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.

Rendering stiffer walls: a hybrid haptic system using continuous and discrete time feedback

Instability in conventional haptic rendering destroys the perception of rigid objects in virtual environments. Inherent limitations in the conventional haptic loop restrict the maximum stiffness that can be rendered. In this paper we present a method to render virtual walls that are much stiffer than those achieved by conventional techniques. By removing the conventional digital haptic loop and replacing it with a part-continuous and part-discrete time hybrid haptic loop, we were able to render stiffer walls. The control loop is implemented as a combinational logic circuit on an field-programmable gate array. We compared the performance of the conventional haptic loop and our hybrid haptic loop on the same haptic device, and present mathematical analysis to show the limit of stability of our device. Our hybrid method removes the computer-intensive haptic loop from the CPU-this can free a significant amount of resources that can be used for other purposes such as graphical rendering and physics modeling. It is our hope that, in the future, similar designs will lead to a haptics processing unit (HPU).

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.

Methodological perspectives for register-based health system performance assessment : Developing a hip fracture monitoring system in Finland

The resources of health systems are limited. There is a need for information concerning the performance of the health system for the purposes of decision-making. This study is about utilization of administrative registers in the context of health system performance evaluation. In order to address this issue, a multidisciplinary methodological framework for register-based data analysis is defined. Because the fixed structure of register-based data indirectly determines constraints on the theoretical constructs, it is essential to elaborate the whole analytic process with respect to the data. The fundamental methodological concepts and theories are synthesized into a data sensitive approach which helps to understand and overcome the problems that are likely to be encountered during a register-based data analyzing process. A pragmatically useful health system performance monitoring should produce valid information about the volume of the problems, about the use of services and about the effectiveness of provided services. A conceptual model for hip fracture performance assessment is constructed and the validity of Finnish registers as a data source for the purposes of performance assessment of hip fracture treatment is confirmed. Solutions to several pragmatic problems related to the development of a register-based hip fracture incidence surveillance system are proposed. The monitoring of effectiveness of treatment is shown to be possible in terms of care episodes. Finally, an example on the justification of a more detailed performance indicator to be used in the profiling of providers is given. In conclusion, it is possible to produce useful and valid information on health system performance by using Finnish register-based data. However, that seems to be far more complicated than is typically assumed. The perspectives given in this study introduce a necessary basis for further work and help in the routine implementation of a hip fracture monitoring system in Finland.

Effect of static deflection on natural frequency of non-linear spring mass system by direct linearization method

An exact expression for the frequency of a non-linear cubic spring mass system is obtained considering the effect of static deflection. An alternative expression for the approximate frequency is also obtained by the direct linearization procedure; it is shown that this is very accurate as compared with the exact method. This approximate frequency equation is used to explain a “dual behaviour” of the frequency amplitude curves.

NADH oxidase system of Agrobacterium tumefaciens

Evidence for the presence and possible participation of a flavoprotein, coenzyme Q, and a cytochrome in the oxidation of NADH in the cell-free extracts of Agrobacterium tumefaciens was presented. Coenzyme Q10 was established as the homologue by several criteria. The characteristics of the cytochrome showed that it was different from the b and c groups of cytochromes. Amytal, antimycin A, and cyanide inhibited the oxidation of NADH, and from their effects on the electron transport components the following sequence has been proposed: NADH → flavoprotein → coenzyme Q10 → cytochrome oxygen.

Anthranilic acid oxidase system of Tecoma stans—II. : Studies on the properties of a purified anthranilic acid oxidase system and its separation into different enzymic components

An enzyme system which catalysed the conversion of anthranilic acid to catechol has been purified 20-fold from a cell-free leaf extract of Tecoma stans. The optimum substrate concentration was 10−3 M and optimum temperature for the reaction was 45°. The presence of a multi-enzyme system was inferred from inhibition studies. The formation of catechol was inhibited by Mg2+, Zn2+, and Co2+ ions, whereas anthranilic acid disappearance was not affected to the same extent. The effect of metal chelating agents like EDTA, cyanide and pyrophosphate showed a similar trend. PCMB inhibited catechol formation but had no effect on anthranilic acid disappearance. The reaction was not inhibited by catalase, nor was it activated by peroxide-donating systems. This ruled out the possibility of peroxidative type of reaction. The overall reaction is markedly activated by NADPH and THFA. This multi-enzyme was separated into three different components, by fractionation with Alumina Cγ and calcium phosphate gels. The overall reaction catalysed by these components can be represented as anthranilic acid→3-hydroxy anthranilic acid→o-aminophenol→catechol.

The emission spectrum of bismuth monofluoride BiF—‘A’ system

The observation of (A-X) system of BiF has been extended up to λ 5316 and twenty new bands belonging to this system have been recorded. The band heads could be represented by the following equation: {Mathematical expression} Seven other faint bands in the region λ 5316-5492 have also been reported, which, however, could not be classified. By our analysis of the present data and from known thermochemical data it has been deduced that the ground state dissociation energy is, in all probability, around 20000 cm.-1 (∼2·5 ev.) and that the dissociation products are the normal Bi and F atoms. The dissociation energy of the upper state and the correlation rules have been used to show that the dissociation products in the upper state are very likely to be Bi atom in the excited state2D3/2 and F atom in its ground state (2P3/2).

The influence of Zr/Ti content on the morphotropic phase boundary in the PZT-PZN system

A quantitative structural investigation was carried out on (1-y)PbZrxTi1-xO3-yPbZn(1/3)Nb(2/3)O(3) where y=0.1 and 0.2 ((1-y)PZT-yPZN). High resolution XRD data have been used for quantitative phase analysis. The nominal compositions were prepared by a two-step low temperature calcining solid-state method. The sintered samples show an average grain size of 1-2 mu m. It is demonstrated that the increase in the concentration of PZN leads to the shift of the morphotropic phase boundary (MPB) of PZT towards the PbZrO3 end member. In the present work, an effort has been made to quantitatively determine the MPB phase contents and to regain the coexistence of tetragonal and monoclinic phases by varying the value of x(i.e. Zr/Ti ratio). The width of the MPB becomes considerably larger for y=0.10 and 0.20 as compared to pure PZT. This is attributed to the considerably lower grain size of our samples resulting from the adopted preparation method. (C) 2010 Elsevier B.V. All rights reserved.

Vibrational analysis of the (B2P{cyrillic}→X2P{cyrillic}) system of NS

A few red degraded bands attributable to NS have been reported earlier by Fowler and Barker, Dressler and Barrow et al, and they occur in the same region (2300 to 2700 Å) as the bands of the known systems (C2∑+-X2P{cyrillic}) and (A2Δ-X2P{cyrillic}). Measurements made on the heads of some of these weak bands led Barrow et al. to believe that these bands may form a system analogous to the β-system of NO and be due to a2P{cyrillic}-2P{cyrillic} transition. The spectrum of NS has now been studied in a little more detail by means of an uncondensed discharge through dry nitrogen and sulphur vapour in the presence of argon and thirty three bands belonging to this system have been recorded in the region 2280 to 2760 Å. It has been found possible to represent the band heads by means of the equation {Mathematical expression}. Taking the lower state doublet interval as 223 cm-1, it is shown that the separation in the upper state is 94 cm-1. The ratio of the force constants in the upper and the ground states is found to be 0·39 and is nearly the same as that in the β-system of NO (0·30). The present vibrational analysis therefore supports the view that these new red degraded bands of NS arise from a (B2P{cyrillic}→X2P{cyrillic}) transition and the observed intensity distribution in the form of a wide parabola is also in qualitative agreement with what is expected from the moderately large Δ re (∼0·12Å) value.

Development and transient performance results of a single stage activated carbon - HFC 134a closed cycle adsorption cooling system

A laboratory model of a thermally driven adsorption refrigeration system with activated carbon as the adsorbent and 1,1,1,2-tetrafluoroethane (HFC 134a) as the refrigerant was developed. The single stage compression system has an ensemble of four adsorbers packed with Maxsorb II specimen of activated carbon that provide a near continuous flow which caters to a cooling load of up to 5W in the 5-18 degrees C region. The objective was to utilise the low grade thermal energy to drive a refrigeration system that can be used to cool some critical electronic components. The laboratory model was tested for it performance at various cooling loads with the heat source temperature from 73 to 93 degrees C. The pressure transients during heating and cooling phases were traced. The cyclic steady state and transient performance data are presented. (C) 2010 Elsevier Ltd. All rights reserved.

Adnominal Person in the Morphological System of Erzya : Adnominaalinen persoona ersän kielen morfologisessa järjestelmässä

This dissertation is a synchronic description of adnominal person in the highly synthetic morphological system of Erzya as attested in extensive Erzya-language written-text corpora consisting of nearly 140 publications with over 4.5 million words and over 285,000 unique lexical items. Insight for this description have been obtained from several source grammars in German, Russian, Erzya, Finnish, Estonian and Hungarian, as well as bounteous discussions in the understanding of the language with native speakers and grammarians 1993 2010. Introductory information includes the discussion of the status of Erzya as a lan- guage, the enumeration of phonemes generally used in the transliteration of texts and an in-depth description of adnominal morphology. The reader is then made aware of typological and Erzya-specifc work in the study of adnominal-type person. Methods of description draw upon the prerequisite information required in the development of a two-level morphological analyzer, as can be obtained in the typological description of allomorphic variation in the target language. Indication of original author or dialect background is considered important in the attestation of linguistic phenomena, such that variation might be plotted for a synchronic description of the language. The phonological description includes the establishment of a 6-vowel, 29-consonant phoneme system for use in the transliteration of annotated texts, i.e. two phonemes more than are generally recognized, and numerous rules governing allophonic variation in the language. Erzya adnominal morphology is demonstrated to have a three-way split in stem types and a three-layer system of non-derivative affixation. The adnominal-affixation layers are broken into (a) declension (the categories of case, number and deictic marking); (b) nominal conjugation (non-verb grammatical and oblique-case items can be conjugated), and (c) clitic marking. Each layer is given statistical detail with regard to concatenability. Finally, individual subsections are dedicated to the matters of: possessive declension compatibility in the distinction of sublexica; genitive and dative-case paradigmatic defectivity in the possessive declension, where it is demonstrated to be parametrically diverse, and secondary declension, a proposed typology modifiers without nouns , as compatible with adnominal person.

Oxidation of catechol in plants : III. Purification and properties of the diphenylene dioxide 2,3-quinone-forming enzyme system from Tecoma leaves

In attempting to determine the nature of the enzyme system mediating the conversion of catechol to diphenylenedioxide 2,3-quinone, in Tecoma leaves, further purification of the enzyme was undertaken. The crude enzyme from Tecoma leaves was processed further by protamine sulfate precipitation, positive adsorption on tricalcium phosphate gel, and elution and chromatography on DEAE-Sephadex. This procedure yielded a 120-fold purified enzyme which stoichiometrically converted catechol to diphenylenedioxide 2,3-quinone. The purity of the enzyme system was assessed by polyacrylamide gel electrophoresis. The approximate molecular weight of the enzyme was assessed as 200,000 by gel filtration on Sephadex G-150. The enzyme functioned optimally at pH 7.1 and at 35 °C. The Km for catechol was determined as 4 × 10−4 Image . The enzyme did not oxidize o-dihydric phenols other than catechol and it did not exhibit any activity toward monohydric and trihydric phenols and flavonoids. Copper-chelating agents did not inhibit the enzyme activity. Copper could not be detected in the purified enzyme preparations. The purified enzyme was not affected by extensive dialysis against copper-complexing agents. It did not show any peroxidase activity and it was not inhibited by catalase. Hydrogen peroxide formation could not be detected during the catalytic reaction. The enzymatic conversion of catechol to diphenylenedioxide 2,3-quinone by the purified Tecoma leaf enzyme was suppressed by such reducing agents as GSH and cysteamine. The purified enzyme was not sensitive to carbon monoxide. It was not inhibited by thiol inhibitors. The Tecoma leaf was found to be localized in the soluble fraction of the cell. Treatment of the purified enzyme with acid, alkali, and urea led to the progressive denaturation of the enzyme.

Equivalent constitutive model-based design of wave-absorbing material system and controller

A design methodology for wave-absorbing active material system is reported. The design enforces equivalence between an assumed material model having wave-absorbing behavior and a set of target feedback controllers for an array of microelectro-mechanical transducers which are integral part of the active material system. The proposed methodology is applicable to problems involving the control of acoustic waves in passive-active material system with complex constitutive behavior at different length-scales. A stress relaxation type one-dimensional constitutive model involving viscous damping mechanism is considered, which shows asymmetric wave dispersion characteristics about the half-line. The acoustic power flow and asymptotic stability of such material system are studied. A single sensor non-collocated linear feedback control system in a one-dimensional finite waveguide, which is a representative volume element in an active material system, is considered. Equivalence between the exact dynamic equilibrium of these two systems is imposed. It results in the solution space of the design variables, namely the equivalent damping coefficient, the wavelength(s) to be controlled and the location of the sensor. The characteristics of the controller transfer functions and their pole-placement problem are studied. (c) 2005 Elsevier Ltd. All rights reserved.