Solvation and axial ligation properties of (2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinato)zinc(II)

he solvation of (2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinato)zinc(II)[Zn(obtpp)], in twelve different solvents results in large red shifts of the B and Q bands of the porphyrin accompanied by enhanced absorbance ratios of the Q bands. These observations are ascribed to the destabilisation of the highest occupied molecular orbital a2u of the porphyrin arising from a flow of charge from the axial ligand to the porphyrin ring through the zinc(II) ion. The binding constants of adducts of [Zn(obtpp)] with neutral bases have been found to be an order of magnitude greater than those observed for the corresponding adducts of (5,10,15,20-tetraphenylporphyrinato)-zinc and vary in the order piperidine > imidazole > pyridine > 3-methylpyridine > pyridine-3-carbaldehyde. The enhanced binding constants and large spectral shifts are interpreted in terms of the electrophilicity of [Zn(obtpp)] induced by the electron-withdrawing bromine substituents in the porphyrin core. The structure of [Zn(obtpp)(PrCN)2] has been determined; it reveals six-co-ordinated zinc(II) with two long Zn–N distance [2.51(4), 2.59(3)Å]. The porphyrin is non-planar and displays a saddle-shaped conformation.

Metallomicelles as potent catalysts for the ester hydrolysis reactions in water

Synthetic amphiphiles have been employed for the investigation of diverse topics, e.g. membrane mimetics, drug delivery, ion sensing and even in certain separation processes. Metal-complexing amphiphiles comprise an interesting class of compounds possessing multiple utilities. Upon solubilization in water they form metallomicelles. For achieving specific catalysis of a variety of reactions, metallomicelles were utilized by applying the principles of coordination chemistry and self-organizing systems. Because of their certain similarities with the natural enzymes, metallomicelles were synthesized as catalysts for many reactions. In particular the metallomicelles play a catalytic role in reactions involving the hydrolysis of activated carboxylate esters, phosphate esters and amides at ambient conditions near neutral pH. Apart from the hydrolysis reactions, these were exploited to play pertinent role as Lewis acid catalysts in cycloaddition reactions, and in other reactions such as phenolic oxidation in presence of hydrogen peroxide. In this review we emphasize with the help of assorted examples, the design, synthesis of metal-complexing amphiphiles and their aggregation behavior leading to catalytic hydrolysis reactions in aqueous media.

Electrochromic, magnetotransport and AC transport properties of vapor phase polymerized PEDOT(VPP PEDOT)

Poly(3,4-ethylenedioxy)thiophene (PEDOT) doped with tosylate ion (PEDOT-tosylate or VPP PEDOT) was synthesized by vapor phase polymerization (VPP) technique on glass as well as on glass/ITO and the electrochromic properties were investigated. Compared with that of PEDOT-PSS spin-coated on glass/ITO, the studies showed that VPP PEDOT has a lower work function and better electrochromic properties. The magneto and AC transport properties studies were done on VPP PEDOT coated on glass substrate. The system shows 2-dimensional variable range hopping and wave function shrinkage of charge carriers.

Effects of mould filling on evolution of the solid-liquid interface during solidification

This work presents a numerical analysis of simultaneous mould filling and phase change for solidification in a two-dimensional rectangular cavity. The role of residual flow strength and temperature gradients within the solidifying domain, caused by the filling process, on the evolution of solidification interface are investigated. An implicit volume of fluid (VOF)-based algorithm has been employed for simulating the free surface flows during the filling process, while the model for solidification is based on a fixed-grid enthalpy-based control volume approach. Solidification modeling is coupled with VOF through User Defined Functions developed in the commercial computational fluid dynamics (CFD) code FLUENT 6.3.26. Comparison between results of the conventional analysis without filling effect and those of the present analysis shows that the residual flow resulting from the filling process significantly influences the progress of the solidification interface. A parametric study is also performed with variables such as cooling rate, filling velocity and filling configuration, in order to investigate the coupled effects of the buoyancy-driven flow and the residual flow on the solidification behavior.

Usefulness of DARPA dataset for intrusion detection system evaluation

The MIT Lincoln Laboratory IDS evaluation methodology is a practical solution in terms of evaluating the performance of Intrusion Detection Systems, which has contributed tremendously to the research progress in that field. The DARPA IDS evaluation dataset has been criticized and considered by many as a very outdated dataset, unable to accommodate the latest trend in attacks. Then naturally the question arises as to whether the detection systems have improved beyond detecting these old level of attacks. If not, is it worth thinking of this dataset as obsolete? The paper presented here tries to provide supporting facts for the use of the DARPA IDS evaluation dataset. The two commonly used signature-based IDSs, Snort and Cisco IDS, and two anomaly detectors, the PHAD and the ALAD, are made use of for this evaluation purpose and the results support the usefulness of DARPA dataset for IDS evaluation.

Increasing ionic conductivity of polymer-sodium salt complex by addition of a non-ionic plastic crystal

Ionic conductivity and other physico-chemical properties of a soft matter composite electrolyte comprising of a polymer-sodium salt complex and a non-ionic plastic crystal are discussed here. The electrolyte under discussion comprises of polyethyleneoxide (PEO)-sodium triflate (NaCF3SO3) and succinonitrile (SN). Addition of SN to PEO-NaCF3SO3 resulted in significant enhancement in ionic conductivity. At 50% SN concentration (with respect to weight of polymer), the polymer-plastic composite electrolyte room temperature (= 25 degrees C) ionic conductivity was similar to 1.1 x 10(-4) Omega(-1) cm(-1), approximately 45 times higher than PEO-NaCF3SO3. Observations from ac-impedance spectroscopy along with X-ray diffraction, differential scanning calorimetry and Fourier transform inrared spectroscopy strongly suggest the enhancement in the composite is ionicconductivity due to enhanced ion mobility via decrease in crystallinity of PEO. The free standing composite polymer-plastic electrolytes were more compliable than PEO-NaCF3SO3 thus exhibiting no detrimental effects of succinonitrile addition on the mechanical stability of PEO-NaCF3SO3. We propose that the exploratory PEO-NaCF3SO3-SN system.discussed here will eventually be developed as a prototype electrolyte.for sodium-sulfur batteries capable of operating at ambient and.sub-ambient conditions. (C) 2010 Elsevier B.V. All rights reserved.

DNA duplex with the potential to change handedness after every half a turn

Polymorphic forms of the DNA duplex with long stretches of structural monotony are known. Several alternating purine-pyrimidine sequences have been shown to adopt left-handed Z-conformation. We report a DNA sequence d(CGCGCGATCGAT)n exhibiting alternating right-handed B and left-handed Z helical conformation after every half a turn. Further, this unusual conformation with change in handedness after every six base pairs was induced at physiological superhelical density.

meso-substituted octabromoporphyrins: Synthesis, spectroscopy, electrochemistry and electronic structure

The free-base, copper(II) and zinc(II) derivatives of 5,10,15,20-tetraarylporphyrin (aryl = phenyl, 4-methylphenyl or 4-chlorophenyl) and the corresponding brominated 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraarylporphyrin derivatives have been synthesized and their spectral and redox properties compared by UV/VIS, H-1 NMR, ESR and cyclic voltammetric methods. Substitution with the electron-withdrawing bromine groups at the pyrrole carbons has a profound influence on the UV/VIS and H-1 NMR spectral features and also on the redox potentials of these systems. On the other hand, electron-withdrawing chloro or electron-donating methyl groups at the para positions of the four phenyl rings have only a marginal effect on the spectra and redox potentials of both the brominated and the non-brominated derivatives. The ESR data for the copper(II) derivatives of ail these systems reveal that substitution at either the beta-pyrrole carbons and/or the para positions of the meso-phenyl groups does not significantly affect the spin-Hamiltonian parameters that describe the metal centre in each case. Collectively, these observations suggest that the highest-occupied (HOMO) and lowest-unoccupied molecular orbitals (LUMO) of the octabromoporphyrins involve the porphyrin pi-ring system as is the case with the non-brominated derivatives.-Investigations have been carried out to probe the electronic structures of these systems by three different approaches involving spectral and redox potential data as well as AMI calculations. The results obtained suggest that the electron-withdrawing beta-bromine substituents stabilize the LUMOs and, to a lesser degree, the HOMOs and that the extent of these changes can be fine-tuned, in a subtle way, by substituting at the meso-aryl rings of a given porphyrin.

Static Balancing of Spring-loaded Planar Revolute-joint Linkages without Auxiliary Links

We present a method to statically balance a general treestructured,planar revolute-joint linkage loaded with linear springs or constant forces without using auxiliary links. The balancing methods currently documented in the literature use extra links; some do not apply when there are spring loads and some are restricted to only two-link serial chains. In our method, we suitably combine any non-zero-free-length load spring with another spring to result in an effective zero-free-length spring load. If a link has a single joint (with the parent link), we give a procedure to attach extra zero-free-length springs to it so that forces and moments are balanced for the link. Another consequence of this attachment is that the constraint force of the joint on the parent link becomes equivalent to a zero-free-length spring load. Hence, conceptually,for the parent link, the joint with its child is removed and replaced with the zero-free-length spring. This feature allows recursive application of this procedure from the end-branches of the tree down to the root, satisfying force and moment balance of all the links in the process. Furthermore, this method can easily be extended to the closed-loop revolute-joint linkages, which is also illustrated in the paper.

A Flexure-based Deployable Stereo Vision Mechanism and Temperature and Force Sensors for Laparoscopic Tools

This paper presents concepts, designs, and working prototypes of enhanced laparoscopic surgical tools. The enhancements are in equipping the tool with force and temperature sensing as well as image acquisition for stereo vision. Just as the pupils of our eyes are adequately spaced out and the distance between them is adjustable, two minute cameras mounted on a mechanism in our design can be moved closer or farther apart inside the inflated abdomen during the surgery. The cameras are fitted to a deployable mechanism consisting of flexural joints so that they can be inserted through a small incision and then deployed and moved as needed.A temperature sensor and a force sensor are mounted on either of the gripping faces of the surgical grasping tool to measure the temperature and gripping force, which need to be controlled for safe laparoscopic surgery. The sensors are small enough and hence they do not cause interference during surgery and insertion.Prototyping and working of the enhanced laparoscopic tool are presented with details

An Improved Compact Compliant Mechanism for an External Pipe-Crawler

An external pipe-crawling device presented in this paper aids the inspection of pipes in hazardous environments and areas inaccessible to humans. The principal component of our design, which uses inchworm type motion, is a compliant ring mechanism actuated using shape memory alloy (SMA) wire. It was fabricated and tested and was reported in our earlier work. But this device had a drawback of low crawling speed (about 1 mm/min) owing to the delay in heating and cooling of the SMA strips in the linear actuation. Additionally, that design also had the difficulties of mounting on pipes with closed ends, large radial span, and the need for housing for electrical insulation and guiding of the SMA wire. In this paper we present a compact design that overcomes the difficulties of the earlier design. In particular, we present a compact compliant mechanism with two halves so as to enable mounting and un-mounting on any closed or open pipe. Another feature is the presence of insulation and guiding of the SMA wire without housing. This design results in a reduction of the radial span of the ring from 22 mm to 12 mm, and the stiffness of the mechanism and the SMA wire are matched. An SMA helical spring is to used in the place of an SMA strip to increase the crawling speed of the device. A microcontroller-based circuitry is also fitted to cyclically.activate the SMA wires and springs.

A Compliant Mechanism Kit with Flexible Beams and Connectors

We present the concept, prototypes, and an optimal design method for a compliant mechanism kit as a parallel to the kits available for rigid-body mechanisms. The kit consists of flexible beams and connectors that can be easily hand-assembled using snap fits. It enables users, using their creativity and mechanics intuition, to quickly realize a compliant mechanism. The mechanisms assembled in this manner accurately capture the essential behavior of the topology, shape, size and material aspects and thereby can lead the way for a real compliant mechanism for practical use. Also described in this paper are the design of the connector to which flexible beams can be added in eight different directions; and prototyping of the spring steel connectors as well as beams using wire-cut electro discharge machining. It is noted in this paper that the concept of the kit also resolves a discrepancy in the finite element (FE) modeling of beam-based compliant mechanisms. The discrepancy arises when two or more beams are joining at one point and thus leading to increased stiffness. After resolving this discrepancy, this work extends the topology optimization to automatically generate designs that can be assembled with the kit. Thus, the kit and the accompanying analysis and optimal synthesis procedures comprise a self-contained educational as well as a research and pragmatic toolset for compliant mechanisms. The paper also illustrates how human creativity finds new ways of using the kit beyond the original intended use and how it is useful even for a novice to design compliant mechanisms.