Dynamic NMR line-shape analysis demonstrates that the villin headpiece subdomain folds on the microsecond time scale

There is considerable interest in small proteins that fold very rapidly. These proteins have become attractive targets for both theoretical and computational studies. The independently folded 36-residue villin headpiece subdomain has been the subject of a number of such studies and is predicted to fold quickly. We demonstrate using dynamic NMR line-shape analysis that the protein folds on the time scale of 10 mus. Folding rates were directly estimated between 56 and 78 degrees C using resolved protein resonances from three different residues at both 500 and 700 MHz. The rates estimated using different residues and different field strengths agree well with each other. The estimated folding rate lies between 0.5 and 2.0 x 105 s-1 over this temperature range. The folding rate depends only weakly on temperature.     

Multicolor luminescence patterning by photoactivation of semiconductor nanoparticle films

Indiscriminate adsorption of nanoparticles (NPs) significantly complicates the preparation of mesoscale NP patterns considered as enabling technology for many devices and processes. Instead of selected chemical functionalization of the substrate surface prior to the assembly of nanocolloids, the required optical properties - in our case, high quantum yield luminescence - are imparted to the layer-by-layer assembled films by spatially selected photoactivation. The films are made by sequential adsorption of a positively charged polyelectrolyte and a negatively charged CdSe/CdS aqueous dispersion with an initial quantum yield of 0.5-2%. The photoactivation process takes place in the presence of oxygen and may be accompanied by photoetching. A 50-500-fold increase in the luminescence intensity of CdSe/CdS citrate-stabilized particles (quantum yield 25-45%) after visible light illumination provides excellent pattern contrast. Micron scale luminescence patterns were produced from NPs of various CdSe core diameters with red, yellow, and green emission. It was also demonstrated that different emission colors such as orange and green can be combined in one image by taking advantage of spatially selective photoetching. The presented optical patterning technique significantly simplifies the preparation of luminescence patterns as compared to conventional methods. The high signal-to-noise ratio associated with it is essential for optical devices, information processing, and biophotonics. The most immediate use of this approach is expected in cryptography and cell monitoring.     

Asymmetric hydrogenation of itaconic acid and enol acetate derivatives with the Rh-TangPhos catalyst

[reaction: see text] The Rh-TangPhos catalyst has been used for asymmetric hydrogenation of itaconic acid and enol acetate derivatives. A variety of chiral 2-substituted succinic acids and chiral acetates have been obtained in excellent ee values (up to 99% ee).     

Oscillations of nonlinear partial difference systems

This paper studies the following two-dimensional nonlinear partial difference systems

     

Symmetric and Rees algebras of Koszul cycles and their Gröbner bases

In this paper we study the symmetric algebra S(E _i ) and Rees algebra R(E _i ) of the modules E _i of i-cycles of the Koszul complex associated with the sequence of indeterminates of a polynomial ring . For i=2 and i=n–2 we show that is a d-sequence on S(E _i ) and R(E _i ) and we determine Gröbner bases and Sagbi bases related to these algebras. Mathematics Subject Classification (2000):13A30, 13D02, 13H10, 13P10The second author is grateful to the National Natural Science Foundation of China for support.Part of this work was made while the third author was visiting the Fachbereich Mathematik und Informatik der Universität Essen, to which he would like to thank for its hospitality.     

Uniqueness of positive radial solutions for Δu−u+u=0 on an annulus

We prove uniqueness of positive radial solutions to the semilinear elliptic equation , subject to the Dirichlet boundary condition on an annulus in . As a by-product, our argument also provides a much simpler, if not the simplest, new proof for the uniqueness of positive solutions to the same problem in a finite ball or in the whole space .     

Vortex sound generation due to a flow impedance discontinuity on a flat surface

The sound generated by the unsteady motion of a vortex filament moving over a flat boundary with a sharp flow impedance discontinuity is studied theoretically. Theoretical results show that the vortex filament undergoes significant accelerating or decelerating motions and radiates sound at the instant when it moves across the plane of impedance discontinuity. The accelerations and decelerations of the vortex filament are shown to be the major mechanisms of sound generation. The sound so produced has a large low-frequency content such that the change in the flow impedance affects only the sound generation process but not the subsequent sound propagation to the far field.     

Asymptotic Normalization Constants in Nuclear Astrophysics

The indirect method of determining astrophysical nuclear reaction rates is discussed. The overall normalization of the astrophysical S-factor for such reactions may be determined from one quantity, the asymptotic normalization coefficient of the overlap function of the bound state wave functions for the initial and final channels. These coefficients can be found also from peripheral transfer reactions whose amplitudes are determined by the same overlap function as the amplitudes of the corresponding astrophysical radiative capture processes. The experimental test of this approach and the last results of S₁₇ measurements are presented.     

Anomalous Vibrational Dependence of the Rotational and Hyperfine Parameters in the B(4)Pi-X(4)Sigma(-) Transition of NbO

The laser excitation spectrum of jet-cooled NbO in the region 16 000-18 000 cm(-1) has been recorded at high resolution, giving rotational and hyperfine constants for the levels v=0-3 of the B(4)Pi state and v=1 of the X(4)Sigma(-) state; zero gaps have also been measured at low resolution for some weaker bands involving higher vibrational levels. Taken together with the laser data for the B-X (0,0) band from Adam et al. (J. Chem. Phys. 94, 6240-6262 (1994)) and the Fourier transform emission data for the doublet manifold from Launila et al. (J. Mol. Spectrosc. 186, 131-143 (1997)), the new data give a very complete picture of the vibrational energy level pattern in this region. Strong irregularities in the vibrational dependences of the B(4)Pi rotational and hyperfine constants can be interpreted in terms of spin-orbit interaction between the B(4)Pi state and the f(2)Pi, e(2)Phi, and d(2)Delta states. The interaction is strong enough that all three doublet states can be seen in absorption from the X(4)Sigma(-) ground state, adding to the complexity of the spectrum. The hitherto unknown sigmadeltasigma* (4)Delta state is estimated to lie near 17 500 cm(-1), from the change of sign in the spin-rotation parameter gamma of the B(4)Pi state between v=2 and 3. Copyright 2001 Academic Press.     

Recording intramolecular mechanics during the manipulation of a large molecule

The technique of single atom manipulation by means of the scanning tunneling microscope (STM) applies to the controlled displacement of large molecules. By a combined experimental and theoretical work, we show that in a constant height mode of manipulation the STM current intensity carries detailed information on the internal mechanics of the molecule when guided by the STM tip. Controlling and time following the intramolecular behavior of a large molecule on a surface is the first step towards the design of molecular tunnel-wired nanorobots.