(PEG)(x)NH4ClO4: A new polymeric fast proton conductor

A new polymer electrolyte (PEG)(x) NH4ClO4(x = 5, 10, 15, 20) has been prepared that shows protonic conduction. The room temperature conductivities are of the order of 10(-7) S/cm, and increase with decrease in salt concentration. NMR line width studies indicate fairly low glass transition temperatures of the polymer salt complexes.

Proton NMR spectral studies on N-(4-methylphenyl)-2- and 3-pyridinecarboxamides

The H-1 NMR spectra of N-(4-methylphenyl)-2-pyridinecarboxamide and N-(4-methyl-phenyl)-3-pyridine carboxamide in CDCl3 and (CD3)(2)CO have been analysed with the help of the COSY spectra. Accurate H-1 chemical shifts and coupling constants have been obtained from the simulated spectra. From H-1 NMR and Nuclear Overhauser Enhancement (NOE) measurements the molecular conformations are inferred. The pyridyl ring is apparently coplanar with the amide group while the 3-pyridyl ring is nearly perpendicular to the amide plane so that the amide proton is nearer to the 2-pyridyl proton H2 than to H4. The orientation of the 4-methylphenyl group could not be determined.

Mutagenic significance of proton acidities in methylated guanine and thymine bases and deoxynucleosides: A theoretical study

Proton changes have been advanced as being the key molecular basis for the mutagenecity of alkylated DNA bases and nucleosides, leading to questions as to which protons are involved and whether the protic changes are tautomeric shifts or abstractions. This semiempirical molecular orbital study seeks to clarify the issue by examining the various possibilities open for these protic changes in a number of methylated guanines and thymines and their deoxynucleosides. Proton shifts leading to tautomer formation are not predicted as being thermodynamically favourable in most cases. The most feasible proton abstractions are predicted to involve the Watson-Crick protons in all cases, which corroborates Watson-Crick proton loss as providing the key molecular basis for the induction of point mutations. The calculated proton acidities correlate well with experimental data. The gas-phase deprotonation enthalpies for a number of alkylated nucleosides are found to correlate linearly with the solvent-phase pK(a) values. The theoretically calculated enthalpies in a simulated aqueous solvent phase of the deprotonation reactions of various nucleic acid bases are also found to have good linear correlations with experimental pK(a) values. The consensus of these calculations is that O-6-alkyldeoxyguanosines, and O-2- and O-4-alkyldeoxythymidines would be mutagenic while N-7-alkyldeoxyguanosines would not be mutagenic (as experiment indicates). The untested N-3-methyldeoxyguanosine is predicted to be mutagenic. (C) 1997 Elsevier Science B.V.

Drug-drug co-crystals: Temperature-dependent proton mobility in the molecular complex of isoniazid with 4-aminosalicylic acid

Two drug-drug co-crystals of the anti-tuberculosis drugs isoniazid (INH), pyrazinamide (PYR) and 4-aminosalicylic acid (PAS) are reported. The first is the 1 : 1 molecular complex of INH and PAS. The second is the monohydrate of the 1 : 1 complex of PYR and PAS. The crystal structures of both co-crystals are characterized by a number of hydrogen bonded synthons. Hydrogen bonding of the COOH center dot center dot center dot N-pyridine type is found in both cases. In the INH : PAS co-crystal, there are two symmetry independent COOH center dot center dot center dot center dot N-pyridine hydrogen bonds. In one of these, the H-atom is located on the carboxylic group and is indicative of a co-crystal. In the second case, partial proton transfer occurs across the hydrogen bond, and the extent of proton transfer depends on the temperature. This is more indicative of a salt. Drug-drug co-crystals may have some bearing in the treatment of tuberculosis.

Proton NMR T-1 studies in methylammonium trichloro stannate(II) (CH3NH3SnCl3)

Proton spin lattice relaxation time (T-1) measurements have been carried out in methylammonium trichloro stannate(II) (CH3NH3SnCl3) as a function of temperature in the range 317-5 K at a Larmor frequency of 10 MHz. The temperature dependence of T-1 shows a phase transition around 220 K and four T-1 minima (294 K, 62 K, 32 K and 12 K). The results are discussed in terms of proton dynamics, namely, uncorrelated reorientation of NH3 and CH3 groups at high temperatures and tunnelling of NH3 and CH3 protons at low temperatures.

Rainbow Connection Number and Radius

Rainbow connection number, rc(G), of a connected graph G is the minimum number of colours needed to colour its edges, so that every pair of vertices is connected by at least one path in which no two edges are coloured the same. In this note we show that for every bridgeless graph G with radius r, rc(G) <= r(r+2). We demonstrate that this bound is the best possible for rc(G) as a function of r, not just for bridgeless graphs, but also for graphs of any stronger connectivity. It may be noted that, for a general 1-connected graph G, rc(G) can be arbitrarily larger than its radius (K_{1,n} for instance). We further show that for every bridgeless graph G with radius r and chordality (size of a largest induced cycle) k, rc(G) <= rk. Hitherto, the only reported upper bound on the rainbow connection number of bridgeless graphs is 4n/5 - 1, where n is order of the graph [Caro et al., 2008]

Spin State Selective Excitation of Single Quantum Transitions Using Multiple Quantum Spectroscopy- an Aid to Analyse Complex Proton NMR spectra of Oriented Molecules

NMR spectra of molecules oriented in liquid-crystalline matrix provide information on the structure and orientation of the molecules. Thermotropic liquid crystals used as an orienting media result in the spectra of spins that are generally strongly coupled. The number of allowed transitions increases rapidly with the increase in the number of interacting spins. Furthermore, the number of single quantum transitions required for analysis is highly redundant. In the present study, we have demonstrated that it is possible to separate the subspectra of a homonuclear dipolar coupled spin system on the basis of the spin states of the coupled heteronuclei by multiple quantum (MQ)−single quantum (SQ) correlation experiments. This significantly reduces the number of redundant transitions, thereby simplifying the analysis of the complex spectrum. The methodology has been demonstrated on the doubly 13C labeled acetonitrile aligned in the liquid-crystal matrix and has been applied to analyze the complex spectrum of an oriented six spin system.

Selective double quantum resolved correlation experiment for the complete separation of entire proton NMR spectra of enantiomers

The present study reports a two dimensional NMR experiment which separates single quantum spectra of enantiomers from that of a racemic mixture. This is a blend of selective double quantum refocusing, for resolving couplings and chemical shift interactions along two dimensions followed by correlation of the selectively excited protons to the entire coupled spin network. The concept is solely based on the presence of distinct intra methyl dipolar couplings of different enantiomers when dissolved in chiral orienting media. The analysis of single enantiomer spectrum obtained from respective F-2 cross sections yield all the spectral information. (C) 2011 Elsevier Inc. All rights reserved.

Strongly magnetized cold degenerate electron gas: Mass-radius relation of the magnetized white dwarf

We consider a relativistic, degenerate electron gas at zero temperature under the influence of a strong, uniform, static magnetic field, neglecting any form of interactions. Since the density of states for the electrons changes due to the presence of the magnetic field (which gives rise to Landau quantization), the corresponding equation of state also gets modified. In order to investigate the effect of very strong magnetic field, we focus only on systems in which a maximum of either one, two, or three Landau level(s) is/are occupied. This is important since, if a very large number of Landau levels are filled, it implies a very low magnetic field strength which yields back Chandrasekhar's celebrated nonmagnetic results. The maximum number of occupied Landau levels is fixed by the correct choice of two parameters, namely, the magnetic field strength and the maximum Fermi energy of the system. We study the equations of state of these one-level, two-level, and three-level systems and compare them by taking three different maximum Fermi energies. We also find the effect of the strong magnetic field on the mass-radius relation of the underlying star composed of the gas stated above. We obtain an exciting result that it is possible to have an electron-degenerate static star, namely, magnetized white dwarfs, with a mass significantly greater than the Chandrasekhar limit in the range 2.3-2.6M(circle dot), provided it has an appropriate magnetic field strength and central density. In fact, recent observations of peculiar type Ia supernovae-SN 2006gz, SN 2007if, SN 2009dc, SN 2003fg-seem to suggest super-Chandrasekhar-mass white dwarfs with masses up to 2.4-2.8M(circle dot) as their most likely progenitors. Interestingly, our results seem to lie within these observational limits.

Proton Conduction in Metal-Organic Frameworks and Related Modularly Built Porous Solids

Proton-conducting materials are an important component of fuel cells. Development of new types of proton-conducting materials is one of the most important issues in fuel-cell technology. Herein, we present newly developed proton-conducting materials, modularly built porous solids, including coordination polymers (CPs) or metalorganic frameworks (MOFs). The designable and tunable nature of the porous materials allows for fast development in this research field. Design and synthesis of the new types of proton-conducting materials and their unique proton-conduction properties are discussed.