Intramolecular isotope effects were determined for the N-demethylation of N-methyl-N-trideuteriomethylaniline catalyzed by two isozymes of cytochrome P-450 and several peroxidases in order to differentiate between deprotonation and hydrogen atom abstraction steps. Lactoperoxidase, hemoglobin, myoglobin, and two isozymes of horseradish peroxidase catalyzed the hydroperoxide-dependent N-demethyla...

Interlocked molecular machines like [2]rotaxanes are intriguing aesthetic molecules. The control of the localization of the macrocycle, which surrounds a molecular axle, along the thread leads to translational isomers of very different properties. Although many moieties have been used as sites of interactions for crown ethers, the very straightforwardly obtained amide motif has more rarely been...

Oxidation of DNA represents a major pathway of genetic mutation. We have applied infrared spectroscopy in 77 K glass with supporting density functional theory (DFT) calculations (EDF1/6-31+G*) to provide an IR signature of the guanine radical cation G(+*), formed as a result of 193 nm photoionization of DNA. Deprotonation of this species to produce the neutral radical G(-H)(*) does not occur in...

The efficiency and stereoselectivity of the conjugate addition of lithium (Z)- or (E)-beta-amino ester enolates, generated by lithium amide conjugate addition to an alpha,beta-unsaturated ester or deprotonation of a beta-amino ester, respectively, to a range of alpha,beta-unsaturated acceptors has been investigated. Deprotonation of a beta-amino ester with LDA, followed by conjugate addition to...

The origin of the stereoselectivity in the lithiation/trapping of 2-alkylideneaziridines bearing a chiral group as the nitrogen substituent was investigated. Optimal reaction conditions were discovered by in situ FT-IR monitoring. In addition, it has been found that the solvent and the alkene substitution pattern are important factors able to impart a switch in stereoselectivity. While lithiati...

The binding dynamics of the 2-aminoanthracenium cation (AH(+)) and 2-aminoanthracene (A) with cucurbit[7]uril (CB[7]) was studied using stopped-flow experiments. The kinetics was followed by measuring the fluorescence changes over time for AH(+) and A, which emit at different wavelengths. The studies at various pH values showed different mechanisms for the formation of the AH(+)@CB[7] complex, ...

Deprotonation of benzoxazole, benzothiazole, benzo[b]thiophene, benzo[b]furan, N-Boc-protected indole and pyrrole, and N-phenylpyrazole using an in situ mixture of ZnCl(2).TMEDA (0.5 equiv) and lithium 2,2,6,6-tetramethylpiperidide (1.5 equiv) in THF at room temperature is described. The reaction was evidenced by trapping with iodine, regioselectively giving the expected functionalized derivati...