Interfacial rheology of mixed layers of food proteins and surfactants

Mixed protein–surfactant adsorption layers at liquid interfaces are described including the thermodynamic basis, the adsorption kinetics and the shear and dilational interfacial rheology. It is shown that due to the protrusion of hydrophobic protein parts into the oil phase the adsorption layers at the water–hexane interface are stronger anchored as compared to the water-air surface. Based on the different adsorption protocols, a sequential and a simultaneous scheme, the peculiarities of complexes between proteins and added surfactants are shown when formed in the solution bulk or at a liquid interface. The picture drawn from adsorption studies is supported by the findings of interfacial rheology.     

Ionization energy and electronic structure of polycytidine

Ribonucleic acid (RNA) polycytidine (poly rC) homopolymer thin films were prepared on highly oriented pyrolytic graphite (HOPG) substrates. The films were grown from aqueous solution directly in a vacuum in multiple steps with use of an electrospray (ES) deposition system. Before poly rC deposition and after each deposition step the sample was characterized with X-ray and ultraviolet photoemission spectroscopy (XPS, UPS). Evaluation of the UP-spectra sequence allowed the determination of ionization energy and highest occupied molecular orbital (HOMO) electronic structure, as well as the charge injection barriers between HOPG and poly rC. Comparison with earlier results on polyadenosine (poly rA) indicates significant differences between ionization energies (poly rC: 8.1 eV; poly rA: 6.8 eV) and orbital alignment at the graphite interface. The larger ionization energy of poly rC results in a larger hole injection barrier and a smaller electron injection barrier relative to the HOPG Fermi level.     

Three-dimensional spin structure on a two-dimensional lattice: Mn/Cu(111)

Based on first-principles vector spin-density total-energy calculations of the magnetic and electronic structure of Cr and Mn transition-metal monolayers on the triangular lattice of a (111) oriented Cu surface, we propose for Mn a three-dimensional noncollinear spin structure on a two-dimensional triangular lattice as magnetic ground state. This new spin structure is a multiple spin-density wave of three row-wise antiferromagnetic spin states and comes about due to magnetic interactions beyond the nearest neighbors and due to higher order spin interactions (i.e., four spin). The magnetic ground state of Cr is a coplanar noncollinear periodic 120 degrees Néel structure.     

A slow positron lifetime study of the annealing behaviour of an amorphous silicon layer grown by MBE

We have studied MBE grown amorphous silicon, which was recrystallized at different temperatures for one hour, with a pulsed positron beam. A positron lifetime of 538±10 ps in the as-grown state is attributed to microvoids containing at least 10 vacancies. An incompletely recrystallized sample annealed at 500°C shows an additional long lifetime from ortho-positronium (o-Ps) pick-off annihilation. The o-Ps component disappears for samples, recrystallized at 700°C and above, and the defect lifetime steadily decreases with higher annealing temperature until a value of 310 ps is reached for the layer annealed at 1200°C. This value is explained by positron trapping at dislocations or small vacancy defects stabilized by dislocations or impurities.Paper presented at the 132nd WE-Heraeus-Seminar on Positron Studies of Semiconductor Defects, Halle, Germany, 29 August to 2 September 1994     

Large tilting modules and representation type

We study finiteness conditions on large tilting modules over arbitrary rings. We then turn to a hereditary artin algebra R and apply our results to the (infinite dimensional) tilting module L that generates all modules without preprojective direct summands. We show that the behaviour of L over its endomorphism ring determines the representation type of R. A similar result holds true for the (infinite dimensional) tilting module W that generates the divisible modules. Finally, we extend to the wild case some results on Baer modules and torsion-free modules proven in Angeleri Hügel, L., Herbera, D., Trlifaj, J.: Baer and Mittag-Leffler modules over tame hereditary algebras. Math. Z. 265, 1–19 (2010) for tame hereditary algebras.     

NMR‐Solution Structures of Fluoro‐Substituted β‐Peptides: A 314‐Helix and a Hairpin Turn. The First Case of a 90° OC?C?F Dihedral Angle in an α‐Fluoro‐Amide Group

To further study the preference of the antiperiplanar (ap) conformation in α‐fluoro‐amide groups, two β‐peptides, 1 and 2 , containing a (2‐F)‐β³hAla and a (2‐F)‐β²hPhe residue, have been synthesized. Their NMR‐solution structures in CD₃OH were determined and compared with those of non‐F‐substituted analogs, 3 and 4a . While we have found in a previous investigation (Helv. Chim. Acta 2005 , 88, 266) that a stereospecifically introduced F‐substituent in the central position of a β‐heptapeptide is capable of ‘breaking’ the 3₁₄‐helical structure by enforcing the F? C? C?O ap‐conformation, we could now demonstrate that the same procedure leads to a structure with the unfavorable ca. 90° F? C? C?O dihedral angle, enforced by the 3₁₄‐helical folding in a β‐tridecapeptide (cf. 1 ; Fig. 4). This is interpreted as a consequence of cooperative folding in the longer β‐peptide. A F‐substituent placed in the turn section of a β‐peptidic hairpin turn was shown to be in an ap‐arrangement with respect to the neighboring C?O bond (cf. 2 ; Fig. 7). Analysis of the non‐F‐substituted β‐tetrapeptides (with helix‐preventing configurations of the two central β²/β³‐amino acid residues) provides unusually tight hairpin structural clusters (cf. 3 and 4a ; Figs. 8 and 9). The skeleton of the β‐tetrapeptide H‐(R)β³hVal‐(R)β²hVal‐(R)β³hAla‐(S)β³hPhe‐OH ( 4a ) is proposed as a novel, very simple backbone structure for mimicking α‐peptidic hairpin turns.     

H/D isotopic effect on the hydrogen bond between tertiary amines and alcohols

The thermodynamical properties (equilibrium constants K, association enthalpies -ΔH, and association entropies -ΔS) and selected spectroscopic parameters (Δν_OH/ν_OH and Δν_OD/ν_OD of the associate band) of hydrogen bonded systems, formed by tertiary amines and benzyl alcohol or isopropanol as well as their O-deuteriated analogous species, have been obtained by ir measurements. In all cases the values of K_H/K_D were found lower than unity, but ΔH_H/ΔH_D higher than unity.     

Magnetically stabilized surface alloys

We investigate the interrelation of magnetism and stability of ultrathin magnetic films and come to the conclusion that under certain circumstances there should exist magnetically stabilized two-dimensional surface alloys. We present ab initio results for the formation energy and the interdiffusion energy of Cu(001)c(2 × 2)3d surface alloy films. Results based on the density functional theory in the local spin density approximation (LSDA) indicate the existence of a thermodynamically stable surface alloy: Cu(001)c(2 × 2) Mn. Although in detail, the results depend on the Cu substrate, the trends presented below have an universal character. Therefore, Cu(100)c(2 × 2) Mn is only an example of a much wider class of magnetic surface alloys. Recently, several of these surface alloys have been found experimentally, showing an unexpectingly large structural corrugation of the surface alloy atoms. This will be discussed as a result of a large magneto-volume effect. We found in addition a non-magnetic surface alloy Ti/Cu(001), which is not yet confirmed experimentally. Total energy calculations were carried out using the full-potential linearized augmented planewave (FLAPW) method in film geometry.