Efficient Aryl Migration from an Aryl Ether to a Carboxylic Acid Group To Form an Ester by Visible-Light Photoredox Catalysis.

We have developed a highly efficient aryl migration from an aryl ether to a carboxylic acid group through retro-Smiles rearrangement by visible-light photoredox catalysis at ambient temperature. Transition metals and a stoichiometric oxidant and base are avoided in the transformation. Inspired by the high efficiency of this transformation and the fundamental importance of C-O bond cleavage, we developed a novel approach to the C-O cleavage of a biaryl ether to form two phenolic compounds, as demonstrated by a one-pot, two-step gram-scale reaction under mild conditions. The aryl migration exhibits broad scope and can be applied to the synthesis of pharmaceutical compounds, such as guacetisal. Primary mechanistic studies indicate that the catalytic cycle occurs by a reductive quenching pathway.

2-(1-(2-Benzhydrylnaphthylimino)ethyl)pyridylnickel halides: synthesis, characterization, and ethylene polymerization behavior.

A series of 2-(1-(2-benzhydrylnaphthylimino)ethyl)pyridine derivatives (L1-L3) was synthesized and fully characterized. The organic compounds acted as bi-dentate ligands on reacting with nickel halides to afford two kinds of nickel complexes, either mononuclear bis-ligated L2NiBr2 (Ni1-Ni3) or chloro-bridged dinuclear L2Ni2Cl4 (Ni4-Ni6) complexes. The nickel complexes were fully characterized, and the single crystal X-ray diffraction revealed for Ni2, a distorted square pyramidal geometry at nickel comprising four nitrogens of two ligands and one bromide; whereas for Ni4, a centrosymmetric dimer possessing a distorted octahedral geometry at nickel was formed by two nitrogens of one ligand, two bridging chlorides and one terminal chloride along with oxygen from methanol (solvent). When activated with diethylaluminium chloride (Et2AlCl), all nickel complexes performed with high activities (up to 1.22 × 10(7) g (PE) mol(-1) (Ni) h(-1)) towards ethylene polymerization; the obtained polyethylene possessed high branching, low molecular weight and narrow polydispersity, suggestive of a single-site active species. The effect of the polymerization parameters, including the nature of the ligands/halides on the catalytic performance is discussed.

Transcription-inhibition and antitumor activities of N-alkylated tetraazacyclododecanes.

A series of alkyl-substituted tetraazacyclododecane congeners were synthesized, and their antitumor activities towards human HeLa cells as well as their effect on the in vitro transcription with T7 RNA polymerase were investigated. A structure-activity-relationship (SAR) study identified the most-active congeners as those with medium alkyl-chain lengths. Three compounds, 5-7, were found to exhibit significant biological activities, with IC50 values towards HeLa cells in the low-micromolar range.

Synthesis and biological studies of N-alkylated cyclic diamines.

Several alkyl-substituted mesocyclic diamines were synthesized, and their interaction with DNA were studied by melting-temperature measurements and the ethidium bromide (EB)-fluorescence competitive method. The supercoiled DNA hydrolytic cleavage by 1,4-dioctyl-1,4-diazepan-6-ol (4) was supported by the evidence from free-radical quenching and T4-ligase ligation. Preliminary pharmacological tests showed that only 1,4-dioctyl-1,4-diazepan-6-ol (4) had antitumor activity against HeLa cell lines in vitro.

[Regulation of nitric oxide-cyclic guanosine monophosphate pathway on cochlear sensitivity].

OBJECTIVE: To investigate the effect of nitric oxide (NO)-cyclic guanosine monophosphate (cGMP) pathway on cochlear sensitivity. Methods Ten groups of guinea pigs were treated with the following solutions by whole cochlear perfusion for 2 hours: (1) Artificial perilymph; (2) L-arginine; 93) Ca(2+)-ATPase inhibitor; (4) Ca(2+)-ATPase inhibitor + L-arginine; (5) Ca(2+)-ATPase inhibitor + cGMP; (6) Ca 2+ ATPase inhibitor + L-arginine + Non-selective NOS inhibitor; (7) eNOS inhibitor; (8) eNOS inhibitor + Ca(2+)-ATPase inhibitor; (9) eNOS inhibitor + Ca(2+)-ATPase inhibitor + L-arginine; (10) eNOS inhibitor + Ca(2+)-ATPase inhibitor + L-arginine + nNOS inhibitor. The compound action potential (CAP) and cochlea microphonics (CM) were measured to assess the changes of cochlear sensitivity. After the perfusion, the cochleae were harvested and prepared for transmission electron microscopy. RESULTS: The average threshold shift of CAP after perfusion Ca(2+)-ATPase inhibitor was 28.5 dB, and it was improved in group 4 with 9 dB by L-arginine, similar with group 5. The threshold shift of CAP in group 8 was 42.5 dB, and it decreased in group 9 by L-arginine, on this foundation nNOS inhibitor was added, increased threshold shift of CAP was 6.5 dB, similar with group 8. The results indicated that L-arginine could rivalry the role of Ca(2+)-ATPase inhibitor through the path of NO-cGMP. Transmission electron microscopy showed that Ca(2+)-ATPase inhibitor + L-arginine combined administration resulted in less vacuolization in out hair cell than that treated with Ca(2+)-ATPase inhibitor only. CONCLUSIONS: The NO-cGMP pathway could regulate cochlear sensitivity; L-arginine may improve the function of Corti's organ via nNOS, and they indicate an important role of supporting cells in the modulation of cochlear function.