A Unique Nickel System having Versatile Catalytic Activity of Biological Significance

A new dinuclear nickel(II) complex, [Ni-2(LH2)(H2O)(2)(OH)(NO3)](NO3)(3) (1), of an ``end-off'' compartmental ligand 2,6-bis(N-ethylpiperazine-iminomethyl)-4-methyl-phenolato, has been synthesized and structurally characterized. The X-ray single crystal structure analysis shows that the piperazine moieties assume the expected chair conformation and are protonated. The complex 1 exhibits versatile catalytic activities of biological significance, viz. catecholase, phosphatase, and DNA cleavage activities, etc. The catecholase activity of the complex observed is very dependent on the nature of the solvent. In acetonitrile medium, the complex is inactive to exhibit catecholase activity. On the other hand, in methanol, it catalyzes not only the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) but also tetrachlorocatechol (TCC), a catechol which is very difficult to oxidize, under aerobic conditions. UV vis spectroscopic investigation shows that TCC oxidation proceeds through the formation of an intermediate. The intermediate has been characterized by an electron spray ionizaton-mass spectrometry study, which suggests a bidentate rather than a monodentate mode of TCC coordination in that intermediate, and this proposition have been verified by density functional theory calculation. The complex also exhibits phosphatase (with substrate p-nitrophenylphosphate) and DNA cleavage activities. The DNA cleavage activity exhibited by complex 1 most probably proceeds through a hydroxyl radical pathway. The bioactivity study suggests the possible applications of complex 1 as a site specific recognition of DNA and/or as an anticancer agent.

A Unique Nickel System having Versatile Catalytic Activity of Biological Significance

A new dinuclear nickel(II) complex, [Ni-2(LH2)(H2O)(2)(OH)(NO3)](NO3)(3) (1), of an "end-off" compartmental ligand 2,6-bis(N-ethylpiperazine-iminomethyl)-4-methyl-phenolato, has been synthesized and structurally characterized. The X-ray single crystal structure analysis shows that the piperazine moieties assume the expected chair conformation and are protonated. The complex 1 exhibits versatile catalytic activities of biological significance, viz. catecholase, phosphatase, and DNA cleavage activities, etc. The catecholase activity of the complex observed is very dependent on the nature of the solvent. In acetonitrile medium, the complex is inactive to exhibit catecholase activity. On the other hand, in methanol, it catalyzes not only the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) but also tetrachlorocatechol (TCC), a catechol which is very difficult to oxidize, under aerobic conditions. UV vis spectroscopic investigation shows that TCC oxidation proceeds through the formation of an intermediate. The intermediate has been characterized by an electron spray ionizaton-mass spectrometry study, which suggests a bidentate rather than a monodentate mode of TCC coordination in that intermediate, and this proposition have been verified by density functional theory calculation. The complex also exhibits phosphatase (with substrate p-nitrophenylphosphate) and DNA cleavage activities. The DNA cleavage activity exhibited by complex 1 most probably proceeds through a hydroxyl radical pathway. The bioactivity study suggests the possible applications of complex 1 as a site specific recognition of DNA and/or as an anticancer agent.

Influence of Spatial Scales on the Performance of Saturated Subsurface Flow and Transport Models

Numerical modeling of saturated subsurface flow and transport has been widely used in the past using different numerical schemes such as finite difference and finite element methods. Such modeling often involves discretization of the problem in spatial and temporal scales. The choice of the spatial and temporal scales for a modeling scenario is often not straightforward. For example, a basin-scale saturated flow and transport analysis demands larger spatial and temporal scales than a meso-scale study, which in turn has larger scales compared to a pore-scale study. The choice of spatial-scale is often dictated by the computational capabilities of the modeler as well as the availability of fine-scale data. In this study, we analyze the impact of different spatial scales and scaling procedures on saturated subsurface flow and transport simulations.

Static analysis of infinite laminated cylindrical shell panel

This paper presents an approximate three-dimensional elasticity solution for an infinitely long, cross-ply laminated circular cylindrical shell panel with simply supported boundary conditions, subjected to an arbitrary discontinuous transverse loading. The solution is based on the principal assumption that the ratio of the thickness of the lamina to its middle surface radius is negligible compared to unity. The validity of this assumption and the range of application of this approximate solution have been established through a comparison with an exact solution. Results of classical and first-order shear deformation shell theories have been compared with the results of the present solution to bring out the accuracy of these theories. It is also shown that for very shallow shell panels the definition of a thin shell should be based on the ratio of thickness to chord width rather than the ratio of thickness to mean radius.

Effect Of Directionality Of Grinding Marks On Friction And Formation Of Transfer Layer

Surface texture influences friction and transfer layer formation during sliding. In the present investigation, basic studies were conducted using inclined pin-on-plate sliding tester to understand the effect of directionality of surface grinding marks of hard material on friction and transfer layer formation during sliding against soft materials. 080 M40 steel plates were ground to attain different surface roughness with unidirectional grinding marks. Then pins made of soft materials such as pure Al, pure Mg and Al-Mg alloy were slid against the prepared steel plates. Grinding angle (i.e., the angle between direction of sliding and grinding marks) was varied between 0 degrees and 90 degrees in the tests. Experiments were conducted under both dry and lubricated conditions on each plate in ambient environment. It was observed that the transfer layer formation and the coefficient of friction, which has two components adhesion and plowing - depend primarily on the directionality of grinding marks of the harder mating surface, and independent of surface roughness of the harder mating surface. For the case of pure Mg, stick-slip phenomenon was observed under dry condition for all grinding angles and it was absent upto 20 degrees grinding angles under lubricated condition. However, for the case of Al, it was observed only under lubricated conditions for angles exceeding 20 degrees. As regards the alloy, namely, Al-Mg alloy, it, was absent in both conditions. For the case of pure Mg and Al, it was observed that the amplitude of stick-slip motion primarily depends on plowing component of friction. The grinding angle effect on coefficient of friction was attributed to the variation of plowing component of friction with grinding angle.

Studies On Friction And Formation Of Transfer Layer In Hcp Metals

Surface texture plays an important role in the frictional behavior and transfer layer formation of contacting surfaces. In the present investigation, basic experiments were conducted using an inclined pin-on-plate sliding apparatus to better understand the role of surface texture on the coefficient of friction and the formation of a transfer layer. In the experiments, soft HCP materials such as pure Mg and pure Zn were used for the pins and a hardened 080 M40 steel was used for the plate. Two surface parameters of the steel plates—roughness and texture—were varied in tests that were conducted at a sliding speed of 2 mm/s in ambient conditions under both dry and lubricated conditions. The morphologies of the worn surfaces of the pins and the formation of the transfer layer on the counter surfaces were observed using a scanning electron microscope. In the experiments, the occurrence of stick-slip motion, the formation of a transfer layer, and the value of friction were recorded. With respect to the friction, both adhesion and plowing components were analyzed. Based on the experimental results, the effect of surface texture on the friction was attributed to differences in the amount of plowing. Both the plowing component of friction and the amplitude of stick-slip motion were determined to increase surface textures that promote plane strain conditions and decrease the textures that favor plane stress conditions.

Correlating The Features Of Topography To Friction By Sliding Experiments

Friction can influence the quality of the finished product to a large extent in certain manufacturing processes. Sheet metal forming is a particular case, where the friction between the hard-die and the relatively soft work-piece can be extremely important. Under such conditions, topography of the harder surface can influence the resistance to traction at the interface. This paper discusses about the correlation between certain features of the surface; topography and coefficient of friction based on experiments involving sliding of a few soft metal pins against a harder material. A brief description of the experimental procedure and the analysis are presented. A hybrid parameter which encapsulates both the amplitude features as well as the relative packing of peaks is shown to correlate well with the coefficient of friction.

Fuzzy optimization model for water quality management of a river system - Closure

A fuzzy waste-load allocation model, FWLAM, is developed for water quality management of a river system using fuzzy multiple-objective optimization. An important feature of this model is its capability to incorporate the aspirations and conflicting objectives of the pollution control agency and dischargers. The vagueness associated with specifying the water quality criteria and fraction removal levels is modeled in a fuzzy framework. The goals related to the pollution control agency and dischargers are expressed as fuzzy sets. The membership functions of these fuzzy sets are considered to represent the variation of satisfaction levels of the pollution control agency and dischargers in attaining their respective goals. Two formulations—namely, the MAX-MIN and MAX-BIAS formulations—are proposed for FWLAM. The MAX-MIN formulation maximizes the minimum satisfaction level in the system. The MAX-BIAS formulation maximizes a bias measure, giving a solution that favors the dischargers. Maximization of the bias measure attempts to keep the satisfaction levels of the dischargers away from the minimum satisfaction level and that of the pollution control agency close to the minimum satisfaction level. Most of the conventional water quality management models use waste treatment cost curves that are uncertain and nonlinear. Unlike such models, FWLAM avoids the use of cost curves. Further, the model provides the flexibility for the pollution control agency and dischargers to specify their aspirations independently.

Consolidation Behavior of Soils

Based on Terzaghi's consolidation theory, percent of consolidation, U, versus the time factor, T, relationship for constant/linear excess pore water pressure distribution, it is possible to generate theoretical log10(H2/t) versus U curves where H is the length of the drainage path of a consolidating layer, and t is the time for different known values of the coefficient of consolidation, cν. A method has been developed wherein both the theoretical and experimental behavior of soils during consolidation can be simultaneously compared and studied on the same plot. The experimental log10(H2/t) versus U curves have been compared with the theoretical curves. The deviations of the experimental behavior from the theory are explained in terms of initial compression and secondary compression. Analysis of results indicates that the secondary compression essentially starts from about 60% consolidation. A simple procedure is presented for calculating the value of cv from the δ-t data using log10(H2/t) versus U plot.

Interference of Two Closely Spaced Strip Footings on Sand Using Model Tests

By using small scale model tests, the interference effect on the ultimate bearing capacity of two closely spaced strip footings, placed on the surface of dry sand, was investigated. At any time, the footings were assumed to (1) carry exactly the same magnitude of load; and (2) settle to the same extent. No tilt of the footing was allowed. The effect of clear spacing (s) between two footings was explicitly studied. An interference of footings leads to a significant increase in their bearing capacity; the interference effect becomes even more substantial with an increase in the relative density of sand. The bearing capacity attains a peak magnitude at a certain (critical) spacing between two footings. The experimental observations presented in this technical note were similar to those given by different available theories. However, in a quantitative sense, the difference between the experiments and theories was seen to be still significant and it emphasizes the need of doing a further rigorous analysis in which the effect of stress level on the shear strength parameters of soil mass can be incorporated properly.

Bending Of Circular Plate On Elastic-Foundation

The governing differential equation of linear, elastic, thin, circular plate of uniform thickness, subjected to uniformly distributed load and resting on Winkler-Pasternak type foundation is solved using ``Chebyshev Polynomials''. Analysis is carried out using Lenczos' technique, both for simply supported and clamped plates. Numerical results thus obtained by perturbing the differential equation for plates without foundation are compared and are found to be in good agreement with the available results. The effect of foundation on central deflection of the plate is shown in the form of graphs.