Stabilization of sphingomyelin interactions by interfacial hydroxyls — A study of phytosphingomyelin properties

AbstractD-ribo-phytosphingosines are biologically significant long-chain bases present in various sphingolipids from yeasts, fungi, plants and mammals. In this study we prepared phytopalmitoylsphingomyelin (phytoPSM) analogs based on the D-ribo-phytosphingosine base. The N-linked acyl chains were either 16:0, 2OH(R)16:0 (natural isomer), or 2OH(S)16:0. The gel-phase of phytoPSM was more stable than that of PSM (Tm 48.6°C and 41.0°C, respectively). The gel-liquid crystalline phase transition enthalpies were 9.1±0.4 and 6.1±0.3kcal/mol for phytoPSM and PSM, respectively. An N-linked 2OH(R)16:0 in phytoPSM destabilized the gel phase relative to phytoPSM (by ~+6°C, based on DPH anisotropy measurements), whereas 2OH(S)16:0 in phytoPSM stabilized it (by ~−6°C). All phytoPSM analogs formed sterol-enriched ordered domains in a fluid ternary bilayer, and those containing phytoPSM or 2OH(S)phytoPSM were more thermostable than the domains containing 2OH(R)phytoPSM or PSM. The affinity of cholestatrienol for POPC bilayers containing 20mol% phytoPSM was higher than for comparable bilayers with an equal amount of PSM. The 2-hydroxylated acyl chains in phytoPSM did not markedly alter sterol affinity. We conclude that phytoPSM is a more ordered sphingolipid than PSM, and is fully capable of interacting with cholesterol

Evidence of a second acceptor state of the E center in Si1-x Gex

We have found evidence of a second acceptor state of the E center in Si1-x Gex by using positron annihilation spectroscopy. To achieve this, we studied proton irradiated n-type Si1−x Gex with a Ge content of 10%–30% and a P dopant concentration of 10 exp 18cm exp −3, in which the number of Ge atoms around irradiation induced E centers was increased by annealing. When measuring the Doppler broadening of the annihilation line, the shape parameter S starts to decrease at 150 K with decreasing measurement temperature. This indicates that a charge transition in the upper half of the Si1−x Gex band gap, above the well known (0/−) level, takes place. Hence, we suggest that the increased concentration of germanium around the E center pulls down the localized second acceptor state into the Si1−x Gex band gap, making the Ge decorated E center a more effective trap for conduction electrons.Peer reviewe

Native point defects in GaSb

We have applied positron annihilation spectroscopy to study native point defects in Te-doped n-type and nominally undoped p-type GaSb single crystals. The results show that the dominant vacancy defect trapping positrons in bulk GaSb is the gallium monovacancy. The temperature dependence of the average positron lifetime in both p- and n-type GaSb indicates that negative ion type defects with no associated open volume compete with the Ga vacancies. Based on comparison with theoretical predictions, these negative ions are identified as Ga antisites. The concentrations of these negatively charged defects exceed the Ga vacancy concentrations nearly by an order of magnitude. We conclude that the Ga antisite is the native defect responsible for p-type conductivity in GaSb single crystals.Peer reviewe

Instability of the Sb vacancy in GaSb

We demonstrate that the instability of the Sb vacancy in GaSb leads to a further increase in the acceptor-type defect concentration in proton irradiated undoped, p-type GaSb. Using positron annihilation spectroscopy in situ with 10 MeV proton irradiation at 35 K, we find that the irradiation produces both native vacancy defects in GaSb. However, the Sb vacancy is unstable above temperatures of 150 K and undergoes a transition resulting in a Ga vacancy and a Ga antisite. The activation energy of this transition is determined to be 0.6 eV +/- 0.1 eV. Our results are in line with the established amphoteric defect model and prove that the instability of the Sb vacancy in GaSb has a profound role on the native defect concentration in GaSb.Peer reviewe

Divacancy clustering in neutron-irradiated and annealed n-type germanium

We have studied the annealing of vacancy defects in neutron-irradiated germanium. After irradiation, the Sb-doped samples [(Sb)=1.5×10 exp 15 cm exp −3] were annealed at 473, 673, and 773 K for 30 min. The positron lifetime was measured as a function of temperature (30–295 K). A lifetime component of 330 ps with no temperature dependence is observed in as-irradiated samples, identified as the positron lifetime in a neutral divacancy and indicating that the divacancy is stable at room temperature (RT). Annealing at 673 K resulted in an increase in the average positron lifetime, and in addition, the annealed samples further showed a larger lifetime component of 430 ps at RT, which is due to larger vacancy clusters. The average positron lifetime in the samples annealed at 473 K has a definite temperature dependence, suggesting that the divacancies become negative as the crystal recovers and the Fermi level moves upwards in the band gap. Annealing at 673 K, reduces the average lifetime and intensity of the defect component τ2 at RT, indicating that the vacancy clusters have started to anneal. Negative divacancies are still present in the samples after this anneal. Annealing at 773 K is enough to remove all observable vacancy defects.Peer reviewe

Direct observations of the vacancy and its annealing in germanium

Weakly n-type doped germanium has been irradiated with protons up to a fluence of 3×10 exp 14 cm exp −2 at 35 K and 100 K in a unique experimental setup. Positron annihilation measurements show a defect lifetime component of 272±4 ps at 35 K in in situ positron lifetime measurements after irradiation at 100 K. This is identified as the positron lifetime in a germanium monovacancy. Annealing experiments in the temperature interval 35–300 K reveal two annealing stages. The first at 100 K is tentatively associated with the annealing of the Frenkel pair, the second at 200 K with the annealing of the monovacancy. Above 200 K it is observed that mobile neutral monovacancies form divacancies, with a positron lifetime of 315 ps.Peer reviewe

Monte Carlo simulations of 2d hard core lattice gases

Monte Carlo simulations are used to study lattice gases of particles with extended hard cores on a two dimensional square lattice. Exclusions of one and up to five nearest neighbors (NN) are considered. These can be mapped onto hard squares of varying side length, $\lambda$ (in lattice units), tilted by some angle with respect to the original lattice. In agreement with earlier studies, the 1NN exclusion undergoes a continuous order-disorder transition in the Ising universality class. Surprisingly, we find that the lattice gas with exclusions of up to second nearest neighbors (2NN) also undergoes a continuous phase transition in the Ising universality class, while the Landau-Lifshitz theory predicts that this transition should be in the universality class of the XY model with cubic anisotropy. The lattice gas of 3NN exclusions is found to undergo a discontinuous order-disorder transition, in agreement with the earlier transfer matrix calculations and the Landau-Lifshitz theory. On the other hand, the gas of 4NN exclusions once again exhibits a continuous phase transition in the Ising universality class -- contradicting the predictions of the Landau-Lifshitz theory. Finally, the lattice gas of 5NN exclusions is found to undergo a discontinuous phase transition.Comment: 13 pages, lots of figure

Point defect balance in epitaxial GaSb

Positron annihilation spectroscopy in both conventional and coincidence Doppler broadening mode is used for studying the effect of growth conditions on the point defect balance in GaSb:Bi epitaxial layers grown by molecular beam epitaxy. Positron annihilation characteristics in GaSb are also calculated using density functional theory and compared to experimental results. We conclude that while the main positron trapping defect in bulk samples is the Ga antisite, the Ga vacancy is the most prominent trap in the samples grown by molecular beam epitaxy. The results suggest that the p–type conductivity is caused by different defects in GaSb grown with different methods.Peer reviewe

Membrane Properties of D-erythro-N-acyl Sphingomyelins and Their Corresponding Dihydro Species

AbstractWe have prepared acyl chain-defined D-erythro-sphingomyelins and D-erythro-dihydrosphingomyelins and compared their properties in monolayer and bilayer membranes. Surface pressure/molecular area isotherms of D-erythro-N-16:0-sphingomyelin (16:0-SM) and D-erythro-N-16:0-dihydrosphingomyelin (16:0-DHSM) show very similar packing properties, except that the expanded-to-condensed phase transition (crystallization) occurs at a lower surface pressure for 16:0-DHSM. The measured surface potential was generally about 100mV less for 16:0-DHSM monolayers compared to 16:0-SM monolayers. The condensed domains (crystals) that formed in 16:0-SM monolayers as a function of compression displayed star-shaped morphology when viewed under an epifluorescence microscope. 16:0-DHSM monolayers did not form similar crystals upon compression. 16:0-DHSM was degraded much faster by sphingomyelinase from Staphylococcus aureus than 16:0-SM (10-fold difference in enzyme activity needed for comparable hydrolytic rate). Cholesterol desorption from 16:0-DHSM to cyclodextrin was slightly slower (∼20%) than the rate measured from 16:0-SM monolayers (at 60mol % cholesterol). The bilayer melting temperature of 16:0-DHSM was 47.7°C (ΔH 8.3kcal/mol) whereas it was 41.2°C for 16:0-SM (ΔH 8.1kcal/mol). Cholesterol/16:0-DHSM bilayers (15mol % sterol) had more condensed domains than comparable 16:0-SM bilayers, as evidenced from the quenching resistance of DPH in DHSM membranes. We conclude that cholesterol interacts more favorably with 16:0-DHSM and that the membranes are more condensed than comparable 16:0-SM-containing membranes