Molecular mechanics force-field development for amino acid zwitterions

Understanding the conformational flexibility of amino acid zwitterions (ZWs) and their associated conformational energies is crucial for predicting their interactions in biological systems. Gas-phase ab initio calculations of ZWs are intractable. Molecular mechanics (MM), on the other hand, is able to handle large systems but lacks the necessary force field parameters to model ZWs. To develop force field parameters that are able to correctly model ZW geometries and energetics we used a novel combinatorial approach: amino acid ZWs were broken down structurally into key functional components, which were parameterized separately. M?ller-Plesset second-order perturbation calculations on small carboxylates, on the glycine cation, and on novel hydrogen bonded systems, coupled with available experimental data, were used to generate MM3(2000) ZW parameters (Allinger N. L.; Yuh, Y. H.; Lii, J.-H. J Am Chem Soc 1989, 111, 8551). The MM3 results from this combinatorial approach gave geometries that are in good agreement with neutron diffraction experiments, plus their frequencies and energies appear to be reasonably modeled. Current limitations and future development of MM force fields are discussed briefly.     

First observation of structural changes around the Tc in TlBaCaCuO4.5+y superconductor studied by57Fe Mössbauer spectroscopy

⁵⁷Fe Mössbauer spectroscopy was used to study⁵⁷Fe doped high T_c TlBaCaCuO_4.5+y superconductor between 70 and 295 K. Significant anomalous changes in the shape of the Mössbauer spectrum were observed around the T_c /105–120 K/. This experimental fact could be reproduced. Our finding can be associated with structural changes taking place around the T_c in TlBaCaCuO_4.5+y superconductor.     

Immobilised metal ion affinity chromatography purification of alcohol dehydrogenase from baker’s yeast using an expanded bed adsorption system

Alcohol dehydrogenase (ADH) from solutions of homogenised packed bakers’ yeast has been successfully purified using immobilised metal-ion affinity chromatography in an expanded bed. Method scouting carried out using pure ADH solutions loaded onto 5-ml HiTrap columns charged with Zn²⁺, Ni²⁺ and Cu²⁺ and eluted using 0–50 mM EDTA gradient found that charging with Zn²⁺ gave the highest recovery and the lowest EDTA concentration required for elution. These results were used to develop a protocol for the expanded bed system and further tested using clarified yeast homogenate loaded onto XK16/20 packed beds (approximately 30 ml) packed with Chelating Sepharose FastFlow matrix in order to determine the optimum elution conditions using EDTA. The ADH was found to elute at 5 mM EDTA and the dynamic and total binding capacities of Streamline chelating for ADH were found to be 235 U/ml and 1075 U/ml matrix, respectively. Expanded bed work based on a step EDTA elution protocol demonstrated that ADH could be successfully eluted from unclarified homogenised bakers’ yeast diluted to 10 mg/ml total protein content with a recovery of 80–100% that was maintained over five consecutive runs with a vigorous clean-in-place procedure between each run.     

Three-dimensional noncollinear antiferromagnetic order in single-crystalline FeMn ultrathin films

We present experimental evidence for a three-dimensional noncollinear antiferromagnetic spin structure in ultrathin single-crystalline fcc Fe50Mn50 layers using magnetic circular dichroism photoelectron emission microscopy and x-ray magnetic linear dichroism. Layer-resolved as-grown domain images of epitaxial trilayers grown on Cu(001) in which FeMn is sandwiched between ferromagnetic layers with different easy axes reveal the presence of antiferromagnetic spin components in the film plane and normal to the film plane. An FeMn spin structure with no collinear order in the film plane is consistent with the absence of x-ray magnetic linear dichroism in Fe L3 absorption in FeMn/Co bilayers.     

On the risk-equivalence of two methods of randomization in statistics

For statistical decision problems, there are two well-known methods of randomization: on the one hand, randomization by means of mixtures of nonrandomized decision functions (randomized decision rules) in the game “statistician against nature,” on the other hand, randomization by means of randomized decision functions. In this paper, we consider the problem of risk-equivalence of these two procedures, i.e., imposing fairly general conditions on a nonsequential decision problem, it is shown that to each randomized decision rule, there is a randomized decision function with uniformly the same risk, and vice versa. The crucial argument is based on rewriting risk-equivalence in terms of Choquet's integral representation theorem. It is shown, in addition, that for certain special cases that do not fulfill the assumptions of the Main Theorem, risk-equivalence holds at least partially.     

Diffractive large transferred momentum photoproduction of vector mesons

The large t behavior of the helicity amplitudes of diffractive photoproduction is estimated relying on models of the photon and meson light-cone wave functions and on the double-logarithmic approximation to the exchanged gluon interaction. The role of large-size color dipole contributions to the photon-meson transition impact factor is discussed.Received: 17 November 2003, Revised: 10 March 2004, Published online: 23 June 2004A. Ivanov: Corresponding author.     

Decagonal quasiferromagnetic microstructure on the penrose tiling

The stable magnetization configurations of a ferromagnet on a quasiperiodic tiling have been derived theoretically. The magnetization configuration is investigated as a function of the ratio of the exchange to the dipolar energy. The exchange coupling is assumed to decrease exponentially with the distance between magnetic moments. It is demonstrated that for a weak exchange interaction the new structure, the quasiferromagnetic decagonal configuration, corresponds to the minimum of the free energy. The decagonal state represents a new class of frustrated systems where the degenerated ground state is aperiodic and consists of two parts: ordered decagon rings and disordered spin-glass-like phase inside the decagons.     

Spin-polarized low-energy electron diffraction: Theory,experiment and analysis of results from W(001)(1 × 1)

The theory of spin-polarized low-energy electron diffraction (SPLEED) is outlined with an emphasis on symmetry-induced properties and models for the effective single-sphere potential. Details are given of the experimental set-up involving a new type of spin polarization detector based on SPLEED. Numerical calculations for the W(001)(1× 1) surface proceeded in close coordination with measurements of spin polarization (normal to the scattering plane) and intensity. A variety of calculated spin polarization and intensity profiles exhibits features, which are very sensitive to changes in the top interlayer spacing, as well as features sensitive to various ingredients of the potential model. The overall agreement between theory and experiment is very good not only for intensities, but also for spin polarization. It implies a contraction of the topmost interlayer spacing of W(001) with respect to the bulk spacing by 7% ± 1.5%, and supports the use of an energy-dependent exchange part and a nonuniform absorption part in the effective ion-core potential.     

Influence of kinematical constraints on multiplicity distributions and neutral charged correlations in the independent cluster emission model

Energy-momentum conservation in the cluster production process is introduced in the independent cluster emission model using the generating functional formalism. In a simple version of the model clusters are produced which decay into a fixed number of pions. The ?? model and a model with isospin conservation in the cluster decay are used to calculate the charge distribution among the secondaries of cluster decay. Multiplicity characteristics like average multiplicity, second moments and associated average neutral multiplicities and second moments are calculated. The results are compared with experimental data.     

Spin reorientation and structural relaxation of atomic layers: pushing the limits of accuracy

The correlation between an ad-layer-induced spin reorientation transition (SRT) and the ad-layer-induced structural relaxation is investigated by combined in situ surface x-ray diffraction and magneto-optical Kerr-effect experiments on Ni/Fe/Ni(111) layers on W(110). The Fe-induced SRT from in-plane to out-of-plane, and the SRT back to in-plane upon subsequent coverage by Ni, are each accompanied by a small lattice relaxation of at most 0.002 A. Such a small strain variation excludes a magnetoelasticity driven SRT, and we suggest the interface anisotropy as a possible driving force.