Six-dimensional vibrational analysis of coupled intermolecular vibrations in a binary cluster

We report on full- (six-) dimensional calculations of the intermolecular vibrations of a binary aromatic-solvent cluster. An exact Hamiltonian for this kind of interaction is modified in a general manner in order to perform calculations of molecules without symmetry. The binary cluster phenol(H2O)1 is used as a test case since its intermolecular vibrations are anharmonic and highly coupled. The formulation of the Schrodinger equation leads to a complex-valued eigenvalue problem with a dimension larger than two million, which is solved by filter diagonalization to obtain both eigenvalues and eigenvectors. With the knowledge of the eigenvectors, an interpretation of all eigenvalues is possible by a characterization with pseudoquantum numbers that are related to the widely used nomenclature of intermolecular normal motions in aromatic(solvent) clusters.     

Measuring the similarity between trajectories using clustering techniques

A clustering method has been developed to group signals that display similar dynamic behavior. The procedure involves using the method of time delay embedding to construct a trajectory in state space from a time series. Certain features that characterize the geometry of the trajectory have been defined. These features were subjected to a series of statistical tests to determine their usefulness in a hierarchical clustering analysis. The latter is aimed at finding groups of similar trajectories. The trajectory-based clustering algorithm has been applied to simulated data, which included both stochastic data generated by a linear AR model, and nonlinear data generated by a Duffing oscillator. The results show that the algorithm works reliably in both cases.     

Crystal and molecular structure of the cycloaddition product between maleic anhydride,cyclopentadiene, and 1,2-bis(dibromomethyl)benzene as DMF solvate (1∶2)

Crystal structure determination reveals that the unknown cycloaddition product between maleic anhydride, cyclopentadiene, and 1,2-bis(dibromomethyl)benzene has a nona-cyclic centrosymmetric structure. The compound was studied as DMF solvate (12). There is no significant intermolecular interaction between the title molecule and the DMF. Packing is in layers for both molecular species. A possible mechanism of formation of the title compound is discussed.     

A unified and quantitative receptor model for the microtubule binding of paclitaxel and epothilone

[formula: see text] Paclitaxel and epothilone represent the two major classes of antimicrotubule agents that promote tubulin polymerization and, presumably, mitotic arrest during cell division. A common minireceptor binding site model at beta-tubulin has been constructed for these structurally divergent compounds. Utilizing 20 amino acids identified in photoaffinity labeling experiments, the 3-D model correlates measured and predicted Ki's with r = 0.99 and rms(delta Gcalc-delta Gexp) = 0.2 kcal/mol. In addition, the model predicts the affinity of compounds not used in the training set and explains much of the SAR for the paclitaxel and epothilone families.     

Liquid chromatographic purification and detection of anabolic compounds.

The role of liquid chromatography within methods of analysis for steroids, related compounds and beta-agonists in biological samples is discussed. Special attention is given to the application of liquid chromatography in sample preparation and extract clean-up. Different forms of liquid chromatography, including immunoaffinity chromatography, are compared and evaluated. Methods for confirmation based on gas chromatography-mass spectrometry and cryotrapping Fourier transform infrared spectrometry are discussed.     

Lateral interactions and multi-isotherms: nitrogen recombination from Rh(111)

Lateral adsorbate-adsorbate interactions result in variation of the desorption rate constants with coverage. This effect can be studied in great detail from the shape of a multi-isotherm. To produce the multi-isotherm, the temperature is increased in a (semi)stepwise fashion to some temperature, followed by maintaining this temperature for a prolonged time. Then, the temperature is stepped to a higher value and held constant at this new temperature. This cycle is continued until all of the adsorbates have desorbed. Using a detailed kinetic Monte Carlo model and an optimization algorithm based on Evolutionary Strategy, we are able to reproduce the shape of the experimentally measured multi-isotherm of nitrogen on Rh(111) and obtain the lateral interactions between the nitrogen atoms.     

Massenspektrometrische Untersuchungen der Gasphase über As2O5

Mass Spectrometric Investigations of the Gaseous Phase above As₂O₅ The gaseous phase above solid As₂O₅ has been investigated in the temperature range between 862 and 939 K by mass spectrometric methods. The presence of gaseous As₄O_x-molecules (6 ≤ × ≤ 10) and O₂ was proved. Using the partial pressures, heats of formation (Δ_fH°(900), kJ · mol^?1; 2nd law calculations) were calculated (As₄O_7,g: -1209,5; As₄O_8,g: -1361,9; As₄O_9,g: -1495,4; As₄O_10,g: -1618,8). The enthalpy of formation of solid As₂O₅ was determined to be Δ_fH°(298) = ?1007,9 kJ · mol^?1. The thermochemical data of the As₄O_x-molecules are discussed in context with possibilities for the synthesis of solid As₄O₁₀.