Pi-stacking induced NMR spectrum splitting in enantiomerically enriched Ru(II) complexes: evaluation of enantiomeric excess

Several chiral octahedral complexes of the general formula [Ru(bpy)2 (Lig)][PF6]2 (Lig = a ligand that can participate in pi-stacking interactions such as eilatin, isoeilatin, and tpphz) were synthesized in both the racemic and enantiomerically pure/enriched forms. Nonracemic mixtures of enantiomers of all these complexes exhibit splitting of the 1H NMR spectra (NMR nonequivalence); i.e., each spectrum contains a major and a minor set of peaks. The origin of this phenomenon is attributed to a fast equilibrium between monomers and discrete dimers held together by pi-stacking interactions, and it is observed for a wide range of pi-stacking interaction strengths. The NMR spectrum splitting exhibited by these complexes can be exploited for the evaluation of their enantiomeric excess simply from the integral ratio, without addition of chiral shift reagents.     

Intramolecular dynamics: time evolution of superposition states in the regular and irregular spectrum

The time evolution of wavefunctions ψ(t) is compared in two systems, one with a regular energy spectrum and one with an irregular spectrum. The behavior of P(t) = {|[ψ(O)|ψ(y]}|² is found to be the same in both systems, P(t) decay is insensitive to the coupling between the degrees of freedom.     

Effects of structure on properties of some new aromatic-aliphatic polybenzimidazoles

Polybenzimidazoles were prepared in poly(phosphoric acid) from isophthalic, m- and p-phenylene diacetic, succinic, adipic, suberic, and sebacic acids and 3,3′-diaminobenzidine, 3,3′,4,4′-tetraaminodiphenyl ether and 3,3′,4,4′-tetraaminodiphenylmethane. The thermal, mechanical, and bonding properties were studied. A 3:1 copolymer of isophthalic and m-phenylenediacetic acid with 3,3′-diaminobenzidine showed the best results as far as isothermal oxidation resistance and thermal and processing characteristics.     

Dendritic effect in polymer-supported catalysis of the intramolecular Pauson-Khand reaction

A remarkable increase in catalytic activity and selectivity in the intramolecular Pauson-Khand reaction is observed for Co complexes, immobilised on second- and third-generation dendron-functionalized polystyrene, as compared with their analogues on non-dendronized support.     

Aqueous enantioselective hydrogenation of methyl 2-acetamidoacrylate with Rh-MeDuPHOS occluded in PDMS

A new chiral heterogeneous catalytic system obtained by occlusion of the Rh-MeDuPHOS complex in a polydimethylsiloxane film was tested in the asymmetric hydrogenation of methyl 2-acetamidoacrylate in aqueous medium.     

Simulations of remote mutants of dihydrofolate reductase reveal the nature of a network of residues coupled to hydride transfer

Recent experimental and theoretical studies have proposed that enzymes involve networks of coupled residues throughout the protein that participate in motions accompanying chemical barrier crossing. Here, we have examined portions of a proposed network in dihydrofolate reductase (DHFR) using quantum mechanics/molecular mechanics simulations. The simulations use a hybrid quantum mechanics‐molecular mechanics approach with a recently developed semiempirical AM1‐SRP Hamiltonian that provides accurate results for this reaction. The simulations reproduce experimentally determined catalytic rates for the wild type and distant mutants of E. coli DHFR, underscoring the accuracy of the simulation protocol. Additionally, the simulations provide detailed insight into how residues remote from the active site affect the catalyzed chemistry, through changes in the thermally averaged properties along the reaction coordinate. The mutations do not greatly affect the structure of the transition state near the bond activation, but we observe differences somewhat removed from the point of C? H cleavage that affect the rate. The mutations have global effects on the thermally averaged structure that propagate throughout the enzyme and the current simulations highlight several interactions that appear to be particularly important. © 2014 Wiley Periodicals, Inc.     

Analytic solution for the nondegenerate quantum control problem

We present an analytic solution for the nondegenerate quantum control problem, i.e., the transfer of a deliberate amount of population, 0%-100%, between arbitrary initial Psi(t)> and final Psi'(t)> states, which can be expanded in terms of nondegenerate energy eigenstates k>. The solution constitutes a robust two-photon multicomponent adiabatic passage, via an intermediate eigenstate 0>, which relies on three types of "null states."