Search results for "Pi interaction"
showing 10 items of 23 documents
Genomic determinants of protein folding thermodynamics in prokaryotic organisms.
2004
Here we investigate how thermodynamic properties of orthologous proteins are influenced by the genomic environment in which they evolve. We performed a comparative computational study of 21 protein families in 73 prokaryotic species and obtained the following main results. (i) Protein stability with respect to the unfolded state and with respect to misfolding are anticorrelated. There appears to be a trade-off between these two properties, which cannot be optimized simultaneously. (ii) Folding thermodynamic parameters are strongly correlated with two genomic features, genome size and G+C composition. In particular, the normalized energy gap, an indicator of folding efficiency in statistical…
Charm and hidden charm scalar mesons in the nuclear medium
2009
We study the renormalization of the properties of low-lying charm and hidden charm scalar mesons in a nuclear medium, concretely of the D-s0(2317) and the theoretical hidden charm state X(3700). We find that for the D-s0(2317), with negligible width at zero density, the width becomes about 100 MeV at normal nuclear-matter density, while in the case of the X(3700) the width becomes as large as 200 MeV. We discuss the origin of this new width and trace it to reactions occurring in the nucleus, while offering a guideline for future experiments testing these changes. We also show how those medium modifications will bring valuable information on the nature of the scalar resonances and the mechan…
Anion–π Interactions in Salts with Polyhalide Anions: Trapping of I 4 2−
2010
The directionality of interaction of electron-deficient π systems with spherical anions (e.g,. halides) can be controlled by secondary effects like NH or CH hydrogen bonding. In this study a series of pentafluorophenyl-substituted salts with polyhalide anions is investigated. The compounds are obtained by aerobic oxidation of the corresponding halide upon crystallization. Solid-state structures reveal that in bromide 2, directing NH-anion interactions position the bromide ion in an η(1)-type fashion over but not in the center of the aromatic ring. The same directing forces are effective in corresponding tribromide salt 3. In the crystal, the bromide ion is paneled by four electron-deficient…
Enhanced electron-transfer properties of cofacial porphyrin dimers through pi-pi interactions
2009
pi-pi assisted: Photoinduced electron transfer from cofacial porphyrin dimers to electron acceptors is prominently accelerated, whereas the back electron transfer is decelerated, relative to the corresponding porphyrin monomer (see figure).The radical cation of zinc tetrapentylporphyrin is dimerized with an excess of the neutral counterpart to form the dimer radical cation in which the unpaired electron is delocalized over both porphyrin rings. The dimeric radical cation exhibits an NIR absorption spectrum characteristic of weak pi-bond formation between the porphyrin rings. When cofacial porphyrin dimers, linked by different spacers, are oxidized such pi-bond formation between the porphyri…
Meson-meson interactions in a nonperturbative chiral approach
1999
A non-perturbative method which combines constraints from chiral symmetry breaking and coupled channel unitarity is used to describe the meson-meson interaction up to about 1.2 GeV. The approach uses the O(p^2) and O(p^4) chiral Lagrangians. The seven free parameters of the O(p^4) Lagrangian are fitted to the data. The results are in good agreement with a vast amount of experimental analyses. The amplitudes develop poles in the complex plane corresponding to the f0, a0, rho, K*, phi, sigma and kappa resonances; the latter two, very broad. The total and partial decay widths of the resonances are also well reproduced. Further extensions and applications of this chiral non-perturbative scheme …
Scalar ΛN and ΛΛ interactions within a chiral unitary approach
2008
We study the central part of the ΛN potential by considering the correlated and uncorrelated two-meson exchange besides the ω exchange contribution. The correlated two-meson is evaluated in a chiral unitary approach. We find that a short range repulsion is generated by the correlated two-meson potential which also produces an attraction in the intermediate distance region. The uncorrelated two-meson exchange produces a sizable attraction in all cases which is counterbalanced by ω exchange contribution.
Greatly enhanced intermolecular π-dimer formation of a porphyrin trimer radical trications through multiple π bonds.
2010
A trefoil-like porphyrin trimer linked by triphenylamine (TPA-TPZn(3)) was synthesized. A three-electron oxidation of TPA-TPZn(3) forms a radical trication (TPA-TPZn(3)(3+)), in which each porphyrin ring undergoes a one-electron oxidation. The radical trication TPA-TPZn(3)(3+) spontaneously dimerizes to afford (TPA-TPZn(3))(2)(6+) in CH(2)Cl(2) . The characteristic charge-resonance band due to the charge delocalization over the π system of (TPA-TPZn(3))(2)(6+) was observed in the NIR region. The initial oxidation potential of TPA-TPZn(3) is negatively shifted relative to that of the corresponding monomer porphyrin, which results from the stabilization of the oxidized state of TPA-TPZn(3) as…
X-Ray and NMR Studies on Host-Guest Inclusion Complex Formation between Crown Ethers and Pyridinium Compounds
1998
Aromatic–aromatic, π–π, and cation–π interactions can be exploited in the preparation of molecular complexes between benzene-substituted crown ethers and pyridium cations. These complexes have been studied in the gas phase, in solution, and in the solid state; the structure of one of the complexes is depicted on the right.
Kinetic solvent effects on the reaction of an aromatic ketone pi,pi* triplet with phenol. rate-retarding and rate-accelerating effects of hydrogen-bo…
2007
Quenching of the 2-benzoylthiophene π,π* triplet, 3BT*, by phenol yields the corresponding ketyl and phenoxyl radicals. Reaction rates were measured in 10 solvents having a range of hydrogen-bond acceptor strengths (β2H values). There appear to be two mechanisms: (i) a bimolecular reaction of 3BT* with “free” (i.e., not H-bonded) phenol in which the 3BT* accepts both a proton and an electron from the phenol, the rate decreasing as β2H increases; (ii) a trimolecular reaction of 3BT* with phenol that is H-bonded to a solvent molecule, PhO−H···S, in which the proton goes to the S and the electron to the 3BT*, the rate increasing as β2H increases.
A Computational Study of Two-State Conformational Changes in 16-Electron [CpW(NO)(L)] Complexes (L=PH3, CO, CH2, HCCH, H2CCH2)
1999
International audience; High-spin and low-spin [CpW(NO) (L)] complexes are calculated to be remarkably close in energy. Several critical conformational changes in the singlet compounds are predicted to proceed more readily by spin crossover to the triplet hypersurface. The relationships between spin state, π bonding, ligand orientation, and geometry at W are explored.