Measurement of five dipolar couplings from a single 3D NMR multiplet applied to the study of RNA dynamics

A new three-dimensional NMR experiment is described that yields five scalar or dipolar couplings from a single cross-peak between three spins. The method is based on the E.COSY principle and is demonstrated for the H1'-C1'-C2' fragment of ribose sugars in a uniformly 13C-enriched 24-nucleotide RNA stem-loop structure, for which a complete set of couplings was obtained for all nonmodified nucleotides. The values of the isotropic J couplings and the 13C1' and 13C2' chemical shifts define the sugar pucker. Once the sugar pucker is known, the five dipolar couplings between C1'-H1', C2'-H2', H1'-H2', C1'-H2', and C2'-H1', together with C1'-C2', C3'-H3', and C4'-H4' available from standard experiments, can be used to derive the five unknowns that define the local alignment tensor, thereby simultaneously providing information on relative orientation and dynamics of the ribose units. Data indicate rather uniform alignment for all stem nucleotides in the 24-nt stem-loop structure, with only a modest reduction in order for the terminal basepair, but significantly increased mobility in part of the loop region. The method is applicable to proteins, nucleic acids, and carbohydrates, provided 13C enrichment is available.     

Anomalous thermopower in the metalliclike phase of a 2D hole system

We report very low temperature ( T) thermopower and resistivity ( rho) measurements on variable-density, two-dimensional hole systems confined to GaAs quantum wells. As the hole density is lowered from 1.49x10(11) cm(-2) to 0.14x10(11) cm(-2), the system crosses from an insulating ( drho / dT less, similar0) to a metallic regime ( drho / dT>0) and finally displays insulating behavior ( drho / dT<0). Diffusion thermopower shows a striking sign reversal in a narrow range of density in the metallic regime, suggesting a qualitative change in the conduction or the scattering mechanism.     

A monopole mass filter with a hyperbolic V-shaped electrode

In this article we compare the classical monopole mass filter of von Zahn and the monopole mass filter with a hyperbolic V-shaped electrode. The experimental results and those of computer simulation for both mass spectrometers are presented. We show that the replacement of a conventional 90 degrees V-shaped electrode by an electrode with a hyperbolic profile substantially improves the peak shape of any given mass, and increases the mass resolution by a factor of 3-4 and the abundance sensitivity by a factor of 100. The potential of high analytical performance combined with electroforming techniques for electrode manufacture indicate future practical uses of such instruments. Copyright 1999 John Wiley & Sons, Ltd.     

Base pairing within the psi32,psi39-modified anticodon arm of Escherichia coli tRNA(Phe)

The base-base hydrogen bond interactions of the psi32,psi39-modified anticodon arm of Escherichia coli tRNAPhe have been investigated using heteronuclear NMR spectroscopy. psi32 and psi39 were enzymatically introduced into a [13C,15N]-isotopically enriched RNA sequence corresponding to the tRNAPhe anticodon arm. Both the psi32-A38 and A31-psi39 nucleotide pairs form Watson-Crick base pairing schemes and the anticodon nucleotides adopt a triloop conformation. Similar effects were observed previously with D2-isopentenyl modification of the A37 N6 that also is native to the tRNAPhe anticodon arm. These results demonstrate that the individual modifications are not sufficient to produce the 32-38 bifurcated hydrogen bond or the U-turn motifs that are observed in crystal structures of tRNAs and tRNA-protein complexes. Thus the formation of these conserved structural features in solution likely require the synergistic interaction of multiple modifications.     

Shape resonances in slow electron scattering by aromatic molecules. I. Anthraquinone derivatives

A series of anthraquinone (C(14)O(2)H(8)) derivatives has been studied by means of electron capture negative ion mass spectrometry (ECNI-MS), photoelectron spectroscopy (PES), and AM1 quantum chemical calculations. Mean lifetimes of molecular negative ions M(-.) (MNI) have been measured. The mechanism of long-lived MNI formation in the epithermal energy region of incident electrons has been investigated. A simple model of a molecule (a spherical potential well with the repulsive centrifugal term) has been applied for the analysis of the energy dependence of cross sections at the first stage of the electron capture process. It has been shown that a temporary resonance of MNI at the energy approximately 0.5 eV corresponds to a shape resonance with lifetime 1-2.10(-13) s in the f-partial wave (l = 3) of the incident electron. The next resonant state of MNI at the energy approximately 1.7 eV has been associated with the electron excited Feshbach resonance (whose parent state is a triplet npi* transition). In all cases the initial electron state of the MNI relaxes into the ground state by means of a radiationless transition, and the final state of the MNI is a nuclear excited resonance with a lifetime measurable on the mass spectrometry timescale. Copyright 1999 John Wiley & Sons, Ltd.     

1H-1H dipolar couplings provide a unique probe of RNA backbone structure

A NMR method is described that permits simultaneous measurement of the geminal 2JH1H2 + 2DH1H2 splitting and the sum of the 1JCH1 + 1DCH1 + 1JCH2 + 1DCH2 couplings for methylene groups, where 2DH1H2 and 1DCH are residual dipolar couplings, occurring when molecules are weakly oriented relative to the magnetic field. By suppressing either the upfield or downfield half of the 1H-1H geminal doublet, the experiment yields improved resolution relative to regular two-dimensional 1H-13C correlation spectra, making it applicable to systems of considerable complexity. The method is demonstrated for measurement of all 2DH5'H5' couplings in a 24-nucleotide 13C-enriched RNA stem loop structure, weakly aligned in liquid crystalline Pf1. The method is equally applicable to methylene groups in 13C-labeled proteins and to natural abundance samples of smaller molecules.     

Domain decomposition algorithms for indefinite weakly singular integral equations: the h and p versions

We extend the approach of Cai and Widlund (Domain decompositionalgorithms for indefinite elliptic problems, SIAM J. Sci. Stat.Comput. 13 (1992), 243-258), which was designed for finite elementdiscretizations, to boundary element discretizations of indefiniteweakly singular integral equations. Both the h and p versionsof the Galerkin approximation are considered. We prove thatthe additive Schwarz method suggested by Cai and Widlund canbe used for this equation as an efficient preconditioner forGMRES, an iterative method of conjugate gradient type. For bothversions, the rates of convergence of this iterative methodare shown to approach 1 only logarithmically as the degreesof freedom tend to infinity.     

Z-restored spin-echo 13C 1D spectrum of straight baseline free of hump, dip and roll

A pulse sequence of z-restored spin echo, -pi-beta-tau-pi-tau-, employing a pi pulse in the middle of the delay (2tau) to form a spin echo and the two pi pulses together to restore the residual longitudinal magnetization back to + z direction, is described. (13)C spectra of organic compounds provide a wealth of structural information; however, (13)C 1D spectra acquired using reverse geometry probes can have significant baseline humps or rolls because of pulse ring-down within the coil. The baseline distortions are especially apparent in spectra acquired using cryogenically enhanced probes. The baseline problem may be alleviated by extending the delay between the last pulse and the starting point of acquisition. However, uses of long delay times introduce large negative first-order phase corrections which themselves produce baseline roll. The prescribed experiment can be used to completely remove the hump, roll or dip in the baseline of the (13)C spectrum and at the same time obtain sensitivity similar to the experiment of a single beta pulse. We believe that this experiment will be of general applications in acquiring high-quality (13)C NMR data with reverse geometry probes and spectral interpretation.     

Anisotropic magnetoresistance of two-dimensional holes in GaAs

Experiments on high-quality GaAs (311)A two-dimensional holes at low temperatures reveal a remarkable dependence of the magnetoresistance, measured with an in-plane magnetic field ( B), on the direction of B relative to both the crystal axes and the current direction. The magnetoresistance features, and in particular the value of B above which the resistivity exhibits an insulating behavior, depend on the orientation of B. To explain the data, the anisotropic band structure of the holes and a repopulation of the spin subbands in the presence of B, as well as the coupling of the orbital motion to B, need to be taken into account.     

Complexation of Pb2+ by Macrocyclic Benzo- and Pyridinophanes

Eleven macrocyclic compounds containing benzene and/or pyridine moieties are synthesized and their application for lead(II) cation binding processes is investigated using cyclic voltammetry and UV–VIS techniques.