Heptaphyrins: Expanded porphyrins with seven heterocyclic rings

Expanded porphyrins containing seven pyrrole/heterocyclic rings linked in a cyclic fashion are termed heptaphyrins. The number ofπ-electrons in heptaphyrins depends on the number ofmeso carbon bridges used to link the heterocyclic rings, accordingly heptaphyrins with 28π-electrons and 30π-electrons are reported to date. Both condensation reactions of the appropriate precursors and acid-catalysed oxidative coupling reactions have been utilized to synthesise the heptaphyrins. The 30π heptaphyrins exhibit rich structural diversity where some of the heterocyclic rings in the macrocycle undergo a 180° ring flipping. An overview of the synthetic methods employed for the synthesis of heptaphyrins, their spectroscopic properties, structural behaviour and aromatic properties are highlighted in this paper. Dedicated to Professor C N R Rao on his 70th birthday     

TDI CAMERA APPLICATION IN DYNAMIC PHOTOMECHANICS

Optical methods for dynamic stress analysis require fast recording of the fringe patterns representing the stress distribution. Various recording techniques exist using fast framing cameras and short light pulse systems.¹ In all of these techniques the wet film processing is tedious and time consuming. Manual data analysis from the fringe patterns is cumbersome. Also, optical processing of the photographs for extracting further information requires complicated optical hardware. Hence, there were efforts from researchers to record the patterns in computer memories. The software image processing methods ease the data analysis and contrast enhancement.^2,3 Here we report the use of a special type CCD camera for dynamic applications. Details of the CCD camera operation are discussed. Application of the camera for dynamic problems is illustrated by performing a simple experiment.     

Multiblock copolymers of poly(2,5‐benzophenone) and disulfonated poly(arylene ether sulfone) for proton‐exchange membranes. I. Synthesis and characterization

Nanophase‐separated, hydrophilic–hydrophobic multiblock copolymers are promising proton‐exchange‐membrane materials because of their ability to form various morphological structures that enhance transport. A series of poly(2,5‐benzophenone)‐activated, telechelic aryl fluoride oligomers with different block molecular weights were successfully synthesized by the Ni(0)‐catalyzed coupling of 2,5‐dichlorobenzophenone and the end‐capping agent 4‐chloro‐4′‐fluorobenzophenone. These telechelic oligomers (hydrophobic) were then copolymerized with phenoxide‐terminated, disulfonated poly(arylene ether sulfone)s (hydrophilic) by nucleophilic, aromatic substitution to form hydrophilic–hydrophobic multiblock copolymers. High‐molecular‐weight multiblock copolymers with number‐average block lengths ranging from 3000 to 10,000 g/mol were successfully synthesized. Two separate glass‐transition temperatures were observed via differential scanning calorimetry in the transparent multiblock copolymer films when each block length was longer than 6000 g/mol. Tapping‐mode atomic force microscopy also showed clear nanophase separation between the hydrophilic and hydrophobic domains and the influence of the block length as it increased from 6000 to 10,000 g/mol. Transparent and creasable films were solvent‐cast and exhibited moderate proton conductivity and low water uptake. These copolymers are promising candidates for high‐temperature proton‐exchange membranes in fuel cells, which will be reported separately in part II of this series. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 284–294, 2007     

Second harmonic generation in elastic surface waves on an isotropic solid

A procedure for solving the problem of non-linear propagation of elastic surface waves is given. An expression for the particle displacement of the second harmonic is obtained. It is shown that the amplitude of the harmonic increases linearly with distance and time and is proportional to the square of the amplitude of the fundamental frequency wave.     

Extraordinary Changes in the Electronic Structure and Properties of CdS and ZnS by Anionic Substitution: Cosubstitution of P and Cl in Place of S

Unlike cation substitution, anion substitution in inorganic materials such as metal oxides and sulfides would be expected to bring about major changes in the electronic structure and properties. In order to explore this important aspect, we have carried out first‐principles DFT calculations to determine the effects of substitution of P and Cl on the properties of CdS and ZnS in hexagonal and cubic structures and show that a sub‐band of the trivalent phosphorus with strong bonding with the cation appears in the gap just above the valence band, causing a reduction in the gap and enhancement of dielectric properties. Experimentally, it has been possible to substitute P and Cl in hexagonal CdS and ZnS. The doping reduces the band gap significantly as predicted by theory. A similar decrease in the band gap is observed in N and F co‐substituted in cubic ZnS. Such anionic substitution helps to improve hydrogen evolution from CdS semiconductor structures and may give rise to other applications as well.     

Improvement in the yield and quality of kalmegh (Andrographis paniculata Nees) under the sustainable production system

Andrographis paniculata Nees is an annual erect herb with wide medicinal and pharmacological applications due to the presence of andrographolide and other active chemical constituents. The large-scale cultivation of the kalmegh is not in practice. The aim of this study was to establish sustainable production systems of A. paniculata cv CIM-Megha with the application of different bioinoculants and chemical fertilisers. A. paniculata herb and andrographolide yield in the dried leaves was found to be highest (218% and 61.3%, respectively) in treatment T₃ (NPK+Bacillus sp.) compared with T₁ (control). The soil organic carbon, soil microbial respiration, soil enzymes activity and available nutrients improved significantly with combined application of bioinoculants and chemical fertilisers.     

Antibacterial activity of conjugated polyelectrolytes with variable chain lengths

Cationic poly(phenylene ethynylene)- (PPE-) based conjugated polyelectrolytes (CPEs) with six different chain lengths ranging in degree of polymerization from ～7 to ～49 were synthesized from organic-soluble precursor polymers. The molecular weight of the precursor polymers was controlled by the amount of a monofunctional "end-capping" agent added to the polymerization reaction. Cationic CPEs were prepared by quaternization of amine groups to tetraalkylammonium groups. Their structure-property relationships were investigated by observing their photophysical properties and antibacterial activity. The polymers were found to exhibit a chain-length dependence in their photophysical properties. It has also been observed that the polymers exhibit effective antibacterial activity against both Gram-positive and Gram-negative bacteria under UV irradiation, whereas they show little antibacterial activity in the dark. An effect of chain length on the light-activated antibacterial activity was also found: The shortest polymer (n=7) exhibited the most effective antibacterial activity against both Gram-positive and Gram-negative bacteria.     

Triangular line graphs and word sense disambiguation

Linguists often represent the relationships between words in a collection of text as an undirected graph G=(V,E), where V is the vocabulary and vertices are adjacent in G if and only if the words that they represent co-occur in a relevant pattern in the text. Ideally, the words with similar meanings give rise to the vertices of a component of the graph. However, many words have several distinct meanings, preventing components from characterizing distinct semantic fields. This paper examines how the structural properties of triangular line graphs motivate the use of a clustering coefficient on the triangular line graph, thereby helping to identify polysemous words. The triangular line graph of G, denoted by T(G), is the subgraph of the line graph of G where two vertices are adjacent if the corresponding edges in G belong to a K₃.     

Weak Convergence Results for Multiple Generations of a Branching Process

We establish limit theorems involving weak convergence of multiple generations of critical and supercritical branching processes. These results arise naturally when dealing with the joint asymptotic behavior of functionals defined in terms of several generations of such processes. Applications of our main result include a functional central limit theorem (CLT), a Darling–Erdös result, and an extremal process result. The limiting process for our functional CLT is an infinite dimensional Brownian motion with sample paths in the infinite product space (C ₀[0,1])^∞, with the product topology, or in Banach subspaces of (C ₀[0,1])^∞ determined by norms related to the distribution of the population size of the branching process. As an application of this CLT we obtain a central limit theorem for ratios of weighted sums of generations of a branching processes, and also to various maximums of these generations. The Darling–Erdös result and the application to extremal distributions also include infinite-dimensional limit laws. Some branching process examples where the CLT fails are also included.