Weber electrodynamics: part III. mechanics,gravitation

Weber electrodynamics predicts the Kaufmann-Bucherer experiments and the fine structure energy level splitting of the H-atom (neglecting spin) without mass change with velocity (i.e., mass ). The Weber potential for the gravitational case yields Newtonian mechanics, confirming Mach's principle. It provides a cosmological condition yielding an estimated radius of the universe of 8 × 10⁹ light years. Despite these successes, the independent evidence for Kaufmann mechanics, where mass changes with velocity (i.e., mass ) is convincing. Perhaps a slight alteration may make the Weber theory compatible with Kaufmann mechanics.     

Proton controlled intramolecular communication in dinuclear ruthenium(II) polypyridine complexes

The synthesis and characterization of two dinuclear ruthenium polypyridyl complexes based on the bridging ligands 5,5'-bis(pyridin-2' '-yl)-3,3'-bis(1H-1,2,4-triazole) and 5,5'-bis(pyrazin-2' '-yl)-3,3'-bis(1H-1,2,4-triazole) and of their mononuclear precursors are reported. The dinuclear compounds have been prepared by a Ni(0) catalyzed coupling of a mononuclear ruthenium(II) polypyridyl complex containing a brominated triazole moiety. Electrochemical and photophysical studies indicate that, in these dinuclear complexes, the protonation state of the bridge may be used to tune the intercomponent interaction between the two metal centers and that these species act as proton driven three-way molecular switches that can be read by electrochemical or luminescence techniques.     

Synthesis and properties of 1,3,5-benzene periodic mesoporous organosilica (PMO): novel aromatic PMO with three point attachments and unique thermal transformations

A new aromatic periodic mesoporous organosilica material containing benzene functional groups that are symmetrically integrated with three silicon atoms in an organosilica mesoporous framework is reported. The material has a high surface area, well-ordered mesoporous structure and thermally stable framework aromatic groups. The functional aromatic moieties were observed to undergo sequential thermal transformation from a three to two and then to a one point attachment within the framework upon continuous thermolysis under air before eventually being converted to periodic mesoporous silica devoid of aromatic groups at high temperatures and longer pyrolysis times. The mesoporosity of the material was characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), and nitrogen porosimetry, whereas the presence and transformation of the aromatic groups in the walls of the materials were characterized by solid-state NMR spectroscopy, mass spectrometry, and thermogravimetric analysis. The attachment of a benzene ring symmetrically onto three siloxanes of the framework was used advantageously as a cross-linker to enhance the thermal stability of the organic group. Some of these properties are investigated in comparison with other aromatic PMOs that have only two point attachments and an amorphous phenylsilica gel that has only one point attachment. The successful synthesis of the first aromatic PMO with its organic group attached within the framework through more than two points is an important step toward the synthesis of PMOs having organic groups with more complex and multiple attachments within the framework.     

On the nature of the Møller-Plesset critical point

It has been suggested [F. H. Stillinger, J. Chem. Phys. 112, 9711 (2000)] that the convergence or divergence of M?ller-Plesset perturbation theory is determined by a critical point at a negative value of the perturbation parameter z at which an electron cluster dissociates from the nuclei. This conjecture is examined using configuration-interaction computations as a function of z and using a quadratic approximant analysis of the high-order perturbation series. Results are presented for the He, Ne, and Ar atoms and the hydrogen fluoride molecule. The original theoretical analysis used the true Hamiltonian without the approximation of a finite basis set. In practice, the singularity structure depends strongly on the choice of basis set. Standard basis sets cannot model dissociation to an electron cluster, but if the basis includes diffuse functions then it can model another critical point corresponding to complete dissociation of all the valence electrons. This point is farther from the origin of the z plane than is the critical point for the electron cluster, but it is still close enough to cause divergence of the perturbation series. For the hydrogen fluoride molecule a critical point is present even without diffuse functions. The basis functions centered on the H atom are far enough from the F atom to model the escape of electrons away from the fluorine end of the molecule. For the Ar atom a critical point for a one-electron ionization, which was not previously predicted, seems to be present at a positive value of the perturbation parameter. Implications of the existence of critical points for quantum-chemical applications are discussed.     

A Complex Pyrrolo-oxazinone and Its Iodo Derivative Isolated from a Tunicate

Two cytotoxic triphenylpyrrolo-oxazinones were isolated from a tunicate and their structures elucidated by spectral methods. Lukianol A ( = 3,7,8-tris(4-hydroxyphenyl)pyrrolo[2,1-c][1,4]oxazin-1 (1H)-one; 1 ) had MIC of 1 μg/ml in KB cytotoxicity tests; MIC value for 2 was 100 μg/ml.     

Chemistry of the phenoxathiins IV. Synthesis of 9-substituted 1 -azaphenoxathiins

In an extension of recently reported syntheses of the I-azaphenoxathiin nucleus as well as several 7-substituted analogs, the synthesis of several 9-substituted members of this series is now reported. In addition, the first ¹³C-nmr spectral evidence of an interaction between a sulfur atom and the oxygen of an ortho-nilro group which has been previously observed only in X-ray erystallographic studies is also described. The possible consequences of this interaction on the reaction pathway leading to the cyclization of the 9-substituted J-azaphenoxathiin nucleus is also presented.     

Methyl groups as probes for proteins and complexes in in-cell NMR experiments

Studying protein components of large intracellular complexes by in-cell NMR has so far been impossible because the backbone resonances are unobservable due to their slow tumbling rates. We describe a methodology that overcomes this difficulty through selective labeling of methyl groups, which possess more favorable relaxation behavior. Comparison of different in-cell labeling schemes with three different proteins, calmodulin, NmerA, and FKBP, shows that selective labeling with [(13)C]methyl groups on methionine and alanine provides excellent sensitivity with low background levels at very low costs.