Cu-II-Azide Polynuclear Complexes of Three Different Building Clusters with the Same Schiff-Base Ligand: Synthesis, Structures, Magnetic Behavior, and Density Functional Theory Studies

Three copper-azido complexes Cu-4(N-3)(8)(L-1)(2)(MeOH)(2)](n) (1), Cu-4(N-3)(8)(L-1)(2)] (2), and Cu-5(N-3)(10)(L-1)(2)](n) (3) L-1 is the imine resulting from the condensation of pyridine-2-carboxaldehyde with 2-(2-pyridyl)ethylamine] have been synthesized using lower molar equivalents of the Schiff base ligand with Cu(NO3)(2)center dot 3H(2)O and an excess of NaN3. Single crystal X-ray structures show that the basic unit of the complexes 1 and 2 contains Cu-4(II) building blocks; however, they have distinct basic and overall structures due to a small change in the bridging mode of the peripheral pair of copper atoms in the linear tetranudear structures. Interestingly, these changes are the result of changing the solvent system (MeOH/H2O to EtOH/H2O) used for the synthesis, without changing the proportions of the components (metal to ligand ratio 2:1). Using even lower proportions of the ligand, another unique complex was isolated with Cu-5(II) building units, forming a two-dimensional complex (3). Magnetic susceptibility measurements over a wide range of temperature exhibit the presence of both antiferromagnetic (very weak) and ferromagnetic exchanges within the tetranuclear unit structures. Density functional theory calculations (using B3LYP functional, and two different basis sets) have been performed on the complexes 1 and 2 to provide a qualitative theoretical interpretation of their overall magnetic behavior.

Sign changes of Fourier coefficients of Hilbert modular forms

Sign changes of Fourier coefficients of various modular forms have been studied. In this paper, we analyze some sign change properties of Fourier coefficients of Hilbert modular forms, under the assumption that all the coefficients are real. The quantitative results on the number of sign changes in short intervals are also discussed. (C) 2014 Elsevier Inc. All rights reserved.

Random vibration testing with controlled samples

This paper proposes a novel experimental test procedure to estimate the reliability of structural dynamical systems under excitations specified via random process models. The samples of random excitations to be used in the test are modified by the addition of an artificial control force. An unbiased estimator for the reliability is derived based on measured ensemble of responses under these modified inputs based on the tenets of Girsanov transformation. The control force is selected so as to reduce the sampling variance of the estimator. The study observes that an acceptable choice for the control force can be made solely based on experimental techniques and the estimator for the reliability can be deduced without taking recourse to mathematical model for the structure under study. This permits the proposed procedure to be applied in the experimental study of time-variant reliability of complex structural systems that are difficult to model mathematically. Illustrative example consists of a multi-axes shake table study on bending-torsion coupled, geometrically non-linear, five-storey frame under uni/bi-axial, non-stationary, random base excitation. Copyright (c) 2014 John Wiley & Sons, Ltd.

Modelling of soldier fly halteres for gyroscopic oscillations

Nature has evolved a beautiful design for small-scale vibratory rategyro in the form of dipteran halteres that detect body rotations via Coriolis acceleration. In most Diptera, including soldier fly, Hermetia illucens, halteres are a pair of special organs, located in the space between the thorax and the abdomen. The halteres along with their connecting joint with the fly's body constitute a mechanism that is used for muscle-actuated oscillations of the halteres along the actuation direction. These oscillations lead to bending vibrations in the sensing direction (out of the haltere's actuation plane) upon any impressed rotation due to the resulting Coriolis force. This induced vibration is sensed by the sensory organs at the base of the haltere in order to determine the rate of rotation. In this study, we evaluate the boundary conditions and the stiffness of the anesthetized halteres along the actuation and the sensing direction. We take several cross-sectional SEM (scanning electron microscope) images of the soldier fly haltere and construct its three dimensional model to get the mass properties. Based on these measurements, we estimate the natural frequency along both actuation and sensing directions, propose a finite element model of the haltere's joint mechanism, and discuss the significance of the haltere's asymmetric cross-section. The estimated natural frequency along the actuation direction is within the range of the haltere's flapping frequency. However, the natural frequency along the sensing direction is roughly double the haltere's flapping frequency that provides a large bandwidth for sensing the rate of rotation to the soldier flies.

Multi-scale modelling of Suzuki segregation in gamma' precipitates in Ni and Co-base superalloys

The high temperature strength of alloys with (gamma +gamma') microstructure is primarily due to the resistance of the ordered precipitate to cutting by matrix dislocations. Such shearing requires higher stresses since it involves the creation of a planar fault. Planar fault energy is known to be dependent on composition. This implies that the composition on the fault may be different from that in the bulk for energetic reasons. Such segregation (or desegregation) of specific alloying elements to the fault may result in Suzuki strengthening which has not been explored extensively in these systems. In this work, segregation (or desegregation) of alloying elements to planar faults was studied computationally in Ni-3(Al, Ti) and Co-3(W, Al) type gamma' precipitates. The composition dependence of APB energy and heat of mixing were evaluated from first principle electronic structure calculations. A phase field model incorporating the first principles results, was used to simulate the motion of an extended superdislocation under stress concurrently with composition evolution. Results reveal that in both systems, significant (de) segregation occurs on equilibration. On application of stress, solutes were dragged along with the APB in some cases. Additionally, it was also noted the velocity of the superdislocation under an applied stress is strongly dependent on atomic mobility (i. e. diffusivity).

Computational design of model Re/Ru bearing Ni-base superalloys

It is well established that Re and Ru additions to Ni-base superalloys result in improved creep performance and phase stability. However, the role of Re and Ru and their synergetic effects are not well understood, and the first step in understanding these effects is to design alloys with controlled microstructural parameters. A computational approach was undertaken in the present work for designing model alloys with varying levels of Re and Ru. Thermodynamic and first principles calculations were employed complimentarily to design a set of alloys with varying Re and Ru levels, but which were constrained by constant microstructural parameters, i.e., phase fractions and lattice misfit across the alloys. Three ternary/quaternary alloys of type Ni-Al-xRe-yRu were thus designed. These compositions were subsequently cast, homogenized and aged. Experimental results suggest that while the measured volume fraction matches the predicted value in the Ru containing alloy, volume fraction is significantly higher than the designed value in the Re containing alloys. This is possibly due to errors in the thermodynamic database used to predict phase fraction and composition. These errors are also reflected in the mismatch between predicted and measured values of misfit.

Significant photocytotoxic effect of an iron(III) complex of a Schiff base ligand derived from vitamin B-6 and thiosemicarbazide in visible light

Iron(III)-Schiff base complexes, namely, Fe(tsc-py)(2)](NO3) (1), Fe(tsc-acpy)(2)](NO3) (2) and Fe(tsc-VB6)(2)](NO3) (3), where tsc-py, tsc-acpy and tsc-VB6 are the respective Schiff bases derived from thiosemicarbazide (tsc) and pyridine-2-aldehyde (tsc-py), 2-acetyl pyridine (tsc-acpy) and vitamin B-6 (pyridoxal, tsc-VB6), have been prepared, structurally characterized and their photocytotoxicity studied in cancer HeLa cells. The single crystal X-ray structures of the complexes 1 and 2 show a distorted octahedral geometry formed by the FeN4S2 core. The low-spin and 1 : 1 electrolytic complexes display a broad absorption band in the visible region. Complexes 1 and 2, without any VB6 moiety are not cytotoxic under light or dark conditions. Complex 3 is significantly photocytotoxic under visible light of 400-700 nm giving an IC50 value of 22.5 mu M in HeLa cells with no dark toxicity (IC50 > 100 mu M). The photo-induced cell death is attributable to apoptotic pathways involving photo-assisted generation of intracellular ROS. The observed photocytotoxicity of complex 3 could be the result of its better photosensitizing property combined with its enhanced uptake into cancer cells via a VB6 transporting membrane carrier (VTC) mediated diffusion pathway due to the presence of the VB6 moiety compared to the two non-vitamin B-6 analogues, complexes 1 and 2.

Iron(III) Complexes of a Pyridoxal Schiff Base for Enhanced Cellular Uptake with Selectivity and Remarkable Photocytotoxicity

Iron(III) complexes of pyridoxal (vitamin B6, VB6) or salicylaldehyde Schiff bases and modified dipicolylamines, namely, Fe(B)(L)](NO3) (15), where B is phenyl-N,N-bis((pyridin-2-yl)methyl)methanamine (phbpa in 1), (anthracen-9-yl)-N,N-bis((pyridin-2-yl)methyl)methanamine (anbpa in 2, 4) and (pyren-1-yl)-N,N-bis((pyridin-2-yl)methyl)methanamine (pybpa in 3, 5) (H2L1 is 3-hydroxy-5-(hydroxymethyl)-4-(((2-hydroxyphenyl)imino)methyl)-2-methylp yridine (13) and H2L2 is 2-(2-hydroxyphenyl-imino)methyl]phenol), were prepared and their uptake in cancer cells and photocytotoxicity were studied. Complexes 4 and 5, having a non-pyridoxal Schiff base, were prepared to probe the role of the pyridoxal group in tumor targeting and cellular uptake. The PF6 salt (1a) of complex 1 is structurally characterized. The complexes have a distorted six-coordinate FeN4O2 core where the metal is in the +3 oxidation state with five unpaired electrons. The complexes display a ligand to metal charge transfer band near 520 and 420 nm from phenolate to the iron(III) center. The photophysical properties of the complexes are explained from the time dependent density functional theory calculations. The redox active complexes show a quasi-reversible Fe(III)/Fe(II) response near -0.3 V vs saturated calomel electrode. Complexes 2 and 3 exhibit remarkable photocytotoxicity in various cancer cells with IC50 values ranging from 0.4 to 5 mu M with 10-fold lower dark toxicity. The cell death proceeded by the apoptotic pathway due to generation of reactive oxygen species upon light exposure. The nonvitamin complexes 4 and 5 display 3-fold lower photocytotoxicity compared to their VB6 analogues, possibly due to preferential and faster uptake of the vitamin complexes in the cancer cells. Complexes 2 and 3 show significant uptake in the endoplasmic reticulum, while complexes 4 and 5 are distributed throughout the cells without any specific localization pattern.

A CAPABILITY APPROACH BASED STAKEHOLDER ANALYSIS FOR THE BASE OF THE PYRAMID: A CASE STUDY OF THE FIREWOOD BASED COOK-STOVES

People living under $2 income per day, referred as Base of the Pyramid (BoP), face undesired situations like lack of nutrition, health, education etc. Design as a process of changing current undesired situation to a desired situation has failed. A crucial reason behind these failures is lack of normative basis to identify and understand the absent or unsatisfied stakeholder. Currently stakeholder analysis in the design is heuristic. This paper uses a normative framework of Capability Approach (CA) for the stakeholder analysis. A brief discussion on stakeholder theory and analysis is used to identify gaps in the literature. The constructs of the CA are discussed for its suitability to the purpose. Along with methodological details, data generated from the stakeholder interviews, focus groups in a case study of dissemination of improved cook-stoves is used to interlink the theory with the practice. The scope of this work is in identifying and investigating the motives of the stakeholders in the involvement in the product. Though a lot of insights to discern and manage crucial stakeholders is inbuilt in the methodology, this work does not claim explicit coverage of these aspects.

Photocytotoxic ternary copper(II) complexes of histamine Schiff base and pyridyl ligands

Ternary copper(Il) complexes of salicylaldehyde-histamine Schiff base (HL) and pyridyl ligands, viz. Cu(bpy)(L)](ClO4) (1) and Cu(dppz)(L)](C104) (2), where bpy is 2,2'-bipyridine (in 1) and dppz is dipyrido3,2-a:2',3'-c]phenazine (in 2), were synthesized, characterized and their DNA binding, photo-activated DNA cleavage activity and photocytotoxicity studied. The 1:1 electrolytic one-electron paramagnetic complexes showed a d-d band near 670 nm in aqueous DMF (1:1 v/v). The crystal structure of complex 1 showed the metal in CuN4O distorted square-pyramidal geometry. Complex 2 intercalatively binds to calf-thymus (ct) DNA with a binding constant (K-b) of similar to 10(5) M-1. It exhibited moderate chemical nuclease activity but excellent DNA photocleavage activity in red light of 647 nm forming (OH)-O-center dot radicals. It showed remarkable photocytotoxicity in human cervical cancer cells (HeLa) giving IC50 of 1.6 mu M in visible light (400-700 nm) with low dark toxicity. The photo-induced cell death is via generation of oxidative stress by reactive oxygen species.

Remarkable photo-induced anticancer activity of vitamin-S6 Schiff base copper(II) complexes of pyridyl bases

Vitamin-B6 (VB6) Schiff base (H2L) copper(II) complexes of pyridyl bases, viz. Cu(bpy)(L)] (1), Cu(phen)(L)] (2) and Cu(dppz)(L)] (3), where bpy is 2,2'-bipyridine, phen is 1,10-phenanthroline and dppz is dipyrido3,2-a:2',3'c]phenazine are synthesized, characterized and their phto-induced anticancer activity studied. The non-electrolytic one electron paramagnetic complexes exhibit a d-d band near 700 nm in DMF. The dppz complex intercalatively binds to calf-thymus DNA with binding constant (K-b) values of similar to 10(6) M-1. This complex exhibits low chemical nuclease activity but excellent DNA photocleavage activity when irradiated with red light of 705 nm forming (OH)-O-center dot radical. It displays remarkable photocytotoxicity in human cervical cancer cells (HeLa) giving IC50 value of 0.9 mu M in visible light (400-700 nm) while being less toxic in darkness (IC50 : 23 mu M). The cellular uptake of the complexes seems to be via VB6 transporting membrane carrier mediated diffusion pathway. Photo-induced cell death follows apoptotic pathway involving photo-generated intracellular reactive oxygen species.