Rotational isomerism about the Ca-CO bond in proline derivatives. 1H and 13C NMR studies of benzyloxycarbonyl-Pro-N-methylamide and pivaloyl-Pro-N-methylamide

The 270 MHz 1H n.m.r. spectrum of benzyloxycarbonyl-Pro-N-methylamide in CDCl3 is exchange broadened at 293° K. Spectral lines due to two species are frozen out at 253° K and a dynamically averaged spectrum is obtained at 323° K. A selective broadening of the Cβ and Cγ resonances in the 13C n.m.r. spectrum is observed at 253° K, with a splitting of the Cβ and Cγ resonances into a pair of lines of unequal intensity. A similar broadening of Cβ and Cγ peaks is also detected in pivaloyl-Pro-N-methylamide where cis-trans interconversion about the imide bond is precluded by the bulky t-butyl group. The rate process is thus attributed to rotation about the Cα-CO bond (ψ) and a barrier (ΔG#) of 14kcal mol-1 is estimated. 13C n.m.r. data for pivaloyl-Pro-N-methylamide in a number of solvents is presented and the differences in the Cβ and Cγ chemical shifts are interpreted in terms of rotational isomerism about the Cα-CO bond.

Characterization of the Entamoeba histolytica Ornithine Decarboxylase-Like Enzyme

Background: The polyamines putrescine, spermidine, and spermine are organic cations that are required for cell growth and differentiation. Ornithine decarboxylase (ODC), the first and rate-limiting enzyme in the polyamine biosynthetic pathway, is a highly regulated enzyme. Methodology and Results: To use this enzyme as a potential drug target, the gene encoding putative ornithine decarboxylase (ODC)-like sequence was cloned from Entamoeba histolytica, a protozoan parasite causing amoebiasis. DNA sequence analysis revealed an open reading frame (ORF) of similar to 1,242 bp encoding a putative protein of 413 amino acids with a calculated molecular mass of 46 kDa and a predicted isoelectric point of 5.61. The E. histolytica putative ODC-like sequence has 33% sequence identity with human ODC and 36% identity with the Datura stramonium ODC. The ORF is a single-copy gene located on a 1.9-Mb chromosome. The recombinant putative ODC protein (48 kDa) from E. histolytica was heterologously expressed in Escherichia coli. Antiserum against recombinant putative ODC protein detected a band of anticipated size similar to 46 kDa in E. histolytica whole-cell lysate. Difluoromethylornithine (DFMO), an enzyme-activated irreversible inhibitor of ODC, had no effect on the recombinant putative ODC from E. histolytica. Comparative modeling of the three-dimensional structure of E. histolytica putative ODC shows that the putative binding site for DFMO is disrupted by the substitution of three amino acids-aspartate-332, aspartate-361, and tyrosine-323-by histidine-296, phenylalanine-305, and asparagine-334, through which this inhibitor interacts with the protein. Amino acid changes in the pocket of the E. histolytica enzyme resulted in low substrate specificity for ornithine. It is possible that the enzyme has evolved a novel substrate specificity. Conclusion: To our knowledge this is the first report on the molecular characterization of putative ODC-like sequence from E. histolytica. Computer modeling revealed that three of the critical residues required for binding of DFMO to the ODC enzyme are substituted in E. histolytica, resulting in the likely loss of interactions between the enzyme and DFMO.

Determination of the thermodynamic stability of TiB2

The standard free energy of formation of titanium boride (TiB2) Was measured by the Electro Motive Force (EMF) method (by using yttria doped thoria (YDT) as the solid electrolyte). Two galvanic cells viz. Cell (I): Pt, TiB2 (s), TiO2 (s), B (s) vertical bar YDT vertical bar NiO (s), Ni (s), Pt and cell (II): Pt, TiB2 (s), TiO2 (s), B (s) vertical bar YDT vertical bar FeO (s). Fe (s), Pt were constructed in order to determine the Delta(f)G degrees, of TiB2. Enthalpy increments on TiB2 were measured by using inverse drop calorimetry over the temperature range 583-1769 K. The heat capacity, entropy and the free energy function have been derived from these experimental data in the temperature range 298-1800 K. The mean value of the standard enthalpy of formation of TiB2 (Delta H-f(298)degrees (TiB2)) was obtained by combining these Delta(f)G degrees, values and the free energy functions of TiB2 derived from the drop calorimetry data. The mean values of Delta H-f(298)degrees (TiB2) derived from the Delta(f)G degrees, data obtained from cell I and II were -322 +/- 1.2 kJ mol(-1) and -323.3 +/- 2.1 kJ mol(-1), respectively. These values were found to be in very good agreement with the assessed data. (C) 2009 Elsevier B.V. All rights reserved.

Thermal Characteristics of SrO-2B(2)O(3) Glasses

Transparent SrO-2B(2)O(3) (SBO) glasses were fabricated via the conventional melt-quenching technique. X-ray diffraction (XRD) and differential thermal analysis (DTA) studies carried out on the as-quenched glasses confirmed their amorphous and glassy nature, respectively. The thermal parameters were evaluated for the as-quenched glass-plates using non-isothermal DTA experiments. The average values of the activation energies for the glass transition and crystallization of these glasses were 800 +/- 10 kJ/mol and 298 +/- 10 kJ/mol respectively. The values of the kinetic parameters that were obtained by different non-isothermal techniques were in close agreement.

Recognition of active and inactive catalytic triads: A template based approach

It Is well established that a sequence template along with the database is a powerful tool for identifying the biological function of proteins. Here, we describe a method for predicting the catalytic nature of certain proteins among the several protein structures deposited in the Protein Data Bank (PDB) For the present study, we considered a catalytic triad template (Ser-His-Asp) found in serine proteases We found that a geometrically optimized active site template can be used as a highly selective tool for differentiating an active protein among several inactive proteins, based on their Ser-His-Asp interactions. For any protein to be proteolytic in nature, the bond angle between Ser O-gamma-Ser H-gamma His N-epsilon 2 in the catalytic triad needs to be between 115 degrees and 140 degrees The hydrogen bond distance between Ser H-gamma His N-epsilon 2 is more flexible in nature and it varies from 2 0 angstrom to 27 angstrom while in the case of His H-delta 1 Asp O-delta 1, it is from 1.6 angstrom to 2.0 angstrom In terms of solvent accessibility, most of the active proteins lie in the range of 10-16 angstrom(2), which enables easy accessibility to the substrate These observations hold good for most catalytic triads and they can be employed to predict proteolytic nature of these catalytic triads (C) 2010 Elsevier B V All rights reserved.

Thermodynamics of the binding of galactopyranoside derivatives to the basic lectin from winged bean (Psophocarpus tetrogonolobus)

The thermodynamics of the binding of D-galactopyranoside (Gal), 2-acetamido-2-deoxygalactopyranoside (GalNAc), methyl-alpha-D-galactopyranoside, and methyl-beta-D-galactopyranoside to the basic agglutinin from winged bean (WBAI) in 0.02 M sodium phosphate and 0.15 M sodium chloride buffer have been investigated from 298.15 to 333.15 K by titration calorimetry and at the denaturation temperature by differential scanning calorimetry (DSC). WBAI is a dimer with two binding sites. The titration calorimetry yielded single-site binding constants ranging from 0.56 +/- 0.14 x 10(3) M-1 for Gal at 323.15 K to 7.2 +/- 0.5 x 10(3) M-1 for GalNAc at 298.15 K and binding enthalpies ranging from -28.0 +/- 2.0 kJ mol-1 for GalNAc at 298.15 K to -14.3 +/- 0.1 kJ mol-1 for methyl-beta-D-galactopyranoside at 322.65 K. The denaturation transition consisted of two overlapping peaks over the pH range 5.6-7.4. Fits of the differential scanning calorimetry data to a two-state transition model showed that the low temperature transition (341.6 +/- 0.4 K at pH 7.4) consisted of two domains unfolding as a single entity while the higher temperature transition (347.8 +/- 0.6 K at pH 7.4) is of the remaining WBAI dimer unfolding into two monomers. Both transitions shift to higher temperatures and higher calorimetric enthalpies with increase in added ligand concentration at pH 7.4. Analysis of the temperature increase as a function of added ligand concentration suggests that one ligand binds to the two domains unfolding at 341.6 +/- 0.6 K and one ligand binds to the domain unfolding at 347.8 +/- 0.6 K.

Insulator-metal transition

A theory of the insulator-metal transition in transition-metal compounds is developed in terms of the collapse of the effective energy gap which is a function of the thermally excited electron-hole pairs. This dependence is shown to arise from the hole-lattice interaction. The reaction of the lattice is found to be equivalent to generating an internal positive pressure (strain). Estimates show that the observed typical behaviour of the conductivity jump and the change of volume at the transition temperature can be explained by the present theory.

Investigation of activated transport in hole doped rare earth manganites in the high temperature paramagnetic regime

Electronic transport in the high temperature paramagnetic regime of the colossal magnetoresistive oxides, La(1-x)A(x)MnO(3), A=Ca, Sr, Ba, x similar or equal to 0.1-0.3, has been investigated using resistivity measurements. The main motivation for this work is to relook into the actual magnitude of the activation energy for transport in a number of manganites and study its variation as a function of hole doping (x), average A-site cation radius (< r(A)>), cationic disorder (sigma(2)) and strain (epsilon(zz)). We show that contrary to current practice, the description of a single activation energy in this phase is not entirely accurate. Our results clearly reveal a strong dependence of the activation energy on the hole doping as well as disorder. Comparing the results across different substituent species with different < r(A)> reveals the importance of sigma(2) as a metric to qualify any analysis based on (r(A)). (c) 2006 Elsevier Ltd. All rights reserved.

Moral Education in the Japanese Primary School Curricular Revision at the Turn of the Twenty-first Century: Aiming at a Rich and Beautiful Kokoro

This study examines values education in Japanese schools at the beginning of the millennium. The topic was approached by asking the following three questions concerning the curricular background, the morality conveyed through textbooks and the characterization of moral education from a comparative viewpoint: 1) What role did moral education play in the curriculum revision which was initiated in 1998 and implemented in 2002? 2) What kinds of moral responsibilities and moral autonomy do the moral texts develop? 3) What does Japanese moral education look like in terms of the comparative framework? The research was based on curriculum research. Its primary empirical data consisted of the national curriculum guidelines for primary school, which were taken into use in 2002, and moral texts, Kokoro no nôto, published by the Ministry of Education in the same context. Since moral education was approached in the education reform context, the secondary research material involved some key documents of the revision process from the mid-1990s to 2003. The research material was collected during three fieldwork periods in Japan (in 2002, 2003 and 2005). The text-analysis was conducted as a theory-dependent qualitative content analysis. Japanese moral education was analyzed as a product of its own cultural tradition and societal answer to the current educational challenges. In order to understand better its character, secular moral education was reflected upon from a comparative viewpoint. The theory chosen for the comparative framework, the value realistic theory of education, represented the European rational education tradition as well as the Christian tradition of values education. Moral education, which was the most important school subject at the beginning of modern school, was eliminated from the curriculum for political reasons in a school reform after the Second World War, but has gradually regained a stronger position since then. It was reinforced particularly at the turn of millennium, when a curriculum revision attempted to respond to educational and learning problems by emphasizing qualitative and value aspects. Although the number of moral lessons and their status as a non-official-subject remained unchanged, the Ministry of Education made efforts to improve moral education by new curricular emphases, new teaching material and additional in-service training possibilities for teachers. The content of the moral texts was summarized in terms of moral responsibility in four moral areas (intrapersonal, interpersonal, natural-supranatural and societal) as follows: 1) continuous self-development, 2) caring for others, 3) awe of life and forces beyond human power, and 4) societal contribution. There was a social-societal and emotional emphasis in what was taught. Moral autonomy, which was studied from the perspectives of rational, affective and individuality development, stressed independence in action through self-discipline and responsibility more than rational self-direction. Japanese moral education can be characterized as the education of kokoro (heart) and the development of character, which arises from virtue ethics. It aims to overcome egoistic individualism by reciprocal and interdependent moral responsibility based on responsible interconnectedness.

Hydropower Project Design Incorporating Submergence Costs

Submergence of land is a major impact of large hydropower projects. Such projects are often also dogged by siltation, delays in construction and heavy debt burdens-factors that are not considered in the project planning exercise. A simple constrained optimization model for the benefit~ost analysis of large hydropower projects that considers these features is proposed. The model is then applied to two sites in India. Using the potential productivity of an energy plantation on the submergible land is suggested as a reasonable approach to estimating the opportunity cost of submergence. Optimum project dimensions are calculated for various scenarios. Results indicate that the inclusion of submergence cost may lead to a substanual reduction in net present value and hence in project viability. Parameters such as project lifespan, con$truction time, discount rate and external debt burden are also of significance. The designs proposed by the planners are found to be uneconomic, whIle even the optimal design may not be viable for more typical scenarios. The concept of energy opportunity cost is useful for preliminary screening; some projects may require more detailed calculations. The optimization approach helps identify significant trade-offs between energy generation and land availability.

Importance of local heating in the compaction of thermally sensitive solids

Local heating is an important parameter in compaction of thermally sensitive solids since local hot spots could conceivably raise the temperature of the system by several hundred degrees. To understand the importance of local hot spots, 20 g of ammonium perchlorate (AP) and potassium perchlorate (KP) were pressed together at 1500 kg cm−2 for 5 min. The surface structural examination of the compact revealed a secondary phase at the interfaces between the grains in the compositions ranging from 50% AP-50% KP to 10% AP-90% KP. The observation of the secondary phase only at the interfaces has been attributed to the short life times of temperature pulses present during the compaction. An interesting aspect of the investigation is the formation of a series of solid solutions of AP-KP.

An SOx (x = 2, 3) sensor using ?-alumina/Na2SO4 couple

A solid-state sensor for SOx (x = 2, 3) species has been designed using ?-alumina as the solid electrolyte and Na2SO4 as the auxiliary electrode. The measured e.m.f. of the cell Pt, O?2 + SO?2 + SO?3|Na2SO4short parallel?-aluminashort parallelNa2SO4|SO?3 + SO?2 + O?2, PT in the temperature range 700 K to 1150 K agrees well with values calculated using the Nernst equation. The sodium sulphate acts both as a protective covering, preventing direct access of the gaseous SOx species to the ?-alumina electrolyte, and as an auxiliary electrode, converting chemical potentials of SOx species and O2 into an equivalent sodium potential. The open-circuit e.m.f. varies non-linearly with temperature for fixed composition of inlet gas mixtures containing SO2, O2 and Ar. The response time (t0.99) of the cell varies between 1.9 ks at 750 K and 0.06 ks at 1100 K. The e.m.f. response is faster when the partial pressure of SOx at the electrode is increased than when it is decreased.