Synthesis of heavily substituted 1,2-amino alcohols in enantiomerically pure form

[reaction: see text] A simple and convenient methodology for the preparation of optically pure 2-amino-2-aryl-1,1-diphenylethanols is presented. Allylamine was found to produce the ring-opening of triaryloxiranes in a regioselective and a stereospecific fashion. Removal of the allyl protecting group provided the free 1,2-amino alcohols in enantiomerically pure form.     

General approach to glycosidase inhibitors. Enantioselective synthesis of deoxymannojirimycin and swainsonine

[reaction: see text] Deoxymannojirimycin (2) and swainsonine (4) have been synthesized from each enantiomer of the same bicyclic carbamate precursor 7. The key intermediate was prepared by a simple and efficient three-step synthesis involving RCM of the diene 8, which in turn is easily accessible in any configuration from enantiomerically enriched 2,3-epoxy-4-penten-1-ol 9.     

Atomic force microscopy study of beta-substituted-T7 oligothiophene films on mica: mechanical properties and humidity-dependent phases

The structural and mechanical properties of Langmuir-Blodgett monolayer and multilayer films of 3",4"-didecyl-5,2'; 5',2"; 5",2'; 5',2"; 5",2''; 5'',2"-heptathiophene-4'-acetic acid on mica have been studied by atomic force microscopy (AFM) as a function of humidity, temperature, and applied force. The molecules orient with the carboxylic acid group pointing toward the mica surface and expose the alkyl side chains to the air interface. As the load applied by the AFM tip increases, the film is compressed easily from an initial height of 2 to 1.2 nm. After compression the films can support much higher loads without loss of height. The state of aggregation of the molecules was found to be sensitive to the environmental humidity, which induced reversible changes. Annealing the samples with monolayer or multilayer films resulted in irreversible changes when the temperature exceeded approximately 100 degrees C.     

Electronic structure of the K3Bi2 metallic phase

The electronic structure of K3Bi2 is discussed on the basis of first-principles DFT calculations. It is shown that the dimers are formally (Bi2)3-, even though this might seem to be in contradiction with the metallic character of the salt. The apparent puzzle is explained by the sizable participation of the K levels in the bonding.     

Gas-phase structures, rotational barriers, and conformational properties of hydroxyl and mercapto derivatives of cyclohexa-2,5-dienone and cyclohexa-2,5-dienthione

The rotational barriers and conformational properties of the hydroxyl and mercapto groups attached to the alpha and beta positions of cyclohexa-2,5-dione and cyclohexa-2,5-dienthione have been studied at the B3LYP/ 6-311++G(d,p) level of theory. The results show that the conformational preferences of these studied systems are the result of a subtle interplay between different competing effects (conjugation, hyperconjugation, and steric repulsions). The applicability of the density functional theory reactivity indices and the maximum hardness principle for the present systems has been analyzed.     

Theoretical study on the excited-state intramolecular proton transfer in the aromatic schiff base salicylidene methylamine: an electronic structure and quantum dynamical approach

The proton-transfer dynamics in the aromatic Schiff base salicylidene methylamine has been theoretically analyzed in the ground and first singlet (pi,pi) excited electronic states by density functional theory calculations and quantum wave-packet dynamics. The potential energies obtained through electronic calculations that use the time-dependent density functional theory formalism, which predict a barrierless excited-state intramolecular proton transfer, are fitted to a reduced three-dimensional potential energy surface. The time evolution in this surface is solved by means of the multiconfiguration time-dependent Hartree algorithm applied to solve the time-dependent Schr?dinger equation. It is shown that the excited-state proton transfer occurs within 11 fs for hydrogen and 25 fs for deuterium, so that a large kinetic isotope effect is predicted. These results are compared to those of the only previous theoretical work published on this system [Zgierski, M. Z.; Grabowska, A. J. Chem. Phys. 2000, 113, 7845], reporting a configuration interaction singles barrier of 1.6 kcal mol(-1) and time reactions of 30 and 115 fs for the hydrogen and deuterium transfers, respectively, evaluated with the semiclassical instanton approach.     

Sample entropy of ECG time series of fearful flyers: preliminary results

Research within the framework of the nonlinear dynamical systems (NDS) in the field of anxiety disorders has shown that greater irregularity/complexity appears in the output from healthy systems. In this study we measured the Heart rate variability (HRV) and the sample sntropy (SampEn) of the ECG mV time series of fearful flyers (N = 15) and a matched control group (N = 15) when confronted with three combinations of feared stimuli (pictures, sounds, and pictures with sounds) as well as relaxing stimuli (pictures and sounds). Fearful flyers had lower SampEn than controls in all conditions, including baseline. Non-phobics showed significant entropy decreases from baseline in two out of three exposure conditions. No differences on HRV were found between groups, and HRV was not sensitive to condition changes. The main finding of the study is that the SampEn calculated on very short ECG mV recordings (10 to 60 seconds, easy to obtain in clinical settings) may be a useful diagnostic measure since it can distinguish fearful from non-fearful flyers.     

Gaussian mean curvature flow

In the Euclidean Space \mathbb Rⁿ⁺¹{\mathbb {R}^{n+1}} with a density e^{e\frac12 n m2 |x|2}, (e = ±1){e^{\varepsilon \frac12 n \mu^2 |x|^2},} {(\varepsilon =\pm1}), we consider the flow of a hypersurface driven by its mean curvature associated to this density. We give a detailed account of the evolution of a convex hypersurface under this flow. In particular, when e = -1{ \varepsilon=-1} (Gaussian density), the hypersurface can expand to infinity or contract to a convex hypersurface (not necessarily a sphere) depending on the relation between the bound of its principal curvatures and μ.