The o-palladated, chloro-bridged dimers [Pd{2-phenylpyridine(-H)}-μ-Cl]2 and [Pd{N,N-dimethylbenzylamine(-H)}-μ-Cl]2 react with cyanuric acid in the presence of base to afford closed, chiral cage-molecules in which 12 organo-Pd(II) centers, located in pairs at the vertices of an octahedron, are linked by four tetrahedrally arranged cyanurato(3-) ligands. Incomplete (Pd10) cages, having structur...

The direct oxidative coupling reaction has been an attractive tool for environmentally benign chemistry. Reported herein is that the hypervalent iodine catalyzed oxidative metal-free cross-coupling reaction of phenols can be achieved using Oxone as a terminal oxidant in 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP). This method features a high efficiency and regioselectivity, as well as functional-g...

The intramolecular alpha-arylation of aldehydes has been accomplished using singly occupied molecular orbital (SOMO) catalysis. Selective oxidation of chiral enamines (formed by the condensation of an aldehyde and a secondary amine catalyst) leads to the formation of a 3pi-electron radical species. These chiral SOMO-activated radical cations undergo enantioselective reaction with an array of pe...

Solubili t ies of silver a n d copper in the i r mol ten salt mix tu res AgCl^Bri j ; a n d C u C U B r i ^ were measured as a f unc t i on of T a n d x. F r o m the t e m p e r a t u r e dependence of t h e solubil i t ies, t h e en tha lp ies a n d ent ropies of dissolution could be ob ta ined as a func t ion of x. Unexpec t ed ly these func t ions v a r y nonmonotonous ly wi th x. The entha ...

Explant cultures of human tissues metabolized chemical carcinogens into the ultimate carcinogenic form as measured by binding to cellular DNA. A wide inter-individual variation in the binding level of many chemical carcinogens to target cell DNA was observed, whereas lesser inter-individual variation was observed in primary epithelial cell cultures derived from the explants. The binding levels ...

The intramolecular alpha-arylation of aldehydes via organo-SOMO catalysis was investigated using density functional theory (B3LYP and M06-2X functionals). The geometries, spin densities, Mulliken charges, and molecular orbitals of the reacting enamine radical cations were analyzed, and the nature of the resulting cyclized radical cation intermediates was characterized. In agreement with experim...

The in vitro accuracy of DNA replication has been investigated through the measurement of the frequency with which noncomplementary nucleotides were incorporated during polynucleotide replication. The effect of beta-propiolactone treatment of deoxynucleotide templates, ribopolynucleotide templates, and the DNA polymerase from avian myeloblastosis virus was determined. Treatment of the deoxynucl...

Antimony(V) and bismuth(V) complexes of lapachol have been synthesized by the reaction of Ph₃SbCl₂ or Ph₃BiCl₂ with lapachol (Lp) and characterized by several physicochemical techniques such as IR, and NMR spectroscopy and X-ray crystallography. The compounds contain six-coordinated antimony and bismuth atoms. The antimony(V) complex is a monomeric derivative, (Lp)(Ph₃Sb)OH, and the bismuth(V) ...

Protein kinase C iota (PKCiota) has been implicated in Ras signaling, however, a role for PKCiota in oncogenic Ras-mediated transformation has not been established. Here, we show that PKCiota is a critical downstream effector of oncogenic Ras in the colonic epithelium. Transgenic mice expressing constitutively active PKCiota in the colon are highly susceptible to carcinogen-induced colon carcin...

Activation of the procarcinogens benzo(a)pyrene and 2-fluorenamine by liver homogenates (S9) prepared from senescent male CFN rats and C57BL/6J mice resulted in an enhanced production of mutagenic metabolites when compared to young rodents, as indicated by an enhancement of the induced re version frequency in a Salmonella typhimurium bioassay. Sim ilar results were observed when carcinogen acti...