Syntheses,characterization, X-ray crystal structures and emission properties of copper(II), zinc(II) and cadmium(II) complexes of pyridyl–pyrazole derived Schiff base ligand – Metal selective ligand binding modes

The varying coordination modes of the title ligand, L [5-methyl-1-(pyridin-2-yl)-N′-[pyridin-2-ylmethylidene]pyrazole-3-carbohydrazide] towards the different metal centers is reported by preparation and characterization of Cu(II), Zn(II) and Cd(II) complexes, [Cu(L)NO₃.H₂O](NO₃) (1) [Zn(L)₂](ClO₄)₂·2DMF (2) and [Cd(L)(I)₂] (3) respectively. In 1, the neutral ligand serves as tetradentate 4 N donor where both pyridine and pyrazole nitrogen atoms of pyridyl–pyrazole part are coordinatively active, leaving the carbonyl oxygen of the carbohydrazide part inactive. The same pyridine and pyrazole N atoms remain abstained from the coordination process towards the Zn(II) and Cd(II) metal centers. For 2 and 3 the ligand behaves as a tridentate NNO donor where the two nitrogen atoms come from azomethine, pyridine of pyridine-2-carbaldehyde parts and O from carbonyl oxygen atoms (carbohydrazide part). The complex 1 and 2 are distorted octahedral while complex 3 adopts distorted square pyramidal geometry. All the complexes are X-ray crystallographically characterized.     

Localization and Environment of Tryptophans in Different Structural States of Concanavalin A

We have investigated the localization and environment of tryptophan residues in different quaternary and conformational states (tetrameric, dimeric, monomeric and unfolded) of metallized and demetallized concanavalin A (ConA) by selective chemical modification, fluorescence, and phosphorescence. ConA has four tryptophan residues (Trp 40, Trp 88, Trp 109 and Trp 182) per subunit. The pattern of oxidation by N-bromosuccinimide (NBS) shows that NBS modifies, in dimer, only Trp 182 which remains inaccessible in tetramer, two (Trp 88 along with Trp 182) in monomer, all four in unfolded form in presence of EDTA, and three (possibly Trp 40 along with Trp 88 and Trp 182) in unfolded form from native or remetallized ConA. Utilizing wavelength-selective fluorescence approach, we have observed a red edge excitation shift (REES) of 6–8 nm for tetramer and dimer. A more pronounced REES (11 nm) is observed for oxidized monomer compared to REES (3 nm) for unoxidized species. Acrylamide quenching shows the Stern-Volmer constant (K_SV) for dimer, monomer, unfolded ConA and unfolded apo-ConA being 3.8, 5.2, 12.8, 14.0 M⁻¹, respectively. Phosphorescence studies at 77 K give more structured spectra, with two (0,0) bands at 406.2 (weak) and 413.2 nm for tetramer. However, a single (0,0) band appears at 413.2 for dimer and 412.6 nm for monomer, while the (0,0) band of the oxidized monomer is red shifted to 414.4 nm. These results may provide important insight into subtlety of organization and environment of tryptophans in the context of folding and structural studies of oligomeric proteins including lectins.     

Gold nanoparticle induced conformational changes in heme protein

Change of α-helical structure of heme protein (Hb) to a β-sheet and random coil conformation because of the interaction of glycine capped gold nanoparticles (20–60 nm) as observed from attenuation total reflectance, absorption, Fourier transform infra red, and Circular Dichroism spectroscopy has been reported in this article. Upon interaction, protein takes a cylindrical shape of length 12 μm and diameter 0.35 μm as revealed from scanning electron microscopy and transmission electron microscopy. The Selected-Area Electron beam Diffraction pattern shows change of crystalline structure in GNP to amorphous nature with the interaction of Hb.     

The magnetization of PrFeAsO0.60F0.12 superconductor

The magnetization of the PrFeAsO_0.60F_0.12 polycrystalline sample has been measured as functions of temperature and magnetic field (H). The observed total magnetization is the sum of a superconducting irreversible magnetization and a paramagnetic magnetization. Analysis of dc susceptibility χ(T) in the normal state shows that the paramagnetic component of magnetization comes from the Pr³⁺ magnetic moments. The intragrain critical current density (J_L) derived from the magnetization data is large. The J_L(H) curve displays a second peak which shifts towards the high-field region with decreasing temperature. In the low-field region, a plateau up to a field H^* followed by a power law H^?5/8 behavior of J_L(H) is the characteristic of the strong pinning. A vortex phase diagram for the present superconductor has been obtained from the magnetization and resistivity data.     

On the characterization of Aloha in underwater wireless networks

Standard analyses of wireless random access protocols that are available in the literature assume negligible propagation delay between any two nodes. This assumption holds good in reasonably short-range terrestrial RF (radio frequency) wireless networks. On the contrary, in wireless communications involving acoustic wave propagation, as in underwater wireless networks, even short distance propagation has appreciably large propagation delay. This observation has led to several recent simulation and experimental studies on underwater Aloha and slotted-Aloha (S-Aloha) protocols and also a few new proposals on random access protocols for underwater wireless ad hoc networks (UWN). To study the efficiency of more advanced multiaccess communication protocols for UWN, it is important to benchmark their performances with respect to the two basic random access protocols, Aloha and S-Aloha. This paper provides an analytic framework to capture the performance of Aloha and S-Aloha protocols in an underwater environment with high and random internodal signal propagation delay. The performance of underwater Aloha and S-Aloha are contrasted with those in short-range terrestrial RF wireless networks. The analysis shows that random internodal propagation delay has no effect on the underwater Aloha performance. It also sheds light on the throughput degradation of underwater S-Aloha with a slotting concept that achieves RF S-Aloha equivalent one-slot vulnerability. Additionally, a modified slotting concept is introduced where the slot size is judiciously reduced such that even by allowing some collisions the overall system throughput can be increased. Our calculations show that, with the modified slotting approach up to 17% throughput performance gain can be achieved over the naive (RF S-Aloha equivalent) slotting approach in UWN. Our analytic results are supported by discrete event simulations.     

Separation of 134Cs and 133Ba radionuclides by calcium alginate beads

The uptake behavior of long-lived radionuclides such as ¹³⁴Cs (2.06 years), ¹³⁷Cs (30 years) or ¹³³Ba (10.54 years) on calcium alginate (CA) beads have been investigated. The CA beads are able to remove ¹³³Ba (92%) at pH 7 after 90 min of exposure from the binary mixture of two. The separation method of short-lived daughter ¹³⁷Ba (2.55 min) from its long-lived parent ¹³⁷Cs (30 years) using this CA beads have also been developed.     

Azimuthal correlation and fractal study of compound hadrons (pions and protons) at Dubna and SPS energy

This paper presents an investigation of compound hadrons (pions and protons) distribution emitted from ²⁴Mg-AgBr and ¹²C-AgBr interactions both at 4.5 AGeV and ³²S-AgBr interactions at 200 AGeV. The study includes azimuthal correlations (two particle and three particle), azimuthal asymmetry and fractal behaviour. This paper reveals some interesting results.     

Optical microscopy, DSC and X-ray diffraction studies in binary mixtures of 4-pentyloxy-4'-cyanobiphenyl with three 4,4'-di(alkoxy)azoxybenzenes

A large number of binary mixtures of 4-pentyloxy-4'-cyanobiphenyl (5OCB) and 4,4'-di(alkoxy)azoxybenzenes (nOAB) with n = 5, 6 and 7 have been studied by optical microscopy, DSC and X-ray diffraction methods. Over a wide concentration range the smectic A (SmA) phase is induced and the nematic (N) phase of the parent compounds is absent. Instead of the tilted smectic C phase of 7OAB an orthogonal SmA phase is observed when only 12% of the host molecules are replaced by 5OCB molecules. Moreover, in some mixtures the thermal stability of the induced SmA phase is found to be more than 1.6 times the stability of the mesophses in the pure compounds. The N-isotropic or Sm-I transition temperatures slowly increases with increasing concentrations, reaching a maximum at x _5OCB = 0.50 and then falling quite rapidly. In all the mixtures the enthalpy changes at the N-I transitions follow the simple additivity rule. In no mixture, except mixture C2, could the SmA-N transition be detected by DSC, although in all the mixtures the ratio T _NA/T _NI is found to be more than 0.95, which is in contradiction to McMillan's theory. Average intermolecular distances are found to have a minimum value near the equimolar concentration. From the concentration dependence of the smectic layer spacings it also appears that in all the mixtures the smectic A_d phase evolves from the smectic A₁ phase with increasing concentrations.     

Energy relaxation method for chemical non‐equilibrium flow computations

In this paper, an algorithm for chemical non‐equilibrium hypersonic flow is developed based on the concept of energy relaxation method (ERM). The new system of equations obtained are studied using finite volume method with Harten–Lax–van Leer scheme for contact (HLLC). The original HLLC method is modified here to account for additional species and split energy equations. Higher order spatial accuracy is achieved using MUSCL reconstruction of the flow variables with van Albada limiter. The thermal equilibrium is considered for the analysis and the species data are generated using polynomial correlations. The single temperature model of Dunn and Kang is used for chemical relaxation. The computed results for a flow field over a hemispherical cylinder at Mach number of 16.34 obtained using the present solver are found to be promising and computationally (25%) more efficient. The present solver captures physically correct solution as the entropy conditions are satisfied automatically during the computations. Copyright © 2007 John Wiley & Sons, Ltd.