Self‐Assembly and Gelation of Poly(aryl ether) Dendrons Containing Hydrazide Units: Factors Controlling the Formation of Helical Structures

Self‐assembly of AB₂ and AB₃ type low molecular weight poly(aryl ether) dendrons that contain hydrazide units were used to investigate mechanistic aspects of helical structure formation during self‐assembly. The results suggest that there are three important aspects that control helical structure formation in such systems with acyl hydrazide/hydrazone linkage: i) J‐type aggregation, ii) the hydrogen‐bond donor/acceptor ability of the solvent, and iii) the dielectric constant of the solvent. The monomer units self‐assemble to form dimer structures through hydrogen‐bonding and further assembly of the hydrogen‐bonded dimers leads to macroscopic chirality in the present case. Dimer formation was confirmed by NMR spectroscopy and by mass spectrometry. The self‐assembly in the system was driven by hydrogen‐bonding and π–π stacking interactions. The morphology of the aggregates formed was examined by scanning electron microscopy, and the analysis suggests that aprotic solvent systems facilitate helical fibre formation, whereas introduction of protic solvents results in the formation of flat ribbons. This detailed mechanistic study suggests that the self‐assembly follows a nucleation–elongation model to form helical structures, rather than the isodesmic model.     

Molecular structure,vibrational spectroscopic and chemical reactivity of nematogenic p-n-alkylbenzoic acids: A comparative computational analysis

Molecular structure and vibrational spectroscopic studies of higher homologous series nematogenic p-n-alkylbenzoic acids (nBAC) that have 6 (6BAC) and 7 (7BAC) carbon atoms in the alkyl chain have been investigated using the Density Functional Becke3-Lee-Yang-Parr (B3LYP) level with the basis set 6-31++G (d.p) and Hartree Fock (HF) with the same basis set. The observed vibrational spectra has been resolved and assigned in detail for comparision with both the molecules. These results indicate that DFT and HF values are slightly different at both the levels. A comparision of chemical reactivity such as HOMO (E_H), LUMO (E_L) energies, energy gap (E_g), ionization energy (I), electron affinity (A), electro negativity (χ), chemical hardness (η), electronic chemical potential (μ), electrophilicity index (ω), and softness (S) has been made. It has been observed that the decrement has occurred in the energy band gap value of isolated molecule with increment in alkyl chain length. This provides valuable information regarding enhancing the stability of liquid crystal materials by maintaining the conductivity.     

Collisional excitation of Na-Rydberg atoms

The scattering of heavy ion with a multilevel Rydberg atom in the presence of an electromagnetic field is studied. The interaction of Rydberg atom and the e.m field is explored using non-perturbative quasi-energy technique. Although the results are presented for selected excitations but in actual calculations we have included many levels of the atom. The effect of various parameters are shown on collisional excitation process. As an illustration detailed calculations are performed for the inelastic proton-Na Rydberg atom collision accompanied by the transfer of photons and the effects of dressing due to the field are considered. The emphasis of the present work is on collision induced transitions especially the case that involves change of orbital as well as principal quantum number. Received 26 December 2001 / Received in final form 8 April 2002 Published online 19 July 2002     

Crystal structure of the 4-chromanone derivative.

The title compound was extracted from a natural product and its structure was characterized by an X-ray diffraction method. It crystallizes in the tetragonal space group P41 with cell parameters a = 15.832(10)A, c = 11.622(10)A, Z = 4; the final residual factor is R1 = 0.0769. The structure has both intra and intermolecular hydrogen bonds.     

Deciding confluence of certain term rewriting systems in polynomial time

We present a characterization of confluence for term rewriting systems, which is then refined for special classes of rewriting systems. The refined characterization is used to obtain a polynomial time algorithm for deciding the confluence of ground term rewrite systems. The same approach also shows the decidability of confluence for shallow and linear term rewriting systems. The decision procedure has a polynomial time complexity under the assumption that the maximum arity of a function symbol in the signature is a constant.     

Magnetic and martensitic transitions in Ni-Fe-Ga alloy

The ferromagnetic shape memory alloy with nominal composition Ni₅₄Fe₁₉Ga₂₇ is investigated by Ac susceptibility and resistivity measurements. The alloy shows long-range ferromagnetic order below 290 K. The anomaly due to the martensitic transition is observed in the susceptibility and resistivity data in the temperature range around 220 K, which is associated with clear thermal hysteresis. Minor hysteresis loop technique was used to investigate the phase coexistence across the martensitic transition, and our analysis indicate that both martensite and austenite phases mutually coexist in the region of hysteresis.     

Thermal decomposition of a generation 4.5 PAMAM dendrimer platinum drug conjugate

A nanoscale multivalent platinum drug based on a poly(amidoamine) [PAMAM] dendrimer (generation 4.5, carboxylate surface) has been synthesized and fully characterized using a variety of spectroscopic, chromatographic and thermal methods. Treatment of the dendrimer with an aqueous solution containing an excess diaquo(cis-1,2-diaminocyclohexane)platinum(II) produces a conjugate containing approximately forty (diaminocyclohexane)platinum(II) moieties at the surface of the dendrimer. This material undergoes smooth two-stage thermal decomposition to provide residual platinum oxide reflecting the platinum loading in the drug.