Elucidating the Origin of Conformational Energy Differences in Substituted 1,3-Dioxanes: A Combined Theoretical and Experimental Study

13C NMR spectroscopy, ab initio quantum mechanics, and molecular mechanics have been used to investigate the trans-4-(trifluoromethyl)-2,2,6-trimethyl-1,3-dioxane chair/twist-boat equilibrium. The molecular mechanics calculations were based upon the MM3 and AMBER force fields. A 6-31G basis set was used for the ab initio calculations, and MP2 correlation corrections were applied. Both the ab initio and AMBER molecular mechanics calculations are consistent with the (13)C NMR chemical shift differences for the trans-4-(trifluoromethyl)-2,2,6-trimethyl-1,3-dioxane conformers. The predicted chair to twist-boat equilibrium suggested by the MM3 calculations is not consistent with the experimental data. These results support the suggestion by Howard et al. (Howard, A. E.; Cieplak, P.; Kollman, P. A. J. Comput.Chem. 1995, 16, 243-261) on the critical role of electrostatic interactions in determining the chair/twist-boat equilibrium.     

Metallic nonsuperconducting phase and D-wave superconductivity in Zn-substituted La1.85Sr0.15CuO4

Measurements of the resistivity, magnetoresistance, and penetration depth were made on films of La1.85Sr0.15CuO4, with up to 12 at. % of Zn substituted for the Cu. The results show that the quadratic temperature dependence of the inverse square of the penetration depth, indicative of d-wave superconductivity, is not affected by doping. The suppression of superconductivity leads to a metallic nonsuperconducting phase, as expected for a pairing mechanism related to spin fluctuations. The metal-insulator transition occurs in the vicinity of k(F)l approximately 1, and appears to be disorder driven, with the carrier concentration unaffected by doping.     

Percolative Superconductivity in Mg1-xB2

Our results from various transport experiments on Mg1-xB2 indicate a surprising effect associated with the presence of a Mg deficiency in MgB2: the phase separation between Mg-vacancy rich and Mg-vacancy poor phases. The Mg-vacancy poor phase is superconducting, but the insulating nature of the Mg-vacancy rich phase probably originates from the Anderson (disorder-induced) localization of itinerant carriers. Furthermore, electron diffraction measurements indicate that within vacancy-rich regions these defects tend to order with intriguing patterns. This electronic phase separation in Mg1-xB2 shows similar, but also distinct characteristics compared with that observed in La(2)CuO(4+delta).     

Synthesis of higher carbon sugars from dihydroxyacetone and d-arabinose: an organocatalytic approach

The reaction of 2,3:4,5-diacetone-d-arabinose with protected dihydroxyacetone catalyzed by l-proline afforded two diastereoisomeric octoses in a 7:1 ratio in 75% yield. The anti (3S,4S) configuration at the newly created stereogenic centers was assigned to the main isomer on the basis of the X-ray analysis. The same reaction when catalyzed with unnatural d-proline provided the same products in a 1:20 ratio.     

Peptide mimetics as enzyme inhibitors: Use of free energy perturbation calculations to evaluate isosteric replacement for amide bonds in a potent HIV protease inhibitor

Summary We present the application of free energy perturbation theory/molecular dynamics to predict the consequence of replacing each of the seven peptide bonds in the potent HIV protease inhibitor JG365: ACE (acetyl)-Ser-Leu-Asn-HEA (hydroxyethylamine analog of Phe-Pro)-Ile-Val-NME (N-methyl) by ethylene or fluoroethylene isosteres. Replacing two of these bonds may well lead to significantly tighter binding; replacing two others is predicted to significantly diminish the binding affinity. Also, for three of the peptide bonds fluoroethylene replacements could lead to increased binding of free energies of the inhibitors. Our results should be considered as predictive since there are, as yet, no experimental results on such peptide replacements as enzyme inhibitors.     

Exciton binding energy in CdMnTe crystals

We report some results of magnetoabsorption and magnetoreflectivity measurements performed on CdMnTe crystals in magnetic field up to 30 T. The exciton energy at low fields in materials containing magnetic ions is calculated on the basis of the Altarelli-Lipari model and compared with the experimental results. It is shown that spin mixing in degenerate bands strongly affects magnetoabsorption.     

Thermal unfolding of proteins

Thermal unfolding of proteins is compared to folding and mechanical stretching in a simple topology-based dynamical model. We define the unfolding time and demonstrate its low-temperature divergence. Below a characteristic temperature, contacts break at separate time scales and unfolding proceeds approximately in a way reverse to folding. Features in these scenarios agree with experiments and atomic simulations on titin.