Neopentylallylsodium

Neopentylallylsodium (NpANa) has been prepared by the reaction of neopentylallyllithium with an equivalent amount of sodium 2,2-dimethyl-1-butoxide in hydrocarbon solvent. NpANa is stable in diethyl ether and THF solvents for extended periods of time, and proton NMR and UV data are reported for NpANa in THF at various temperatures. A more substantial degree of ionic delocalization is indicated for NpANa as compared to NpALi and apparently is greater for the trans isomer of NpANa. UV absorption maxima for NpANa and NpALi are explained in terms of cis/trans ratios rather than in terms of ion pairing.     

The preparation,isomerization, and characterization of some phosphagerma- and arsagermacarboranes

Treatment of the disodium salts of 7,8- and 7,9-B₉H₉CHE^2? with germanium diiodide in refluxing benzene results in the formation of 1,2,3- and 1,2,7-GeB₉H₉CHE (E = P or As), icosahedral boranes containing three different heteroatoms in the cage. Heating 1,2,7-GeB₉H₉CHP at 512° for 8 hours in an evacuated sealed tube yields a mixture of three new isomers one of which has been isolated and characterized.     

Use of Dimethylsilyl Ethers for Characterizing Primary Aliphatic Alcohols: A comparison of mass spectrometric fragmentation of di- and trimethylsilyl derivatives

Mass spectral fragmentation patterns of dimethylsilyl (DMS) ethers of primary unbranched, branched, and secondary unbranched aliphatic alcohols in the C₅ to C₁₀ range are compared with those of the corresponding trimethylsilyl (TMS) derivatives. Unlike their TMS analogues, DMS ethers of primary alcohols exhibit pronounced rupture of the C? C bond adjacent to the oxygen atom within the alkyl moiety (loss of an alkyl radical R) in marked preference to cleavage within the silyl substituent (loss of CH₃). Within this class of compounds, complementary preparation of DMS derivatives can therefore be used to establish or to confirm the site, and thus the primary nature of the hydroxyl group, whereas preparation of TMS ethers may be of advantage in deducing molecular size. For the derivatives of secondary alcohols this diagnostically useful difference in fragmentation behaviour is not observed.     

Synthetic enantiopure aziridinomitosenes: preparation, reactivity, and DNA alkylation studies

An enantiocontrolled route to aziridinomitosenes had been developed from l-serine methyl ester hydrochloride. The tetracyclic target ring system was assembled by an internal azomethine ylide cycloaddition reaction based on silver ion-assisted intramolecular oxazole alkylation and cyanide-induced ylide generation via a labile oxazoline intermediate (62 to 66). Other key steps include reductive detritylation of 26, methylation of the N-H aziridine 56, oxidation of the sensitive cyclohexenedione 68 to quinone 70, and carbamoylation using Fmoc-NCO. Although the aziridinomitosene tetracycle is sensitive, a range of protecting group manipulations and redox chemistry can be performed if suitable precautions are taken. A study of DNA alkylation by the first C-6,C-7-unsubstituted aziridinomitosene 11a has been carried out, and evidence for DNA cross-link formation involving nucleophilic addition to the quinone subunit is described.     

Determination of affinity constants and response factors of the noncovalent dimer of gramicidin by electrospray ionization mass spectrometry and mathematical modeling

The dimerization of gramicidin, a 15-residue membrane peptide, in solution can be viewed as a model for protein-protein interactions. We reported previously that the dimer can be observed when electrosprayed from organic solvents and that the abundances of the dimer depends on the dielectric constant of the solvent. Here, we report an effort to determine an affinity constant for the dimerization of gramicidin by using gas-phase abundance. Two issues affecting the determination are the electrospray-induced dissociation of the dimer and discrimination in the electrospray of the dimer compared with the monomer. Other methods developed for the purpose of determining affinity from mass spectral abundance do not address the dissociation of the complex in the gas phase or can not be applied for cases of low affinity constant, K(a). We present a mathematical model that uses the ratio of the signal intensities of the dimer and the monomer during a titration. The model also incorporates the dissociation and an electrospray ionization-response factor of the dimer for extracting the affinity constant for the dimerization of gramicidin. The dimerization constants from the new method agree within a factor of two with values reported in the literature.     

Thermodynamics of black holes in anti-de Sitter space

The Einstein equations with a negative cosmological constant admit black hole solutions which are asymptotic to anti-de Sitter space. Like black holes in asymptotically flat space, these solutions have thermodynamic properties including a characteristic temperature and an intrinsic entropy equal to one quarter of the area of the event horizon in Planck units. There are however some important differences from the asymptotically flat case. A black hole in anti-de Sitter space has a minimum temperature which occurs when its size is of the order of the characteristic radius of the anti-de Sitter space. For larger black holes the red-shifted temperature measured at infinity is greater. This means that such black holes have positive specific heat and can be in stable equilibrium with thermal radiation at a fixed temperature. It also implies that the canonical ensemble exists for asymptotically anti-de Sitter space, unlike the case for asymptotically flat space. One can also consider the microcanonical ensemble. One can avoid the problem that arises in asymptotically flat space of having to put the system in a box with unphysical perfectly reflecting walls because the gravitational potential of anti-de Sitter space acts as a box of finite volume.     

Algorithm for Optimal Triangulations in Scattered Data Representation and Implementation

Scattered data collected at sample points may be used to determine simple functions to best fit the data. An ideal choice for these simple functions is bivariate splines. Triangulation of the sample points creates partitions over which the bivariate splines may be defined. But the optimality of the approximation is dependent on the choice of triangulation. An algorithm, referred to as an Edge Swapping Algorithm, has been developed to transform an arbitrary triangulation of the sample points into an optimal triangulation for representation of the scattered data. A Matlab package has been completed that implements this algorithm for any triangulation on a given set of sample points.     

Electrostatic energy of a complex and infinitely extended electronic system

Formulae concerning the evaluation of the total electrostatic energy per supercell in an infinitely extended system made up of identical atoms are developed in a consistent manner, which emphasizes and takes care of several delicate points connected with the occurrence of divergent and spurious constant terms. The treatment is carried out within a k-space formulation of density functional theory and special attention is devoted to a consistent re-derivation of the Madelung energy result of the Wigner solid associated with a realistic identical atom system. Two formulae of practical interest for computer applications are obtained and discussed.     

Science at the Hard X-ray Diffraction Limit (XDL2011), Part 1

There is growing excitement in the synchrotron materials science community about the potential of nearly diffraction-limited, high-repetition rate, hard X-ray sources, such as an Energy Recovery Linac (ERL) or an Ultimate Storage Ring (USR), and that these sources will pave the way to scientific insights and discoveries not possible with existing facilities. These future sources will deliver highly coherent, nearly diffraction-limited X-ray beams that will power ultra-intense, nanometer-scale X-ray probes and imaging capabilities approaching atomic resolution. They will produce X-ray pulses at MHz to GHz repetition rates and span pulse durations from below 50 femtoseconds to tens of picoseconds, enabling new classes of experiments in hard X-ray science.