The zirconium hydride dimer [Cp2ZrH2]2 reacts with C6F6 at ambient temperature to give Cp2Zr(C6F5)F as the major product along with Cp2ZrF2, C6F5H and H2. Neither the reaction rate nor the product ratio is affected by changes in H2 pressure or the concentration of C6F6. The reaction follows zero-order kinetics. The new compound Cp2Zr(C6F5)F has been structurally characterized. [Cp2ZrH2]2 reacts with C6F5H to give Cp2Zr(p-C6F4H)F, Cp2ZrF2, C6F4H2, and H2. The zirconium hydride Cp3ZrH has been structurally characterized and also reacts with C6F6. The products of the reaction are CpH, Cp2Zr(C6F5)F, C6F5H, Cp2ZrF2, Cp4Zr, and Cp3ZrF. The reaction rate is first order in [Cp3ZrH] and [C6F6], but the product ratio is unaffected by the concentration of C6F6. Possible mechanisms of these reactions are discussed.

The preparation and properties of the racemic lattice inclusion host 6α,13α-dibromo-5bα,6,12bα,13-tetrahydropentaleno[1,2-b:4,5-bЈ]diquinoline (8) are described. Strong hydrogen bonding interactions are not possible for this versatile host compound. Instead, weaker interactions (such as aryl offset face-face, aryl edge-face, halogen-halogen, halogen-π, and C−H···N synthons) compete against each other to generate the inclusion structure of lowest energy. The guests are contained within molecular pens formed by two hosts enclosing each guest. These host molecules are not directly linked at the corners of the pen, but rather assemble with their neighbours into layers of pens by means of aryl offset faceface interactions. The C−H···N weak hydrogen bond plays a dominant role in these structures by linking adjacent layers edge-edge through two distinct types of double motifs. One

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Retinal degenerations (RD) are a complex heterogeneous group of diseases in which retinal photoreceptors and the supporting retinal pigment epithelial cells die irreversibly, causing visual loss for millions of people. Mutations on more than 150 genes have been discovered for RD and there are many forms that possess complex etiology involving more than one gene and environmental effect. For years many have searched for some common intracellular second messenger for these many forms of cell death which could be targeted for therapy. Ceramide is a novel cellular second messenger which signals for apoptosis. Several lines of evidence suggest an integral role of ceramide in photoreceptor apoptosis and cell death. Understanding their role in the pathogenic pathways of retinal degenerative diseases is important for development of targeted therapeutics.

The preparation of 1,4,8,11-tetrabromo-5b[small alpha],6,12b[small alpha],13-tetrahydropentaleno[1,2-b:4,5-b[prime or minute]]diquinoline is described. This is a further member of the tetrahalo aryl host family, and forms crystalline lattice inclusion compounds with many guests. The X-ray structures of the allyl cyanide, 1,2,3-trichloropropane, chlorobenzene, toluene, benzene-water, methyl chloroform and carbon tetrachloride inclusion compounds are described, and compared with that of the solvent-free apohost. Although several different structural types are produced, the recently reported pi-halogen dimer (PHD) interaction plays an important role in all of these, except for that of pure (where the packing energy is the least favourable of the series).

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Molecular recognition has central role on the development of rational drug design. Binding affinity and interactions are two key components which aid to understand the molecular recognition in drug-receptor complex and crucial for structure-based drug design in medicinal chemistry. Herein, we report the binding affinity and the nonbonding interactions of azelaic acid and related compounds with the receptor DNA polymerase I (2KFN). Quantum mechanical calculation was employed to optimize the modified drugs using B3LYP/6-31G(d,p) level of theory. Charge distribution, dipole moment and thermodynamic properties such as electronic energy, enthalpy and free energy of these optimized drugs are also explored to evaluate how modifications impact the drug properties. Molecular docking calculation was performed to evaluate the binding affinity and nonbonding interactions between designed molecules and the receptor protein. We notice that all modified drugs are thermodynamically more stable and some of them are more chemically reactive than the unmodified drug. Promise in enhancing hydrogen bonds is found in case of fluorine-directed modifications as well as in the addition of trifluoroacetyl group. Fluorine participates in forming fluorine bonds and also stimulates alkyl, pi-alkyl interactions in some drugs. Designed drugs revealed increased binding affinity toward 2KFN. A1, A2 and A3 showed binding affinities of -8.7, -8.6 and -7.9 kcal/mol, respectively against 2KFN compared to the binding affinity -6.7 kcal/mol of the parent drug. Significant interactions observed between the drugs and Thr358 and Asp355 residues of 2KFN. Moreover, designed drugs demonstrated improved pharmacokinetic properties. This study disclosed that 9-octadecenoic acid and drugs containing trifluoroacetyl and trifluoromethyl groups are the best 2KFN inhibitors. Overall, these results can be useful for the design of new potential candidates against DNA polymerase I.