Complexes of rare-earth perchlorates with ditbutyl amides of di, tri and tetraglycolic acids

New complexes of lanthanide perchlorates with di-t-butyl amides of di, tri and tetraglycolic acids have been synthesised. The complexes have the general formula Ln(DiGA)3(ClO4)3; Ln(TriGA)2 (ClO4)3 and Ln(TetGA)2 (C1O4)3, where Ln = La-Yb and Y and DiGA = N,N′, di-t-butyl diglycolamide, TriGA N,N′, di-t-butyl triglycolamide and TetGA = N,N′ di-t-butyl tetraglycolamide, respectively. The complexes have been characterized by analysis, electrolytic conductance, infrared,1H and13C nuclear magnetic resonance and electronic spectral data.Infrared spectra indicate the coordination of all the available ether oxygens and the amide carbonyls in each of the ligands, to the metal ions. IR and conductance data show that the perchlorate groups in all the complexes are ionic.1H and13C NMR data support the IR data regarding the mode of coordination of ligands to the metal ions. Electronic spectral shapes have been interpreted in terms of nine, eight and ten coordination in DiGA, TriGA and TetGA complexes respectively.

Endonuclease Active Site Plasticity Allows DNA Cleavage with Diverse Alkaline Earth and Transition Metal Ions

A majority of enzymes show a high degree of specificity toward a particular metal ion in their catalytic reaction. However, Type II restriction endonuclease (REase) R.KpnI, which is the first member of the HNH superfamily of REases, exhibits extraordinary diversity in metal ion dependent DNA cleavage. Several alkaline earth and transition group metal ions induce high fidelity and promiscuous cleavage or inhibition depending upon their concentration. The metal ions having different ionic radii and co-ordination geometries readily replace each other from the enzyme's active site, revealing its plasticity. Ability of R KpnI to cleave DNA with both alkaline earth and transition group metal ions having varied ionic radii could imply utilization of different catalytic site(s). However, mutation of the invariant His residue of the HNH motif caused abolition of the enzyme activity with all of the cofactors, indicating that the enzyme follows a single metal ion catalytic mechanism for DNA cleavage. Indispensability of His in nucleophile activation together with broad cofactor tolerance of the enzyme indicates electrostatic stabilization function of metal ions during catalysis. Nevertheless, a second metal ion is recruited at higher concentrations to either induce promiscuity or inhibit the DNA cleavage. Regulation of the endonuclease activity and fidelity by a second metal ion binding is a unique feature of R.KpnI among REases and HNH nucleases. The active site plasticity of R.KpnI opens up avenues for redesigning cofactor specificities and generation of mutants specific to a particular metal ion.

Measurement of Stress-Strain Response of A Rammed Earth Prism In Compression Using Fiber Bragg Grating Sensors

A comparative study of strain response and mechanical properties of rammed earth prisms, has been made using Fiber Bragg Grating (FBG) sensors (optical) and clip-on extensometer (electro-mechanical). The aim of this study is to address the merits and demerits of traditional extensometer vis-à-vis FBG sensor; a uni-axial compression test has been performed on a rammed earth prism to validate its structural properties from the stress - strain curves obtained by two different methods of measurement. An array of FBG sensors on a single fiber with varying Bragg wavelengths (..B), has been used to spatially resolve the strains along the height of the specimen. It is interesting to note from the obtained stress-strain curves that the initial tangent modulus obtained using the FBG sensor is lower compared to that obtained using clip-on extensometer. The results also indicate that the strains measured by both FBG and extensometer sensor follow the same trend and both the sensors register the maximum strain value at the same time.

Gibbs energies of formation of rare earth MPt5 compounds

The Gibbs energies of formation of MPt5 (MNd, Dy, Ho, Er) intermetallic compounds were determined in the temperature range 900–1100 K using the solid state cell Ta,M+MF3¦CaF2¦MPt5+Pt+MF3,Ta For M ≡ Sm, a mixture of Gd + GdF3 was used as the reference electrode. In the case of Eu, a mixture of Eu + EuF2 served as the reference electrode. The trifluorides of Sm and Eu are not stable in equilibrium with the metal. The fluoride phase coexisting with a SmPt5 + Pt mixture is SmF3, whereas EuF2 is the equilibrium phase in contact with EuPt5 + Pt. All the MPt5 compounds studied (except EuPt5) exhibit similar stability. Europium is divalent in the pure metal and trivalent in EuPt5. The energy required for the promotion of divalent Eu to the trivalent state accounts for the less negative Gibbs energy of formation of EuPt5. The enthalpies of formation of all the MPt5 compounds obtained in this study are in good agreement with Miedema's model.

Design parameters for earth-wire power tapping

The paper deals with the calculation of the induced voltage on, and the equivalent capacitance of, an earth wire isolated for purposes of tapping small amounts of power from high-voltage lines. The influence of heights, diameters and spacings of conductors on these quantities have been studied and presented in the form of graphs.

Study of surface oxidation of rare-earth-metals by photoelectron-spectroscopy

Surface oxidation of La, Ce, Sm and Tb metals has been investigated by He(II) ultraviolet photoelectron spectroscopy (u.p.s.) and X-ray photoelectron spectroscopy (X.p.s.). Oxidation of La gives rise to La2O3 on the surface. While Ce2O3 appears to be the stable oxide on the surface, we find evidence for formation of CeO2 at high oxygen exposure. Valence band of Sm clearly shows the presence of both divalent and trivalent states due to interconfigurational fluctuation. Exposure of Sm to oxygen first depletes the divalent Sm at the surface. While Sm2O3 is the stable oxide on the surface of Sm, Tb2O3 is the stable oxide on the surface of Tb (and not any of the higher oxides).

Is diatom earth a collapsible material?

Analysis of compressibility data of diatom earth and Ariake clay of similar water holding capacities has been made in this paper. Analysis suggests that in the case of clays with sheet minerals such as in Ariake clays, due to compression, cluster growth takes place, whereas with diatom earth the breakdown of cluster accounts for bilinear compression characteristics. It has been hypothesized that the interactive void ratio in the case of diatom earth is likely to be far smaller than that in the case of Ariake clay where most of the pore water is herd by micropores enclosed by clay particle clusters. In a way diatom earth reflects the behaviour of clay of very law physico-chemical potential with far reduced collapse potential. Even the compressibility at higher stress range both in undisturbed and remolded states are likely to be due to breakdown of clusters with little contribution from the physico - chemical potential. Diatom earth is not a collapsible material at stress levels of engineering interest despite the in -situ water content is at par or even higher than soft sensitive Ariake clay with comparatively low cementation consequently with pronounced collapsible potential.

Down-to-earth temperatures: The mechanics of the thermal environment

This lecture describes some recent attempts at unravelling the mechanics of the temperature distribution near ground, especially during calm, clear nights. In particular, a resolution is offered of the so-called Ramdas paradox, connected with observations of a temperature minimum some decimetres above bare soil on calm clear nights, in apparent defiance of the Rayleigh criterion for instability due to thermal convection. The dynamics of the associated temperature distribution is governed by radiative and convective transport and by thermal conduction, and is characterised by two time constants, involving respectively quick radiative adjustments and slow diffusive relaxation. The theory underlying the work described here suggests that surface parameters like ground emissivity and soil thermal conductivity can exert appreciable influence on the development of nocturnal inversions.