Siloxane polymers containing azo moieties synthesized by click chemistry for photo responsive and liquid crystalline applications

Three new types of siloxane‐based photoactive liquid crystalline polymers containing azo side groups were synthesized through the click chemistry route. The polymers having molecular weight range of 14,000–34,000 g mol^?1 were soluble in most of the polar solvents like chloroform, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, and dichloromethane. The photoresponsive trans–cis photoisomerization under UV radiation and cis–trans relaxation process in dark for the polymers were studied. The isomerization rate constants were found to be 0.01–0.04 sec^?1 and 1.16*10^?4–4.67*10^?4 sec^?1, respectively. It has been noted that the polymers showed high intensity absorption for n‐π* in chloroform. Both trans and cis forms of azide monomers having azo moiety exhibited molar extinction coefficient ( ? _max) in the range of 22,000–33,000 L mol^?1 cm^?1. The thermotropic behavior of the polymers was studied by polarizing optical microscope (POM) and differential scanning calorimetry (DSC) experiments. Polymer P1 showed liquid crystalline textures of nematic droplets, whereas P2 showed smectic focal conic texture and nematic droplets. Polymer P1 was also studied for photomechanical bending on exposure to UV radiation. The polymers showed initial degradation temperature in the range of 210–275°C. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Click chemistry‐based synthesis of azo polymers for second‐order nonlinear optics

Four linear polymers containing pendant azo moiety were synthesized through click chemistry for second‐order nonlinear optical study. The polymers were found soluble in most of the polar organic solvents such as tetrahydrofuran (THF), chloroform, and dimethyl formamide (DMF). The polymers showed thermal stability up to 300 °C and glass transition temperatures (T_g) in the range of 120–140 °C. The molecular weights (M_w) of these polymers (measured by gel permeation chromatography) were in the range 37,900–55,000 g/mol. The polymers were found to form optically transparent films by solution casting from THF solution. Order parameters were calculated from UV–vis absorption spectra. The morphology changes in the films after poling were characterized by atomic force microscopy. The angular dependence, temperature dependence, and time dependence of second harmonic generation (SHG) intensity were obtained by using 1064 nm Nd:YAG laser. The SHG intensity remained unchanged up to 95 °C. At room temperature, it remained stable up to 8 days after initial drop of about 14%. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Perfect 1‐Factorizations of a Family of Cayley Graphs

A 1‐factorization of a graph G is a decomposition of G into edge‐disjoint 1‐factors (perfect matchings), and a perfect 1‐factorization is a 1‐factorization in which the union of any two of the 1‐factors is a Hamilton cycle. We consider the problem of the existence of perfect 1‐factorizations of even order 4‐regular Cayley graphs, with a particular interest in circulant graphs. In this paper, we study a new family of graphs, denoted , which are Cayley graphs if and only if k is even or . By solving the perfect 1‐factorization problem for a large class of graphs, we obtain a new class of 4‐regular bipartite circulant graphs that do not have a perfect 1‐factorization, answering a problem posed in 7 . With further study of graphs, we prove the nonexistence of P1Fs in a class of 4‐regular non‐bipartite circulant graphs, which is further support for a conjecture made in 7 .     

Synthesis and characterisation of pentacoordinated ruthenium(II) hydrazone derivatives

Several new pentacoordinated ruthenium(II) compounds, Ru(PPh₃)₂L, of Schiff bases LH₂ are reported. The Schiff bases used have been derived from isonicotinoyl hydrazone and β-diketones or salicylaldehyde, or azines and mixed azines obtained from salicylaldehyde, benzoylacetone or 2-hydroxyacetophenone. These new compounds are highly coloured crystalline solids, stable and monomeric in toluene. They readily absorb carbon monoxide gas to give a carbonyl derivative of the type Ru(PPh₃)₂CO(L) in quantitative yields.     

The <Emphasis Type="Italic">recombination activation gene 1</Emphasis> (<Emphasis Type="Italic">Rag1</Emphasis>) is expressed in a subset of zebrafish olfactory neurons but is not essential for axon targeting or amino acid detection

Background  

Rag1 (Recombination activation gene-1) mediates genomic rearrangement and is essential for adaptive immunity in vertebrates. This gene is also expressed in the olfactory epithelium, but its function there is unknown.     

Polarographic reduction of pyruvic acid

The application of Delahay’s theory of kinetic polarographic currents as applied to the reduction of pyruvic acid has been examined. It is shown that the agreement between Delahay’s theory and the available data is more satisfactory, if one assumes that the current is controlled by the rate of the reaction between pyruvate ion and water molecule forming pyruvic acid and hydroxyl ion, than when one assumes the mechanism suggested by the earlier workers involving the rate of reaction between pyruvate ion and hydrogen-ion, both from the point of view of the magnitude of the diffusion current as well as its pH dependence. The results give an indication of the latter reaction being sluggish due to the activation energy requirements.     

Synthesis,characterisation and reactions of pentacoordinated iridium(I) complexes

Stable, pentacoordinated iridium(I) complexes have been synthesised by the replacement of the chlorine in IrCO(PPh₃)₂Cl by bidentate chelating ligands such as β-diketones, N-benzoyl-N-phenyl hydroxylamine, salicylaldehyde, 8-hydroxyquinoline, 2-hydroxybenzophenone and 2-hydroxy 4-methoxybenzophenone. Most of them gave stable oxygen adducts IrCO(PPh₃)₂(L)O₂ and all of them underwent oxidative addition with bromine in methylene chloride giving IrCO(PPh₃)₂(L)Br₂. These chelated iridium(I) compounds reacted with liquid sulphur dioxide to produce two types of SO₂ insertion products.     

Higher Dimensional Unified Description of Early Universe with Variable <Emphasis Type="Italic">G</Emphasis> and Λ

A homogeneous and isotropic Friedmann-Robertson-Walker (FRW) model with varying gravitational and cosmological constant is studied in the context of higher dimensional space time. Exact solution of the field equations are obtained by using the “gamma law” equation of state p=(γ−1)ρ, where γ is adiabatic parameter varies continuously as the universe expands. The functional form γ which is assumed to be the function of scale factor R as proposed by Carvalho (1996) is used to analyse the behavior of scale factor R, cosmological constant Λ and the gravitational constant G for two different phases: inflation and radiation. The various physical aspects of the early cosmological models has also been discussed in the framework of higher dimensional space time.     

Synthesis and characterization of Y‐type polymers for second‐order nonlinear optical applications

A series of dicyanomethylene‐substituted polymers having Y‐type molecular architecture were synthesized by Knoevenagel condensation reaction. The polymers were found to be soluble in organic solvents like tetrahydrofuran and chloroform. From gel permeation chromatography, the molecular weights of the polymers were found to be in the range of 15,300–33,800 g/mol. Thermal analysis showed that the polymers were stable up to 350 °C with glass transition temperature (T_g) in the range of 129–212 °C. These polymers were found to form good optical quality films. The order parameter was calculated to be in the range of 0.01–0.48. Atomic force microscopy indicated prominent morphology changes due to alignment of dipoles after poling. By using Nd:YAG laser of 1064 nm, angular dependence and temperature dependence of second‐harmonic generation intensity were investigated. The geometry optimization, shape of polymers, and restricted torsion angle between acceptor and donor substituents (push–pull system) were calculated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013