Multiple forms of aldolase in organ extracts of the rat. On aldolases, 8

The aldolase activities of crude rat tissue extracts were separated by starch gel electrophoresis. Aldolase was located on the gel by a specific staining method. Nine bands of different electrophoretic mobility were stainable by this technique. Organ specific isoenzyme patterns could be demonstrated.     

Anisotropy of the electrical resistivity in PrAl2 and DyAl2

The anisotropy of the spontaneous resistivity is measured in the ferromagnetic range for PrAl₂ and DyAl₂ single crystals. For PrAl₂ we observed a change of sign in the temperature dependence of θ₆ ? θ_⊥ which cannot be obtained from existing quadrupole scattering models.     

Sampling of rare events using hidden restraints

A method to enhance sampling of rare events is presented. It makes use of distance or dihedral-angle restraints to overcome an energy barrier separating two metastable states or to stabilize a transition state between the two metastable states. In order not to perturb these metastable end states themselves, a prefactor is introduced into the restraining energy function, which smoothly increases the weight of this function from zero to one at the transition state or on top of the separating energy barrier and then decreases the weight again to zero at the final state. The method is combined with multi-configurational thermodynamic integration and applied to two biomolecular systems, which were difficult to treat using standard thermodynamic integration. As first example the free energy difference of a cyclic alpha-aminoxy-hexapeptide-ion complex upon changing the ion from Cl- to Na+ was calculated. A large conformational rearrangement of the peptide was necessary to accommodate this change. Stabilizing the transition state by (hidden) restraints facilitates that. As a second example, the free energy difference between the 4C1 and the 1C4 conformation of beta-D-glucopyranoside was calculated. In unrestrained simulations the change from the 4C1 into the 1C4 conformation was never observed because of the high energy barrier separating the two states. Using (hidden) restraints, the transition from the 4C1 into the 1C4 state and back could be enforced without perturbing the end states. As comparison, for the same transitions the potential of mean force as obtained by using dihedral-angle constraints is provided.     

Vibrational spectra and crystal structure of the di‐amino acid peptide cyclo(L‐Met‐L‐Met): comparison of experimental data and DFT calculations

Experimental Raman and FT‐IR spectra of solid‐state non‐deuterated and N‐deuterated samples of cyclo(L ‐Met‐L ‐Met) are reported and discussed. The Raman and FT‐IR results show characteristic amide I vibrations (Raman: 1649 cm⁻¹, infrared: 1675 cm⁻¹) for molecules exhibiting a cis amide conformation. A Raman band, assigned to the cis amide II vibrational mode, is observed at ∼1493 cm⁻¹ but no IR band is observed in this region. Cyclo(L ‐Met‐L ‐Met) crystallises in the triclinic space group P1 with one molecule per unit cell. The overall shape of the diketopiperazine (DKP) ring displays a (slightly distorted) boat conformation. The crystal packing employs two strong hydrogen bonds, which traverse the entire crystal via translational repeats. B3‐LYP/cc‐pVDZ calculations of the structure of the molecule predict a boat conformation for the DKP ring, in agreement with the experimentally determined X‐ray structure. Copyright © 2009 John Wiley & Sons, Ltd.     

Direct experimental evidence for atomic tunneling of europium in crystalline Eu8Ga16Ge30

M?ssbauer-effect and microwave absorption experimental evidence unambiguously demonstrates the presence of slow, approximately 450 MHz, tunneling of magnetic europium between four equivalent sites in Eu8Ga16Ge30, a stoichiometric clathrate. Remarkably, six of the eight europium atoms, or 11% of the constituents in this solid, tunnel between these four sites separated by 0.55 A. The off centering of the atoms or ions in crystalline clathrates appears to be a promising route for producing Rabi oscillators in solid-state materials.     

Interfaces in perovskite heterostructures

Recent advances in film synthesis have made it possible to investigate the properties of well-controlled interfaces in perovskite metal-oxides. A review of published experimental data and computational results indicate that so far most interfaces that have been analyzed in ferroelectric materials—while necessary to impose large lattice strain on the polar material—contribute little to the ferroelectricity and may instead be detrimental to the desired properties. In contrast, a very different situation arises at interfaces that show changes in the electronic configuration as a consequence of a compositional discontinuity. Data is shown for LaMnO₃/SrTiO₃ superlattices as an example of electronic effects that produce enhanced properties, further illustrating the richness of interfacial properties that can be obtained at interfaces (as shown in numerous published results for different but related interfaces).     

X-Ray Crystallographic Structure of the Cyclic Di-amino Acid Peptide: <Emphasis Type=Italic>N,N</Emphasis>′-Diacetyl-cyclo(Gly-Gly)

Abstract  

The cyclic di-amino acid peptide N,N′-diacetyl-cyclo(Gly-Gly), C₈H₁₀N₂O₄, crystallizes in the triclinic space group P[`1] Pbar{1} with unit cell parameters a = 9.4855(4) ?, b = 10.0250(3) ?, c = 10.0763(4) ?, α = 73.682(2)°, β = 82.816(2)°, γ = 81.733(2)°, V = 906.40(6) ?<sup>3</sup>, Z = 4 (2 molecules, A and B, per asymmetric unit), D<sub>c</sub> = 1.452 g cm<sup>−3</sup> and linear absorption coefficient 0.118 mm<sup>−1</sup>. The crystal structure determination was carried out with MoKα X-ray data measured at 120(2) K. In the final refinement cycle the data/restraints/parameter ratios were 4124/0/258 and goodness-of-fit on F<sup>2</sup> = 1.0008. Final R indices for [I > 2σ(I)] were R<sub>1</sub> = 0.0501, wR<sub>2</sub> = 0.1007 and R indices (all data) R<sub>1</sub> = 0.0864, wR<sub>2</sub> = 0.11180. The largest electron density difference peak and hole were 0.241 and −0.232 e ?<sup>−3</sup>, respectively. The DKP rings in both molecules A and B have boat conformations with pseudo mm2 (C<sub>2v</sub>) symmetry if the N atoms and CH<sub>2</sub> groups are considered identical. In each case, the prow and stern of the boat are the α-carbons C(3) and C(6). The overall molecular symmetry of molecules A and B is approximately C<sub>2</sub> with the twofold symmetry axis of the DKP boat being maintained through the centre of the DKP ring. Details of the molecular geometry are compared with that of the parent compound cyclo(Gly-Gly) in which the DKP ring is planar with exact symmetry [`1] bar{1} (C_i).     

Quantum wire heterostructure for optoelectronic applications

Quantum wire (QWR) heterostructures suitable for optoelectronic applications should meet a number of requirements, including defect free interfaces, large subband separation, long carrier lifetime, efficient carrier capture. The structural and opticl properties of GaAs/AlGaAs and InGaAs/GaAs quantum wire (QWR) heterostructures grown by organometallic chemical vapor deposition on nonplanr substrates, which satisfy many of these criteria, are described. These crescent-shaped QWRs are formed in situ during epitaxial growth resulting in virtually defect free interfaces. Effective wire widths as small as 10nm have been achieved, corresponding to electron subband separations greater than K_BT at room temperature. The enhanced density of states at the QWR subbands manifests itself in higher optical absorption and emission as visualized in photoluminescence (PL), PL excitation, amplified spontaneous emission and lasing spectra of these structures. Effective carrier capture into the wires via connected quantum well regions, which is important for enhancing the otherwise extremely small capture cross section of these wires, has also been observed. Room temperature operation of GaAs/AlGaAs and strained InGaAs/GaAs QWR lasers with threshold currents as low as 0.6mA has been demonstrated.