Hypothetical C(60) Metal-Cluster Fullerides and General Aspects of Tetrahedral Cluster Bonding

It is geometrically feasible to insert metal-metal-bonded M(4) tetrahedra and M(6) octahedra into the tetrahedral and octahedral holes, respectively, of the fcc C(60) lattice. The electronic structure of the hypothetical tetrahedral variants C(60)(M(4))(2), M = Rh, Co, is analyzed with approximate molecular orbital methods and band structure calculations. These compounds feature M-M and M-C(60) bonding and a variable degree of electron transfer to or from C(60). The C(60)(M(4))(2) phases should be metallic, but we have no way of predicting if they will be superconducting. A number of discrete molecular tetrahedral cluster compounds which serve as models for the solid state materials are analyzed. There is a clear indication that tetranuclear and even mononuclear Rh, Ir, and Co arene complexes should be relatively unstable.     

Banach algebras of singular integral operators with piecewise continuous coefficients. General contour and weight

The Banach algebra generated by one-dimensional linear singular integral operators with matrix valued piecewise continuous coefficients in the spaceL _p (,) with an arbitrary weight is studied. The contour consists of a finite number of closed curves and open arcs with satisfy the Carleson condition. The contour may have a finite number of points of selfintersection. The symbol calculus in this algebra is the main result of the paper.     

Evaluation of heats of transition in scanning calorimetry

A procedure for the evaluation of heats of transition in scanning calorimetry has been developed. A formula for evaluation of the energy of fusion of a compound at its melting point is derived that takes into account the baseline shift that is attributable to the heat capacity change on melting. Several other calorimeter parameters of importance are discussed. These include heat exchange between calorimeter vessel and jacket, the time constant of the instrument, the scanning rate, and the heater placement.     

Acetylcholinesterase complexed with bivalent ligands related to huperzine a: experimental evidence for species-dependent protein-ligand complementarity

Acetylcholinesterase (AChE) inhibitors improve the cognitive abilities of Alzheimer patients. (-)-Huperzine A [(-)-HupA], an alkaloid isolated from the club moss, Huperzia serrata, is one such inhibitor, but the search for more potent and selective drugs continues. Recently, alkylene-linked dimers of 5-amino-5,6,7,8-tetrahydroquinolinone (hupyridone, 1a), a fragment of HupA, were shown to serve as more potent inhibitors of AChE than (-)-HupA and monomeric 1a. We soaked two such dimers, (S,S)-(-)-bis(10)-hupyridone [(S,S)-(-)-2a] and (S,S)-(-)-bis(12)-hupyridone [(S,S)-(-)-2b] containing, respectively, 10 and 12 methylenes in the spacer, into trigonal TcAChE crystals, and solved the X-ray structures of the resulting complexes using the difference Fourier technique, both to 2.15 A resolution. The structures revealed one HupA-like 1a unit bound to the "anionic" subsite of the active-site, near the bottom of the active-site gorge, adjacent to Trp84, as seen for the TcAChE/(-)-HupA complex, and the second 1a unit near Trp279 in the "peripheral" anionic site at the top of the gorge, both bivalent molecules thus spanning the active-site gorge. The results confirm that the increased affinity of the dimeric HupA analogues for AChE is conferred by binding to the two "anionic" sites of the enzyme. Inhibition data show that (-)-2a binds to TcAChE approximately 6-7- and > 170-fold more tightly than (-)-2b and (-)-HupA, respectively. In contrast, previous data for rat AChE show that (-)-2b binds approximately 3- and approximately 2-fold more tightly than (-)-2a and (-)-HupA, respectively. Structural comparison of TcAChE with rat AChE, as represented by the closely related mouse AChE structure (1maa.pdb), reveals a narrower gorge for rat AChE, a perpendicular alignment of the Tyr337 ring to the gorge axis, and its conformational rigidity, as a result of hydrogen bonding between its hydroxyl group and that of Tyr341, relative to TcAChE Phe330. These structural differences in the active-site gorge explain the switch in inhibitory potency of (-)-2a and 2b and the larger dimer/(-)-HupA potency ratios observed for TcAChE relative to rat AChE. The results offer new insights into factors affecting protein-ligand complementarity within the gorge and should assist the further development of improved AChE inhibitors.