IDENTIFICATION OF A PUTATIVE MEMBRANE-INSERTED SEGMENT IN THE ALPHA-TOXIN OF STAPHYLOCOCCUS-AUREUS

To gain a fuller understanding of the regions of the Staphylococcus aureus alpha-toxin important in pore formation, we have used Forster dipole-dipole energy transfer to demonstrate that a central glycine-rich region of alpha-toxin (the so-called ''hinge'' region) inserts deeply into the bilayer on association of toxin with liposomes. Mutant alpha-toxins with unique cysteine (C) residues at positions 69 and 130 [Palmer, M., et al. (1993) J. Biol. Chem. 268, 11959) were reacted with the C-specific fluorophore acrylodan, which acted as an energy donor. The chosen acceptor was N-(7-nitrobenz-2-oxa-13-diazol-4-yl)-1,2-bis(hexadecanoyl) -sn-glycero-3-phosphoethanolamine (NBD-PE). Measurement of the degree of donor quenching with increasing NBD-PE in the inner bilayer leaflet enables the distance of closest approach between donor and acceptor to be estimated. For toxin labeled with acrylodan at position 130 (in the hinge region), this distance is approximately 5 +/- 2 Angstrom, showing that the probe is close to the inner surface of the liposomes. A second probe labeled at position 69 (in the N-terminal domain) shows negligible energy transfer, indicating a distance of closest approach >40 Angstrom. This implies that this N-terminal region remains ''outside'' the liposome. We propose a model in which the central region of the alpha-toxin inserts into the membrane and possibly participates in forming the wall of the pore.

Separation of dielectric and space charge polarizations in CaCu3Ti4O12/CaTiO3 composite polycrystalline systems

The complex analysis of dielectric/capacitance is a very useful approach to separate different polarization contributions existing in polycrystalline ceramics. In this letter, the authors use this type of spectroscopic analysis to separate the bulk's dielectric dipolar relaxation contributions from the polarization contribution due to space charge in the grain boundaries of a CaCu3Ti4O12/CaTiO3 polycrystalline composite system. The bulk dielectric dipolar relaxation was attributed to the self-intertwined domain structures from the CaCu3Ti4O12 phase coupled to the dipole relaxation from the CaTiO3 phase, while the space charge relaxation was attributed to the Schottky-type potential barrier responsible for the highly non-Ohmic properties observed in this composite polycrystalline system.

Structural studies of NaPO3-MoO3 glasses by solid-state nuclear magnetic resonance and raman spectroscopy

Vitreous samples were prepared in the (100 - x)% NaPO3-x% MoO3 (0 <= x <= 70) glass-forming system by a modified melt method that allowed good optical quality samples to be obtained. The structural evolution of the vitreous network was monitored as a function of composition by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), Raman scattering, and solid-state nuclear magnetic resonance (NMR) for P-31, Na-23, and Mo-95 nuclei. Addition of MoO3 to the NaPO3 glass melt leads to a pronounced increase in the glass transition temperatures up to x = 45, suggesting a significant increase in network connectivity. For this same composition range, vibrational spectra suggest that the Mo6+ ions are bonded to some nonbridging oxygen atoms (Mo-O- or Mo=O bonded species). Mo-O-Mo bond formation occurs only at MoO3 contents exceeding x = 45. P-31 magic-angle spinning (MAS) NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages. These sites are denoted as Q(2Mo)((2)), Q(1Mo)((2)), and Q(0Mo)((2)), respectively. For x < 0.45, the populations of these sites can be described along the lines of a binary model, according to which each unit of MoO3 converts two Q(nMo)((2)) sites into two Q((n+1)Mo)((2)) sites (n = 0, 1). This structural model is consistent with the presence of tetrahedral Mo(=O)(2)(O-1/2)(2) environments. Indeed, Mo-95 NMR data suggest that the majority of the molybdenum species are four-coordinated. However, the presence of additional six-coordinate molybdenum in the MAS NMR spectra indicates that the structure of these glasses may be more complicated and may additionally involve sharing of network modifier oxide between the network formers phosphorus and molybdenum. This latter hypothesis is further supported by Na-23{P-31} rotational echo double resonance (REDOR) data, which clearly reveal that the magnetic dipole-dipole interactions between P-31 and Na-23 are increasingly diminished with increasing molybdenum content. The partial transfer of modifier from the phosphate to the molybdate network former implies a partial repolymerization of the phosphate species, resulting in the formation of Q(nMo)((3)) species and accounting for the observed increase in the glass transition temperature with increasing MoO3 content that is observed in the composition range 0 <= x <= 45. Glasses with MoO3 contents beyond x = 45 show decreased thermal and crystallization stability. Their structure is characterized by isolated phosphate species [most likely of the P(OMo)(4) type] and molybdenum oxide clusters with a large extent of Mo-O-Mo connectivity.

Development of basis sets to calculations of the electronic structure of YMnO3

The generator coordinate Hartree-Fock method was used to develop 20s17p, 30s20p14d, and 30s21p16d Gaussian basis sets for the O ((3)p), Mn (S-6), and Y (D-2) atoms, respectively. The Gaussian basis sets were contracted to 20s17p/9s7p, 30s20p14d/11s7p7d, and 30s21p16d/14s7p7d and utilized in calculations of total energy and orbital energies of the (MnO1+)-Mn-5 and (YO1+)-Y-3 fragments to evaluate its quality in molecular studies. Finally, the contracted basis set for O atom was supplemented with one polarization function of d symmetry and used along with the other contracted basis sets (for Mn and Y) to calculate dipole moments, total energy, and total atomic charges in YMnO3 in space group D-6h. The analysis of those properties showed that is reasonable to believe that YMnO3 present behavior of piezoelectric material. (C) 2003 Elsevier B.V. All rights reserved.

Stress-induced ordering due heavy interstitial atoms in Nb-0.3 wt.% Ti alloys

The mechanical properties of metals with bee structure, such as niobium and their alloys, are changed of a significant way by the introduction of heavy interstitial elements. These interstitial elements (oxygen, for example) present in the metallic matrix occupy octahedral sites and constitute an elastic dipole of tetragonal symmetry and might produce anelastic relaxation. Polycrystalline samples of Nb-0.3 wt.% Ti (Nb-Ti) alloy with oxygen in solid solution were analysed. The anelastic spectroscopy measurements had been made in a torsion pendulum, with frequencies in the Hz range, in a temperature range between 300 and 700 K. The results showed thermally activated relaxation structures were identified four relaxation process attributed to stress-induced ordering of single oxygen, nitrogen and carbon atoms around niobium and stress-induced ordering of single oxygen atoms around titanium atoms. (c) 2005 Elsevier B.V. All rights reserved.

Efficient plasmonic coupling between Er3+:(Ag/Au) in tellurite glasses

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

An insight into the theoretical investigation of possible piezoelectric effect in samarium titanate (SmTiO3)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Study of the annealing temperature effect on the structural and luminescent properties of SrWO4:Eu phosphors prepared by a non-hydrolytic sol-gel process

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Investigation on the structure of liquid N-methylformamide-dimethylsulfoxide mixtures

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Quantum chemical modeling of perovskite: An investigation of piezoelectricity in ferrite of yttrium

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Contribution of an extrinsic mechanism for the electrical polarization in BiMn2O5 ceramics

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nuclear coherent versus incoherent effects in peripheral RHI collisions

We derive simple and physically transparent expressions for the contribution of the strong interaction to one-nucleon-removal processes in peripheral relativistic heavy-ion collisions. The coherent contribution, i.e., the excitation of a giant dipole resonance via meson exchange, is shown to be negligible as well as the interference between Coulomb and nuclear excitation. The incoherent nucleon-knockout contribution is also derived suggesting the nature of the nuclear interaction in this class of processes. We also justify the simple formulae used to fit the data of the E814 Collaboration. © 1995 Elseier Science B.V. All rights reserved.

The theory of vibronic transitions in rare earth compounds

The theory of vibronic transitions in rare earth compounds is re-examined in the light of a more reliable representation for the ligand field Hamiltonian than the crude electrostatic model. General expressions that take into account the relevant contributions from the forced electric dipole and dynamic coupling mechanisms are derived for the vibronic intensity parameters. These include additional terms, from charge and polarizability gradients, which have not been considered in previous work. Emphasis is given to the relative signs of these various contributions. Under certain approximations these expressions may be conveniently written in terms of accessible ligand field parameters. A comparison with experimental values for the compounds Cs2NaEuCl6 and LiEuF4 is made and satisfactory agreement between theory and experiment is found. A discussion is given on the sensitivity of the calculated intensities to the values of radial integrals, interconfigurational energy differences and ligand field parameters that may be used. Finally, the problem in which a vibronic and an electronic level are in resonance, or near resonance, is analyzed. Suitable expressions to describe the effects of the even-rank components of the vibronic Hamiltonian are obtained. It is found that, depending on the strength of the vibronic interaction and the resonance conditions, the admixture between these two levels may lead to intensities of nearly equal values. © 1995.

Light and thermal excitation of depolarization current in indirect bandgap Alx Ga1-xAs

Monochromatic light excitation in conjunction with thermally stimulated depolarization current measurements are applied to indirect bandgap AlxGa1-xAs. The obtained average activation energy for dipole relaxation is in very close agreement with the DX center binding energy. Monochromatic light induces state transition in the defect and makes possible the identification of dipoles observed in the dark. Charge relaxation currents are destroyed by photoionization of Al0.5Ga0.5As using either 647 nm Kr+ or 488 nm Ar+ laser lines, which are above the DX center threshold photoionization energy. It suggests that correlation may exist among charged donor states DX--d+. Sample resistance as a function of temperature is also measured in the dark and under illumination and shows the probable X valley effective mass state participation in the electron trapping. Ionization with energies of 0.8 eV and 1.24 eV leads to striking current peak shifts in the thermally stimulated depolarization bands. Since vacancies are present in this material, they may be responsible for the secondary band observed in the dark as well as participation in the light induced recombination process.

Energy transfer between Pr3+ ions in a fluoroindate glass

The efficiency of energy transfer (ET) between Pr3+ ions in a fluoroindate glass is determined. ET rates, WET, were determined for dilute samples and the results show a dependence of WET on the Pr3+ concentration. ET processes which contribute to resonance fluorescence and frequency upconversion emission were studied. The origin of the interaction energy among the Pr3+ ions was determined to be dipole - dipole. © 1998 Elsevier Science B.V. All rights reserved.