Probing molecular free energy landscapes by periodic loading

Single molecule pulling experiments provide information about interactions in biomolecules that cannot be obtained by any other method. However, the reconstruction of the molecule's free energy profile from the experimental data is still a challenge, in particular, for the unstable barrier regions. We propose a new method for obtaining the full profile by introducing a periodic ramp and using Jarzynski's relation for obtaining equilibrium quantities from nonequilibrium data. Our simulated experiments show that this method delivers significant more accurate data than previous methods, under the constraint of equal experimental effort.     

Use of an ionic liquid in a two-phase system to improve an alcohol dehydrogenase catalysed reduction

Due to favourable partition coefficients the highly enantioselective reduction of 2-octanone, catalysed by an alcohol dehydrogenase from Lactobacillus brevis, is faster in a biphasic system containing buffer and the ionic liquid [BMIM][(CF(3)SO(2))(2)N] compared to the reduction in a biphasic system containing buffer and methyl tert-butyl ether.     

Sub-Doppler fluorescence on the atomic <Emphasis Type="Italic">D</Emphasis><Subscript>2</Subscript> line of a submicron rubidium-vapor layer

An extremely thin cell (ETC) with the thickness of a Rb atomic vapor layer in the range of 100–300 nm was fabricated. It is demonstrated that a simple laser-diode technique with a single resonant light beam is sufficient to observe separately all of the atomic hyperfine transitions of the D ₂ line of Rb (780 nm) and also allows us to measure the relative transition probabilities of the hyperfine transitions. The onset of collisional self-broadening of the hyperfine transitions as the number density of atoms increases was studied. The detrimental role of the atoms with slow longitudinal velocity in the sub-Doppler response of the Rb ETC is demonstrated by studies in which the cell is tilted from normal incidence of the laser beam. It is also shown that using an ETC allows us to resolve in a moderate external magnetic field the Zeeman splitting of the hyperfine transitions of the ⁸⁷Rb D ₁ transition F _g=1F _e=1,2. Received: 19 February 2003 / Revised version: 4 April 2003 / Published online: 2 June 2003 RID="*" ID="*"Corresponding author. Fax: +374/32-31172, E-mail: david@ipr.sci.am     

A supramolecular cup-and-ball C60-porphyrin conjugate system

In addition to the ammonium-crown ether recognition, pi-stacking interactions between the C60 sphere and the porphyrin moiety have been evidenced in a supramolecular complex obtained from a porphyrin-crown ether conjugate and a fullerene derivative bearing an ammonium unit.     

Reversal of diastereoselectivities in intra- and intermolecular reactions of 2-adamantanylidenes primarily caused by electron-donating and electron- withdrawing substituents on C5

[reaction: see text] A reversal of diastereoselectivity was observed for novel 5-(trimethylsilyl)adamantan-2-ylidene (1c) with regard to 5-hydroxyadamantan-2-ylidene (1a). Ostensibly in intermolecular reactions, 5-substituted 2-adamantanylidenes (1) are sterically unbiased. However, inductive effects originating from the pendant group bend the divalent carbon bridge of 1 either toward (ERG's, e.g., -Si(CH(3))(3)) or away from (EWG's, e.g., -OH) the gamma-position. Hence, the more exposed side is more susceptible to intermolecular reaction and the other side concomitantly undergoes intramolecular 1,3-CH insertions more readily.     

The Centroaffine Volume of Generalized Geodesic Balls Under Inversion at the Sphere

On an analytic Riemannian manifold (M,g), several authors have studied the Taylor expansion for the volume of geodesic balls under the exponential mapping. In the foregoing paper [1] we studied a more general structure (M,D,g), where D is a torsion-free and Ricci-symmetric connection. We calculated the Taylor expansion up to order (n+4) for the volume of what we called a generalized geodesic ball under the exponential mapping in case that all metric notions are Riemannian, while the exponential mapping is induced from the connection D. For the structure $(M,D,{\cal G})$ the coefficients of the Taylor expansion are much more complicated than in the Riemannian case. It is one of the main objectives of the present paper to study centroaffine hypersurfaces in Euclidean space, their geometric invariants which appear in the very complicated coefficient of order (n+4), and their behaviour under polarization (inversion at the unit sphere). Our results complement applications in the foregoing paper [1], where mainly the coefficients up to order (n+2) and geometric consequences have been studied.     

Inhibition of decoherence due to decay in a continuum

We propose a scheme for slowing down decay into a continuum. We make use of a sequence of ultrashort 2pi pulses applied on an auxiliary transition of the system so that there is a destructive interference between the two transition amplitudes--one before the application of the pulse and the other after the application of the pulse. We give explicit results for a structured continuum. Our scheme can also inhibit unwanted transitions.