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     

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     

Synthesis and characterisation of urethane-methacrylates I

The paper describes the synthesis of urethane methacrylate resins by reaction of tolylene diisocyanate (TDI), butanol-1 (B) and 2-hydroxyethylmethacrylate (HEMA) by a two step procedure. Characterisation was done using FT-IR, FT-NMR, Mass Spectroscopy. The effect of temperature on the UV-curing behaviour was investigated by differential photocalorimetry. An activation energy of 8.4 kJ/mole was found in the temperature range of 50–100°C. Free radical polymerisation in presence of benzoyl peroxide was also investigated. The polymers were stable upto 200°C in N₂ atmosphere. A two step decomposition was observed in the temperature range of 200–500°C.

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Zusammenfassung Vorliegende Arbeit beschreibt die Synthese von Urethan-methacrylat-Harzen durch die Reaktion von Toluylendiisocyanat (TDI), Butanol-1 (B) und 2-Hydroxyethylmethacrylat (HEMA) in einem zweistufigen Herstellungsverfahren. Charakterisiert wurden die Produkte mittels FT-IR, FT-NMR und Massenspektroskopie. Anhand von Differentialfotokalorimetrie wurde der Einfluß der Temperatur auf das UV-Aushärtungsverhalten untersucht. Im Temperaturbereich 50–100°C wurde eine Aktivierungsenergie von 8.4 kJ/mol gefunden. Weiterhin wurde auch die Radikalkettenpolimerisation in Gegenwart von Benzoylperoxid untersucht. In Stickstoffatmosphäre sind die Polymere bis 200°C stabil. Im Temperaturbereich 200–500°C wurde eine zweistufige Zersetzung beobachtet.

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The Instrument system of E. I. DuPont de Nemours & Co. is acknowledged for differential photocalorimeter studies.     

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.     

Morphological,mechanical, and in vitro cytocompatibility analysis of poly(vinyl alcohol)–silica glass hybrid scaffolds reinforced with cellulose nanocrystals

Cellulose nanocrystal-reinforced poly(vinyl alcohol)/silica glass hybrid scaffolds were fabricated using the freeze-drying method. In this study, we develop molecular-level-based hybrid scaffolds with possible bioactivity behavior by adding silica sol–gel. The results showed a highly porous structure and a significant improvement in mechanical performance (stiffness) of hybrid scaffolds with an increased content of cellulose nanocrystals followed by the addition of silica-based bioactive glass. In vitro cell study with MC3T3-E1 cells on hybrid scaffolds for 1 and 3 days revealed good cell adhesion and growth. Thus, the obtained hybrid scaffold may be a competitive candidate for bone tissue engineering applications.     

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.