyethene, polyacrylates and polymethyl acrylates are versatile materials that find wide variety of applications in several areas. Therefore, polymerization of ethene, acrylates and methacrylates has achieved a lot attention during past years. Numbers of metal catalysts have been introduced in order to control the polymerization and to produce tailored polymer structures. Herein an overview on the possible polymerization pathways for ethene, acrylates and methacrylates is presented. In this thesis iron(II) and cobalt(II) complexes bearing tri- and tetradentate nitrogen ligands were synthesized and studied in the polymerization of tertbutyl acrylate (tBA) and methyl methacrylate (MMA). Complexes are activated with methylaluminoxane (MAO) before they form active combinations for polymerization reactions. The effect of reaction conditions, i.e. monomer concentration, reaction time, temperature, MAO to metal ratio, on activity and polymer properties were investigated. The described polymerization system enables mild reaction conditions, the possibility to tailor molar mass of the produced polymers and provides good control over the polymerization. Moreover, the polymerization of MMA in the presence of iron(II) complex with tetradentate nitrogen ligands under conditions of atom transfer radical polymerization (ATRP) was studied. Several manganese(II) complexes were studied in the ethene polymerization with combinatorial methods and new active catalysts were found. These complexes were also studied in acrylate and methacrylate polymerizations after MAO activation and converted into the corresponding alkyl (methyl or benzyl) derivatives. Combinatorial methods were introduced to discover aluminum alkyl complexes for the polymerization of acrylates and methacrylates. Various combinations of aluminum alkyls and ligands, including phosphines, salicylaldimines and nitrogen donor ligands, were prepared in situ and utilized to initiate the polymerization of tBA. Phosphine ligands were found to be the most active and the polymerization MMA was studied with these active combinations. In addition, a plausible polymerization mechanism for MMA based on ESI-MS, 1H and 13C NMR is proposed.

Magmatic evolution of topaz-bearing granite stocks within the Wiborg rapakivi granite batholith

This study brings new insights into the magmatic evolution of natural F-enriched peraluminous granitic systems. The Artjärvi, Sääskjärvi and Kymi granite stocks within the 1.64 Ga Wiborg rapakivi granite batholith have been investigated by petrographic, geochemical, experimental and melt inclusion methods. These stocks represent late-stage leucocratic and weakly peraluminous intrusive phases typical of rapakivi granites worldwide. The Artjärvi and Sääskjärvi stocks are multiphase intrusions in which the most evolved phase is topaz granite. The Kymi stock contains topaz throughout and has a well-developed zoned structure, from the rim to the center: stockscheider pegmatite equigranular topaz granite porphyritic topaz granite. Geochemically the topaz granites are enriched in F, Li, Be, Ga, Rb, Sn and Nb and depleted in Mg, Fe, Ti, Ba, Sr, Zr and Eu. The anomalous geochemistry and mineralogy of the topaz granites are essentially magmatic in origin; postmagmatic reactions have only slightly modified the compositions. The Kymi equigranular topaz granite shows the most evolved character, and the topaz granites at Artjärvi and Sääskjärvi resemble the less evolved porphyritic topaz granite of the Kymi stock. Stockscheiders are found at the roof contacts of the Artjärvi and Kymi stocks. The stockscheider at Artjärvi is composed of biotite-rich schlieren and pegmatite layers parallel to the contact. The schlieren layering is considered to have formed by velocity-gradient sorting mechanism parallel to the flow, which led to the accumulation of mafic minerals along the upper contact of the topaz granite. Cooling and contraction of the topaz granite formed fractures parallel to the roof contact and residual pegmatite magmas were injected along the fractures and formed the pegmatite layers. The zoned structure of the Kymi stock is the result of intrusion of highly evolved residual melt from deeper parts of the magma chamber along the fractured contact between the porphyritic granite crystal mush and country rock. The equigranular topaz granite and marginal pegmatite (stockscheider) crystallized from this evolved melt. Phase relations of the Kymi equigranular topaz granite have been investigated utilizing crystallization experiments at 100 to 500 MPa as a function of water activity and F content. Fluorite and topaz can crystallize as liquidus phases in F-rich peraluminous systems, but the F content of the melt should exceed 2.5 - 3.0 wt % to facilitate crystallization of topaz. In peraluminous F-bearing melts containing more than 1 wt % F, topaz and muscovite are expected to be the first F-bearing phases to crystallize at high pressure, whereas fluorite and topaz should crystallize first at low pressure. Overall, the saturation of fluorite and topaz follows the reaction: CaAl2Si2O8 (plagioclase) + 2[AlF3]melt = CaF2 (fluorite) + 2Al2SiO4F2 (topaz). The obtained partition coefficient for F between biotite and glass D(F)Bt/glass is 1.89 to 0.80 (average 1.29) and can be used as an empirical fluormeter to determine the F content of coexisting melts. In order to study the magmatic evolution of the Kymi stock, crystallized melt inclusions in quartz and topaz grains in the porphyritic and the equigranular topaz granites and the marginal pegmatite were rehomogenized and analyzed. The homogenization conditions for the melt inclusions from the granites were 700 °C, 300 MPa, and 24 h, and for melt inclusions from the pegmatite, 700 °C, 100 MPa, and 24/96 h. The majority of the melt inclusions is chemically similar to the bulk rocks (excluding H2O content), but a few melt inclusions in the equigranular granite show clearly higher F and low K2O contents (on average 11.6 wt % F, 0.65 wt % K2O). The melt inclusion compositions indicate coexistence of two melt fractions, a prevailing peraluminous and a very volatile-rich, possibly peralkaline. Combined petrological, experimental and melt inclusion studies of the Kymi equigranular topaz granite indicate that plagioclase was the liquidus phase at nearly water-saturated (fluid-saturated) conditions and that the F content of the melt was at least 2 wt %. The early crystallization of biotite and the presence of muscovite in crystallization experiments at 200 MPa contrasts with the late-stage crystallization of biotite and the absence of muscovite in the equigranular granite, indicating that crystallization pressure may have been lower than 200 MPa for the granite.

Velocity ratio in the analysis of linear dynamical systems

The transfer matrix method is known to be well suited for a complete analysis of a lumped as well as distributed element, one-dimensional, linear dynamical system with a marked chain topology. However, general subroutines of the type available for classical matrix methods are not available in the current literature on transfer matrix methods. In the present article, general expressions for various aspects of analysis-viz., natural frequency equation, modal vectors, forced response and filter performance—have been evaluated in terms of a single parameter, referred to as velocity ratio. Subprograms have been developed for use with the transfer matrix method for the evaluation of velocity ratio and related parameters. It is shown that a given system, branched or straight-through, can be completely analysed in terms of these basic subprograms, on a stored program digital computer. It is observed that the transfer matrix method with the velocity ratio approach has certain advantages over the existing general matrix methods in the analysis of one-dimensional systems.

Ratio of Diffusion Coefficient to Mobility for Electrons in SF6-Air and Freon-Nitrogen Mixtures

The ratio of diffusion coefficient to mobility (D/¿) for electrons has been measured in SF6-air and freon-nitrogen mixtures for various concentrations of SF6 and freon in the mixtures over the range 140¿ E/p¿ 220 V.cm-1 - torr-1. In SF6-air mixtures, the values of D/¿ were always observed to lie intermediate between the values for the pure gases. However, in freon-nitrogen mixtures, with a small concentration (10 percent) of freon in the mixture, the values of D/¿ are found to lie above the boundaries determined by the pure gases. In this mixture, over the lower E/p range (140 to 190) the electrons appear to lose a large fraction of their energy by the excitation of the complex freon molecules, while at higher E/p values (200 to 240), the excitation and consequent deexcitation of nitrogen molecules and its metastables seem to cause an increased rate of ionization of freon molecules.

Influence of Joint Thickness and Mortar-Block Elastic Properties on the Strength and Stresses Developed in Soil-Cement Block Masonry

Soil-cement blocks are employed for load bearing masonry buildings. This paper deals with the study on the influence of bed joint thickness and elastic properties of the soil-cement blocks, and the mortar on the strength and behavior of soil-cement block masonry prisms. Influence of joint thickness on compressive strength has been examined through an experimental program. The nature of stresses developed and their distribution, in the block and the mortar of the soil-cement block masonry prism under compression, has been analyzed by an elastic analysis using FEM. Influence of various parameters like joint thickness, ratio of block to mortar modulus, and Poisson's ratio of the block and the mortar are considered in FEM analysis. Some of the major conclusions of the study are: (1) masonry compressive strength is sensitive to the ratio of modulus of block to that of the mortar (Eb/Em) and masonry compressive strength decreases as the mortar joint thickness is increased for the case where the ratio of block to mortar modulus is more than 1; (2) the lateral tensile stresses developed in the masonry unit are sensitive to the Eb/Em ratio and the Poisson's ratio of mortar and the masonry unit; and (3) lateral stresses developed in the masonry unit are more sensitive to the Poisson's ratio of the mortar than the Poisson's ratio of the masonry unit.

Zero-crossings in turbulent signals

A primary motivation for this work arises from the contradictory results obtained in some recent measurements of the zero-crossing frequency of turbulent fluctuations in shear flows. A systematic study of the various factors involved in zero-crossing measurements shows that the dynamic range of the signal, the discriminator characteristics, filter frequency and noise contamination have a strong bearing on the results obtained. These effects are analysed, and explicit corrections for noise contamination have been worked out. New measurements of the zero-crossing frequency N0 have been made for the longitudinal velocity fluctuation in boundary layers and a wake, for wall shear stress in a channel, and for temperature derivatives in a heated boundary layer. All these measurements show that a zero-crossing microscale, defined as Λ = (2πN0)−1, is always nearly equal to the well-known Taylor microscale λ (in time). These measurements, as well as a brief analysis, show that even strong departures from Gaussianity do not necessarily yield values appreciably different from unity for the ratio Λ/λ. Further, the variation of N0/N0 max across the boundary layer is found to correlate with the familiar wall and outer coordinates; the outer scaling for N0 max is totally inappropriate, and the inner scaling shows only a weak Reynolds-number dependence. It is also found that the distribution of the interval between successive zero-crossings can be approximated by a combination of a lognormal and an exponential, or (if the shortest intervals are ignored) even of two exponentials, one of which characterizes crossings whose duration is of the order of the wall-variable timescale ν/U2*, while the other characterizes crossings whose duration is of the order of the large-eddy timescale δ/U[infty infinity]. The significance of these results is discussed, and it is particularly argued that the pulse frequency of Rao, Narasimha & Badri Narayanan (1971) is appreciably less than the zero-crossing rate.

Velocity ratio-cum-transfer matrix method for the evaluation of a muffler with mean flow

The paper deals with a method for the evaluation of exhaust muffers with mean flow. A new set of variables, convective pressure and convective mass velocity, have been defined to replace the acoustic variables. An expression for attenuation (insertion loss) of a muffler has been proposed in terms of convective terminal impedances and a velocity ratio, on the lines of the one existing for acoustic filters. In order to evaluate the velocity ratio in terms of convective variables, transfer matrices for various muffler elements have been derived from the basic relations of energy, mass and momentum. Finally, the velocity ratiocum-transfer matrix method is illustrated for a typical straight-through muffler.