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.

Selection of intrusion detection system threshold bounds for effective sensor fusion

The motivation behind the fusion of Intrusion Detection Systems was the realization that with the increasing traffic and increasing complexity of attacks, none of the present day stand-alone Intrusion Detection Systems can meet the high demand for a very high detection rate and an extremely low false positive rate. Multi-sensor fusion can be used to meet these requirements by a refinement of the combined response of different Intrusion Detection Systems. In this paper, we show the design technique of sensor fusion to best utilize the useful response from multiple sensors by an appropriate adjustment of the fusion threshold. The threshold is generally chosen according to the past experiences or by an expert system. In this paper, we show that the choice of the threshold bounds according to the Chebyshev inequality principle performs better. This approach also helps to solve the problem of scalability and has the advantage of failsafe capability. This paper theoretically models the fusion of Intrusion Detection Systems for the purpose of proving the improvement in performance, supplemented with the empirical evaluation. The combination of complementary sensors is shown to detect more attacks than the individual components. Since the individual sensors chosen detect sufficiently different attacks, their result can be merged for improved performance. The combination is done in different ways like (i) taking all the alarms from each system and avoiding duplications, (ii) taking alarms from each system by fixing threshold bounds, and (iii) rule-based fusion with a priori knowledge of the individual sensor performance. A number of evaluation metrics are used, and the results indicate that there is an overall enhancement in the performance of the combined detector using sensor fusion incorporating the threshold bounds and significantly better performance using simple rule-based fusion.

Selective attention in a synchronising bushcricket: physiology, behaviour and ecology

Synchronising bushcricket males achieve synchrony by delaying their chirps in response to calling neighbours. In multi-male choruses, males that delay chirps in response to all their neighbours would remain silent most of the time and be unable to attract mates. This problem could be overcome if the afferent auditory system exhibited selective attention, and thus a male interacted only with a subset of neighbours. We investigated whether individuals of the bushcricket genus Mecopoda restricted their attention to louder chirps neurophysiologically, behaviourally and through spacing. We found that louder leading chirps were preferentially represented in the omega neuron but the representation of softer following chirps was not completely abolished. Following chirps that were 20 dB louder than leading chirps were better represented than leading chirps. During acoustic interactions, males synchronised with leading chirps even when the following chirps were 20 dB louder. Males did not restrict their attention to louder chirps during interactions but were affected by all chirps above a particular threshold. In the field, we found that males on average had only one or two neighbours whose calls were above this threshold. Selective attention is thus achieved in this bushcricket through spacing rather than neurophysiological filtering of softer signals.

Selective dissemination of XML documents based on genetically learned user model and Support Vector Machines

Extensible Markup Language ( XML) has emerged as a medium for interoperability over the Internet. As the number of documents published in the form of XML is increasing, there is a need for selective dissemination of XML documents based on user interests. In the proposed technique, a combination of Adaptive Genetic Algorithms and multi class Support Vector Machine ( SVM) is used to learn a user model. Based on the feedback from the users, the system automatically adapts to the user's preference and interests. The user model and a similarity metric are used for selective dissemination of a continuous stream of XML documents. Experimental evaluations performed over a wide range of XML documents, indicate that the proposed approach significantly improves the performance of the selective dissemination task, with respect to accuracy and efficiency.

Sensor network deployment for agronomical data gathering in semi-arid regions

We share our experience in planning, designing and deploying a wireless sensor network of one square kilometre area. Environmental data such as soil moisture, temperature, barometric pressure, and relative humidity are collected in this area situated in the semi-arid region of Karnataka, India. It is a hope that information derived from this data will benefit the marginal farmer towards improving his farming practices. Soon after establishing the need for such a project, we begin by showing the big picture of such a data gathering network, the software architecture we have used, the range measurements needed for determining the sensor density, and the packaging issues that seem to play a crucial role in field deployments. Our field deployment experiences include designing with intermittent grid power, enhancing software tools to aid quicker and effective deployment, and flash memory corruption. The first results on data gathering look encouraging.

Parametric analysis of acoustic emission signals for evaluating damage in composites using a PVDF film sensor

With the increased utilization of advanced composites in strategic industries, the concept of Structural Health Monitoring (SHM) with its inherent advantages is gaining ground over the conventional methods of NDE and NDI. The most attractive feature of this concept is on-line evaluation using embedded sensors. Consequently, development of methodologies with identification of appropriate sensors such as PVDF films becomes the key for exploiting the new concept. And, of the methods used for on-line evaluation acoustic emission has been most effective. Thus, Acoustic Emission (AE) generated during static tensile loading of glass fiber reinforced plastic composites was monitored using a Polyvinylidene fluoride (PVDF) film sensor. The frequency response of the film sensor was obtained with pencil lead breakage tests to choose the appropriate band of operation. The specimen considered for the experiments were chosen to characterize the differences in the operation of the failure mechanisms through AE parametric analysis. The results of the investigations can be characterized using AE parameter indicating that a PVDF film sensor was effective as an AE sensor used in structural health monitoring on-line.

Selective dissemination of XML documents using GAs and SVM

XML has emerged as a medium for interoperability over the Internet. As the number of documents published in the form of XML is increasing there is a need for selective dissemination of XML documents based on user interests. In the proposed technique, a combination of Self Adaptive Migration Model Genetic Algorithm (SAMCA)[5] and multi class Support Vector Machine (SVM) are used to learn a user model. Based on the feedback from the users the system automatically adapts to the user's preference and interests. The user model and a similarity metric are used for selective dissemination of a continuous stream of XML documents. Experimental evaluations performed over a wide range of XML documents indicate that the proposed approach significantly improves the performance of the selective dissemination task, with respect to accuracy and efficiency.

Selective Homonuclear Decoupling in H-1 NMR: Application to Visualization of Enantiomers in Chiral Aligning Medium and Simplified Analyses of Spectra in Isotropic Solutions

The proton NMR spectral complexity arising due to severe overlap of peaks hampers their analyses in diverse situations, even by the application of two-dimensional experiments. The selective or complete removal of the couplings and retention of only the chemical shift interactions in indirect dimension aids in the simplification of the spectrum to a large extent with little investment of the instrument time. The present study provides precise enantiodiscrimination employing more anisotropic NMR parameters in the chiral liquid crystalline medium and differentiates the overlapped peaks of many organic molecules and peptides dissolved in isotropic solvents.

Correlation of structural disorder with the reversible discharge capacity of nickel hydroxide electrode

Hydrothermal treatment of a slurry of badly crystalline (beta(bc)) nickel hydroxide at different temperatures (65-170 degrees C) results in the progressive ordering of the structure by the step-wise elimination of disorders. Interstratification is eliminated at 140 degrees C, while cation vacancies are eliminated at 170 degrees C. A small percentage of stacking faults continue to persist even in `crystalline' samples. Electrochemical investigations show that the crystalline nickel hydroxide has a very low (0.4 e/Ni) reversible charge storage capacity. An incidence of at least 15% stacking faults combined with cation vacancies is essential for nickel hydroxide to perform close to its theoretical (1 e/ Ni) discharge capacity. (c) 2005 The Electrochemical Society.

Extraordinary high strain rate superplasticity in electrodeposited nano-nickel and alloys

Superplastic materials exhibit very large elongations to failure,typically >500%, and this enables commercial forming of complex shaped components at slow strain rates of similar to 10(-4) s(-1). We report extraordinary record superplastic elongations to failure of up to 5300% at both high strain rates and low temperature in electrodeposited nanocrystalline Ni and some Ni alloys. Superplasticity is not related to the presence of sulfur or a low melting phase at grain boundaries. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Potentiometric and spectrophotometric investigation of nickel-monoethanol-amine complexes

A detailed study of nickel-monoethanolamine complexes has been made employing potentiometric and spectrophotometric methods. The conditions for the formation of mono as well as polynuclear complexes have been investigated by potentiometric method. Evidence is presented for the formation of the following complexes and their stability constants are determined: NiA2+, Ni22+, Ni32+, NiA42+, NiA52+, NiA22+, Ni2A24+ and Ni3A36+. Combining potentiometric data with the spectrophotometric data, absorption spectra of the pure mononuclear complexes NiA2+ to NiA42+ and NiA2+6 have been computed. The absorption spectrum of NiA2+6 has been discussed on the basis of ligand field and molecular orbital theories. The absorption spectra of intermediate complexes have been interpreted on the basis of average ligand field theory. There has been good agreement between the experimental (10,400 cm-1) value of 10 Dq of NiA2+6 and the calculated value of 10 Dq (11,400 cm-1) on the basis of M.O. theory.

Nitrosation of N,N′-ethylenebis-(acetylacetoneimine) complexes of copper (II) and nickel(II) and characterization of the products

Isonitroso derivatives of copper(II) and nickel(II) complexes of N,N′-ethylenebis(acetylacetoneimine) have been prepared by nitrosation of the respective complexes using nitric oxide as well as nitrite ion. The condensation of isonitrosoacetylacetone in the presence and in the absence of nickel(II) has been investigated. The i.r. and electronic spectra and magnetic moment of the nickel(II) and copper(II) complexes have been studied. The nature of bonding of the ligand to the metal ion is discussed. The complexes have planar structures.

Studies on the hydrolysis of metal ions - Part II-Nickel

A detailed investigation of the hydrolysis of nickel in the lower concentration range has been made. The results have been analysed on the basis of 'Core + links' theory and on the assumption of the formation of one predominant complex. Evidence is obtained for the formation of Ni2 (OH)62- and its stability constant is calculated to be 1038.78

Nickel(II) complexes of 1-benzyl-2-phenylbenzimidazole

Nickel(II) complexes of 1-benzyl-2-phenylbenzimidazole (BPBI) of the general formula [Ni(BPBI)2X2](X=Cl-, Br-, NCS- or NO3-) have been prepared and their magnetic moments, i.r. and electronic spectra studied. [Ni(BPBI)2Cl2] has a pseudotetrahedral structure while [Ni(BPBI)2 Br2] exists as square planar and speudotetrahedral isomers. [Ni(BPBI)2I2] and [NI(BPBI)2(NCS)2] have square planar stereochemistry. The nitrato complex [Ni(BPBI)2(NO)3)2] exists in two different octahedral modifications in the solid state.