Unfolding of Plasmodium falciparum triosephosphate isomerase in urea and guanidinium chloride solutions. Evidence for a novel disulfide exchange reaction in a covalently crosslinked mutant

The conformational stability of Plasmodium falciparum triosephosphate isomerase (TIMWT) enzyme has been investigated in urea and guanidinium chloride (GdmCl) solutions using circular dichroism, fluorescence, and size-exclusion chromatography. The dimeric enzyme is remarkably stable in urea solutions. It retains considerable secondary, tertiary, and quaternary structure even in 8 M urea. In contrast, the unfolding transition is complete by 2.4 M GdmCl. Although the secondary as well as the tertiary interactions melt before the perturbation of the quaternary structure, these studies imply that the dissociation of the dimer into monomers ultimately leads to the collapse of the structure, suggesting that the interfacial interactions play a major role in determining multimeric protein stability. The Cm(urea)/Cm(GdmCl) ratio (where Cm is the concentration of the denaturant required at the transition midpoint) is unusually high for triosephosphate isomerase as compared to other monomeric and dimeric proteins. A disulfide cross-linked mutant protein (Y74C) engineered to form two disulfide cross-links across the interface (13-74‘) and (13‘-74) is dramatically destablized in urea. The unfolding transition is complete by 6 M urea and involves a novel mechanism of dimer dissociation through intramolecular thiol−disulfide exchange.

Infinite dimensional slow modulations in a well known delayed model for cutting tool vibrations

We apply the method of multiple scales (MMS) to a well-known model of regenerative cutting vibrations in the large delay regime. By ``large'' we mean the delay is much larger than the timescale of typical cutting tool oscillations. The MMS up to second order, recently developed for such systems, is applied here to study tool dynamics in the large delay regime. The second order analysis is found to be much more accurate than the first order analysis. Numerical integration of the MMS slow flow is much faster than for the original equation, yet shows excellent accuracy in that plotted solutions of moderate amplitudes are visually near-indistinguishable. The advantages of the present analysis are that infinite dimensional dynamics is retained in the slow flow, while the more usual center manifold reduction gives a planar phase space; lower-dimensional dynamical features, such as Hopf bifurcations and families of periodic solutions, are also captured by the MMS; the strong sensitivity of the slow modulation dynamics to small changes in parameter values, peculiar to such systems with large delays, is seen clearly; and though certain parameters are treated as small (or, reciprocally, large), the analysis is not restricted to infinitesimal distances from the Hopf bifurcation.

Sodium-alginate-based proton-exchange membranes as electrolytes for DMFCs

Novel mixed-matrix membranes prepared by blending sodium alginate (NaAlg) with polyvinyl alcohol (PVA) and certain heteropolyacids (HPAs), such as phosphomolybdic acid (PMoA), phosphotungstic acid (PWA) and silicotungstic acid (SWA), followed by ex-situ cross-linking with glutaraldehyde (GA) to achieve the desired mechanical and chemical stability, are reported for use as electrolytes in direct methanol fuel cells (DMFCs). NaAlg-PVA-HPA mixed matrices possess a polymeric network with micro-domains that restrict methanol cross-over. The mixed-matrix membranes are characterised for their mechanical and thermal properties. Methanol cross-over rates across NaAlg-PVA and NaAlg-PVA-HPA mixed-matrix membranes are studied by measuring the mass balance of methanol using a density meter. The DMFC using NaAlg-PVA-SWA exhibits a peak power-density of 68 mW cm(-2) at a load current-density of 225 mA cm(-2), while operating at 343 K. The rheological properties of NaAlg and NaAlg-PVA-SWA viscous solutions are studied and their behaviour validated by a non-Newtonian power-law.

Origin of nonmetallicity in PrBa2Cu3O7 from a study of Gd1−xPrxBa2Cu3O7 using soft x-ray absorption at the oxygen K-edge

We present the x-ray absorption data at the oxygen K-edge using total yield technique for Gd1−xPrxba2Cu3O7 (x= 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0). The data clearly to oxygen that the holes doped in the GdBa2Cu3O7 due to oxygen composition are not removed by Pr doping even for the x = 1.0 sample, suggesting that Pr is predominantly in the formally trivalent state. However, the data also clearly indicate the evidence of hybridization effects between the Pr3+ and the adjacent CuO2 layers. This is suggested to be responsible for the progressive suppression of Tc and the metallicity with Pr doping in these systems.

Phase relations in the system BiO1.5–SrO–CuO at 1123 K

Phase relations in the system Bi-Sr-Cu-O at 1123 K have been investigated using optical microscopy, electron-probe microanalysis (EPMA) and powder X-ray diffraction (XRD) of equilibrated samples. Differential thermal analysis (DTA) was used to confirm liquid formation for compositions rich in BiO1.5. Compositions along the three pseudo-binary sections and inside the pseudo-ternary triangle have been examined. The attainment of equilibrium was facilitated by the use of freshly prepared SrO as the starting material. The loss of Bi2O3 from the sample was minimized by double encapsulation. A complete phase diagram at 1123 K is presented. It differs significantly from versions of the phase diagram published recently.

Radiative interactions in boundary layers

A detailed description of radiative interactions in laminar compressible boundary layers for moderate Mach numbers is presented by way of asymptotic analysis and supporting solutions. The radiation field is described by the differential approximation. While the asymptotic analysis is valid for large N (the ratio of photon mean free path to molecular mean free path) and arbitrary Boltzmann number, Bo (the ratio of convective heat flux to radiation heat flux), the solutions are obtained for Bo [double less-than sign] 1, the case of strong radiative interactions. The asymptotic analysis shows the existence of an optically thin boundary layer for large N and all Bo. For Bo [double less-than sign] 1, two outer regions are observed — one optically thin (at short distances from the leading edge) and the other optically thick (at large distances from the leading edge). An interesting feature not pointed out in the previous literature is the existence of a wall layer at large distances from the leading edge where convective heat flux can be ignored to the leading order of approximation. The radiation field in all cases can be very well approximated by a one-dimensional description. The solutions have been constructed using the ideas of matched asymptotic expansions by approximate analytical procedures and numerical methods. It is shown that, to the leading order of approximation, the radiation slip method yields exactly the same result as the more complicated matching procedure. Both the cases of linear and nonlinear radiation have been considered, the former being of interest in developing approximate methods which are subsequently generalized to handle the nonlinear problem. Detailed results are presented for both cases.

Valokuvallistettu luonto : I. K. Inhan tuotanto luonnon merkityksellistäjänä

Photographized nature I. K. Inha s work as a signification of nature The dissertation examines, through the work of the Finnish photographer and writer I. K. Inha (formerly Konrad Into Nyström) (1865 1930), the different ways in which the signification of nature is achieved. The principal material consists of Inha s work from 1890 to 1925, from which a number of photographs and texts are considered and upon which the photographization of nature is contemplated. The dissertation addresses the issue of how nature is conceived and how the act of photographizing it can be defined. The methodical context of the study is composed of three thematic baskets that structure the material and which consist of narrations on Finnish national perception, nature conservation and understanding the world. In the first case nature is seen as the natural environment encompassing lakes, seashores, forests, and hills, which at the time were often perceived from a utilitarian viewpoint. By the photographization they generated a pictorial narrative that could be shared. The natural environment was thus turned into landscape by means of photography, following the global pictorial concepts picturesque and sublime, as well as the national canons that had been developed in literature and the visual arts. In the narrations concerning nature conservation, the photographization did not merely occur within the limits of presuppositions, but rather nature was given the opportunity to unfold itself. While the photograph was being established as a basis for supporting nature conservation or to highlight the destruction of nature at the hand of Man, an attempt was made to represent subjects that were difficult to convey in photographs, such as nature s power or the miracle of growth. The thesis suggests, that in the third case the concept of nature broke away from its strict interconnection with the natural environment and led to a contemplation of nature that is perceivable in a person. In this context the photograph and the photographization are interpreted as an attempt to understand a person and his or her very existence in the world, while this same existential wonder is seen as being embodied in Inha s portrait of a rune singer and in his photographs of forest interior and water. Further, the thesis asks whether photographing nature could be interpreted as an action similar to the idea of the phenomenological reduction as a means of bypassing the photographer s prevailing way of being.

Ion-acoustic solutions and shock waves in multicomponent plasmas

The present investigation of ion-acoustic waves is based on the study of the nonlinearity of plasma waves in a dispersive medium. Here the authors study ion-acoustic solitary waves in a warm ion plasma with non-isothermal electrons and then the results for solitary waves in a plasma with isothermal electrons are obtained. Incorporating the previous results obtained from the solitary wave solutions, the authors generalize the effect of negative ions on ion-acoustic waves in plasmas consisting of either a warm or cold ion species. A reflection phenomenon of ions in these waves is also studied. These results can be generalized, but the discussion is limited to a particular model of the plasma.

Local approximability of max-min and min-max linear programs

In a max-min LP, the objective is to maximise ω subject to Ax ≤ 1, Cx ≥ ω1, and x ≥ 0. In a min-max LP, the objective is to minimise ρ subject to Ax ≤ ρ1, Cx ≥ 1, and x ≥ 0. The matrices A and C are nonnegative and sparse: each row ai of A has at most ΔI positive elements, and each row ck of C has at most ΔK positive elements. We study the approximability of max-min LPs and min-max LPs in a distributed setting; in particular, we focus on local algorithms (constant-time distributed algorithms). We show that for any ΔI ≥ 2, ΔK ≥ 2, and ε > 0 there exists a local algorithm that achieves the approximation ratio ΔI (1 − 1/ΔK) + ε. We also show that this result is the best possible: no local algorithm can achieve the approximation ratio ΔI (1 − 1/ΔK) for any ΔI ≥ 2 and ΔK ≥ 2.

Removal of hexavalent chromium using coffee husk

The potential to remove chromium(VI) from aqueous solutions through biosorption using coffee husk was investigated. The effects of pH, contact time, initial concentration and adsorbent dosage on the adsorption of Cr(VI) were studied. The data obeyed Langmuir and Freundlich adsorption isotherms. The Langmuir adsorption capacity was found to be 44.95 mg/g. The Freundlich constants K-f and n were 1.027 mg/g (litre/mg)(n)] and 1.493, respectively. Desorption studies indicated the removal of 60% of the hexavalent chromium. Infrared spectral studies revealed the presence of functional groups, such as hydroxyl and carboxyl groups, on the surface of the biomass, which facilitates biosorption of Cr(VI).