High pressure neutron-scattering experiments on phospholipid model biomembranes

Abstract

By use of neutron small-angle scattering (SANS) the structural properties of saturated and unsaturated phosphatidylcholine model biomembrane systems have been investigated in the temperature range from 0°C to 70°C and at pressures up to 3.5 kbar. The effect of chemical constitution of the hydrocarbon chains of the lipids and the effect of cholesterol on the thermotropic and barotropic phase behaviour is discussed.     

Role of the hydrogen in the light-induced defects in undoped hydrogenated amorphous silicon

We have investigated the effect of the deposition temperature (i.e. the hydrogen content) on the light-induced effects in undoped hydrogenated amorphous silicon (a-Si:H). Combined junction capacitance-temperature (C-T), ESR and IR absorption measurements are carried out in both the dark annealed state (A) and the saturated light-soaked state (B), as well as after partial annealing of the samples, starting from state B. The experimental results indicate that the films deposited at the highest substrate temperature (i.e. the lowest H content) exhibit a completely different behaviour from those deposited at lower substrate temperature (i.e. with higher H concentration), when the samples are left for long times at room temperature in the dark after partial annealing. These results are discussed in detail in relation to the different models proposed to explain the light-induced effects in a-Si:H.     

Adsorption and dissociation of Si2H6 on Ge(001)2 × 1

Adsorption and thermally-induced dissociation of disilane (Si₂H₆) on clean Ge(001)2 × 1 surfaces have been investigated using a combination of Auger electron spectroscopy (AES), electron energy loss spectroscopy (EELS), reflection high-energy electron diffraction (RHEED), and scanning tunneling microscopy (STM). With initial Si₂H₆ exposure at room temperature, the Si surface coverage increased monotonically, the EELS surface dangling bond peak intensities continuously decreased, and the intensity of half-order RHEED diffraction rods decreased. The low-coverage Si₂H₆ sticking probability at 300 K on Ge(001) was found to be 0.5 while the saturation coverage was 0.5 ML. A new EELS feature, GSH, involving Si-H and Ge-H bond states was observed at Si₂H₆ exposures φ 3.4 × 10¹³ cm⁻². In contrast to Si₂H₆ -saturated Si(001), the saturated Ge(001) surface significant fraction of dimerized bonds. Adsorbed overlayers were highly disordered with the primary species on saturated surfaces being SiH₂, GeH, and undissociated SiH₃· Si₂H₆-saturated Ge(001)2 × 1 substrates were annealed for l min at temperatures T_a between 425 and 825 K. Admolecules were mobile at T_a = 545 K giving rise to significant ordering in one-dimensional chains. By T_a = 605 K, essentially all of the admolecules were captured into coarsened islands. Dangling-bond EELS peaks reappeared by 625 K and the intensities of the half-order RHEED diffraction rods increased. Ge segregation to the surface, which began at T_a 625 K, occurred rapidly at T_a 675 K. All H was desorbed by 725 K.     

Experimental and theoretical study of the structure and vibrational spectra of valpromide,C7H15CONH2

In this work, we present results of the conformational and vibrational properties of valpromide (Vpd), an amide with antiepileptic activity, studied by IR and Raman spectroscopy at 300 and 77 K, and 300 K, respectively. Experimental data are compared against ab initio calculations performed at B3LYP level with the inclusion of solvatation effects. Experimental results, reinforced by theoretical calculations, point out that Vpd has three conformers on the potential energy surface, with different structures that can be identified in the CO and NH spectral regions. These conformers are defined by different angular arrays of the dihedral angles formed with the CO, C N and C〈 H, C C of the aliphatic chain bonds. The existence of different conformations and structures are discussed on the basis of results derived from electronic localization function (ELF) and natural orbital bond (NBO) analysis. Copyright © 2008 John Wiley & Sons, Ltd.     

K-induced surface structural change of Si(1 1 1)-7 × 7 probed by second-harmonic generation

The growth of thin K films on Si(1 1 1)-7 × 7 has been investigated by selecting the input and output polarizations of second-harmonic generation (SHG) at room temperature (RT) and at an elevated temperature of 350 °C. The SH intensity at 350 °C showed a monotonic increase with K coverages up to a saturated level, where low energy electron diffraction (LEED) showed a 3 × 1 reconstructed structure. The additional deposition onto the K-saturated surface at 350 °C showed only a marginal change in the SH intensity. These variations are different from the multi-component variations up to 1 ML and orders of magnitude increase due to excitation of plasmons in the multilayers at RT. The variations of SHG during desorption of K at 350 °C showed a two-step decay with a marked shoulder which most likely corresponds to the saturation K coverage of the Si(1 1 1)-3 × 1-K surface. The dominant tensor elements contributing to SHG are also identified for each surface.     

Structural stability of stepped nickel surfaces

The structural stability of stepped Ni(755) and Ni(771) surfaces in the temperature range 20–500°C and during adsorption of oxygen and different forms of carbon has been studied using scanning tunneling microscopy and low-energy electron diffraction. A phase transition from the structure with double steps at room temperature to the structure with single steps at a temperature above 350°C has been observed on the clean Ni(755) surface. This transition disappears after oxygen adsorption at a temperature above 350dgC. In this case, the structure on the Ni(755) surface with single steps is stabilized in contrast to Ni(771), which tends to faceting during oxygen adsorption. It has been shown that fullerenes C60 form an array of one-dimensional chains at the upper boundaries of steps of the substrate, when they are adsorbed on the Ni(755) surface.     

Adsorption and two-body recombination of atomic hydrogen on 3He-4He mixture films

We present the first systematic measurement of the binding energy E(a) of hydrogen atoms to the surface of saturated 3He- 4He mixture films at temperatures 70-400 mK. E(a) is found to decrease almost linearly from 1.14(1) K down to 0.39(1) K, when the population of the ground surface state of 3He grows from zero to 6x10(14) cm(-2), yielding the value 1.2(1)x10(-15) K cm(2) for the mean-field parameter of H- 3He interaction in 2D. Measuring by ESR the rate constants K(aa) and K(ab) for second-order recombination of hydrogen atoms in hyperfine states a and b, we find the ratio K(ab)/K(aa) to be independent of the 3He content and to grow with temperature.     

Unconventional carrier-mediated ferromagnetism above room temperature in ion-implanted (Ga,Mn)P:C

Ion implantation of Mn ions into hole-doped GaP has been used to induce ferromagnetic behavior above room temperature for optimized Mn concentrations near 3 at. %. The magnetism is suppressed when the Mn dose is increased or decreased away from the 3 at. % value, or when n-type GaP substrates are used. At low temperatures the saturated moment is on the order of 1 Bohr magneton, and the spin wave stiffness inferred from the Bloch-law T(3/2) dependence of the magnetization provides an estimate T(c)=385 K of the Curie temperature that exceeds the experimental value, T(c)=270 K. The presence of ferromagnetic clusters and hysteresis to temperatures of at least 330 K is attributed to disorder and proximity to a metal-insulating transition.     

Interaction-induced partitioning and magnetization jumps in the mixed-spin oxide FeTiO3-Fe2O3

In this study we report on jumps in the magnetic moment of the hemo-ilmenite solid solution (x)FeTiO(3)-(1-x)Fe(2)O(3) above Fe(III) percolation at low temperature (T<3 K). The first jumps appear at 2.5 K, one at each side of the magnetization loop, and their number increases with decreasing temperature and reaches 5 at T=0.5 K. The jumps occur after field reversal from a saturated state and are symmetrical in the trigger field and intensity with respect to the field axis. Moreover, an increase of the sample temperature by 2.8% at T=2.0 K indicates the energy released after the ignition of the magnetization jump, as the spin-currents generated by the event are dissipated in the lattice. The magnetization jumps are further investigated by Monte Carlo simulations, which show that these effects are a result of magnetic interaction-induced partitioning on a sublattice level.     

Controllable propagation of light pulses in Er-doped fibers with saturable absorption

We report controllable (slow or fast) propagation of low-intensity probe-light pulses through erbium-doped fiber periodically saturated by the synchronized master-pulse sequence. These two pulse sequences could have significantly different carrier wavelengths within the fundamental absorption spectrum 1470-1570 nm of Er(+3) ions. The effect of fractional delay or advancement grew with the fiber optical absorption at the probe wavelength and could be significantly stronger than that at the saturating wavelength. The probe-pulse advancement was observed in the case when the saturating and probe waves were modulated approximately in antiphase. The observed effects are explained in the framework of a simple model of a periodically saturated homogeneously broadened absorption line.     

Characteristics of driven polymer surfaces: growth and roughness

Using a Monte Carlo simulation, the growth and roughness characteristics of polymer surfaces are studied in 2+1 dimensions. Kink-jump and reptation dynamics are used to move polymer chains under a driving field where they deposit onto an impenetrable attractive wall. Effects of field (E), chain length (L(c)), and the substrate size (L) on the growing surfaces are studied. In low field, the interface width (W) shows a crossover from one power-law growth in time (W approximately t(beta(1))) to another (W approximately t(beta(2))), before reaching its asymptotic value (W(s)), with beta(1)( approximately 0.5+/-0.1)相似文献   

Correlation of dielectric properties,Raman spectra and calorimetric measurements of β-cyclodextrin-polyiodide complexes (β-cyclodextrin)2 ·BaI7 ·11H2O and (β-cyclodextrin)2 ·CdI7·15H2O

The frequency and temperature dependence of real and imaginary parts of the dielectric constant (ε′,?ε″), the phase shift (?) and the ac-conductivity (σ) of polycrystalline complexes (β-CD)₂·BaI₇·11H₂O and (β-CD)₂·CdI₇·15H₂O (β-CD?=?β-cyclodextrin) has been investigated over the frequency and temperature ranges 0–100?kHz and 140–420?K in combination with their Raman spectra, DSC traces and XRD patterns. The ε′(T), ε″(T) and ?(T) values at frequency 300?Hz in the range T<330?K show two sigmoids, two bell-shaped curves and two minima respectively revealing the existence of two kinds of water molecule, the tightly bound and the easily movable. Both complexes show the transition of normal hydrogen bonds to flip-flop type at 201?K. In the β-Ba complex most of the eleven water molecules remain tightly bound and only a small number of them are easily movable. On the contrary, in the β-Cd case the tightly bound water molecules are transformed gradually to easily movable. Their DSC traces show endothermic peaks with onset temperatures 118°C, 128°C for β-Ba and 106°C, 123°C, 131°C for β-Cd. The peaks 118°C, 106°C, 123°C are related to the easily movable and the tightly bound water molecules, while the peaks at 128°C, 131°C are caused by the sublimation of iodine. The activation energy of Ba²⁺ ions is 0.52?eV when all the water molecules exist in the sample and 0.99?eV when the easily movable water molecules have been removed. In the case of β-Cd the corresponding activation energies are 0.57?eV and 0.33?eV. The Raman peaks at 179?cm^?1, 170?cm^?1 and 165–166?cm^?1 are due to the charge transfer interactions in the polyiodide chains.     

Unconventional magnetic correlations in DyB2C and HoB2C

Layered borocarbides RB2C (R=Dy, Ho, and Er) have been studied by powder neutron diffraction at 2-30 K. ErB2C has two-sublattice antiferromagnetic order below T(N)=16.3 K, but DyB2C and HoB2C show a coexistence of a conventional canted k=(000) ferromagnetic structure and unconventional magnetic correlations. The k=(000) phase orders at T(c)=8.5 K (DyB2C) and 7.1 K (HoB2C), but low-Q diffraction peaks from the unconventional correlations appear above T(c) with different critical temperatures for different peaks: at 8, 10.5, and 15.7 K for HoB2C. This scattering is fitted as diffraction from a Warren-type random magnetic layer lattice and may result from quadrupolar interactions between R3+ spins.     

利用单分子光学探针测量幂律分布的聚合物动力学

研究聚合物薄膜纳米尺度的动力学特性对于高性能材料的制备具有重要的意义.本文利用尼罗红单分子作为光学探针吸附在聚丙烯酸甲酯(PMA)聚合物链上,研究该聚合物薄膜的动力学特性.通过单分子散焦宽场荧光成像显微镜技术测量了单分子随PMA聚合物链转动弛豫的三维再取向特性,当环境温度高于PMA的玻璃点温度19 K时,发现处于PMA聚合物薄膜中的单分子光学探针的转动态和非转动态的持续时间概率密度服从指数截止的幂律分布.研究结果表明该温度下PMA聚合物薄膜的纳米环境动力学仍存在空间和时间异构性.     

Growth of CuO chains on Ag(110) surfaces

The (AgO) chains grown along the 〈001〉 direction on Ag(110) disappeared by the reaction with Cu atoms at room temperature, and new one-dimensional chains grew in the 〈110〉 direction. The STM images at different bias potentials suggest the growth of (CuO) chains in the 〈110〉 direction on the Ag(110) surface. The (CuO) chains on the Ag(110) surface disappeared by heating to 470 K, but they reappeared by exposing to O₂ at room temperature.     

Microscopical investigations of nisin-loaded nanoliposomes prepared by Mozafari method and their bacterial targeting

Nanoencapsulation may improve activity of protein or polypeptide antimicrobials against a variety of microorganisms. In this study, nanoliposomes prepared from different lipids (Phospholipon 90H, Phospholipon 100H, dipalmitoylphosphatidylcholine (DPPC), stearylamine (SA), dicetyl phosphate (DCP) and cholesterol) by a new, non-toxic and scalable method, were tested for their capacity to encapsulate nisin Z and target bacteria (Bacillus subtilis and Pseudomonas aeruginosa). Factors affecting the entrapment efficiency (charge and cholesterol concentration in the vesicles) and stability of nanoliposomes were assessed. The nanoliposomes and their bacterial targeting were visualised, using different microscopes under air and liquid environments. Nisin was entrapped in different nanoliposomes with encapsulation efficiencies (EE) ranging from 12% to 54%. Anionic vesicles possessed the highest EE for nisin while increase in cholesterol content in lipid membranes up to 20% molar ratio resulted in a reduction in EE. Stability of nanoliposome-encapsulated nisin was demonstrated for at least 14 months at 4 °C (DPPC:DCP:CHOL vesicles) and for 12 months at 25 °C (DPPC:SA:CHOL vesicles).     

Adsorption of CO and H2 on Pt(110)(1 × 2) studied by photoemission of adsorbed xenon (PAX)

The adsorption of hydrogen and carbon monoxide on Pt(110)(1 × 2) at 97 K has been studied by photoemission of adsorbed xenon (PAX). For both species, it appears that adsorption takes place first in the valleys between the microfacets of this reconstructed surface. Only when these sites are saturated, does adsorption take place on other sites (microfacets or ridges) of the surface.     

Phase transitions in molecular crystals of dicarboxylic acids

A comparative analysis of phase transitions in molecular crystals of saturated dicarboxylic acids with {COOH(CH₂) _n COOH} chains of different lengths has been performed by differential scanning calorimetry, which revealed a number of new effects related with specific features of the phase transitions. A quantitative analysis of temperature dependence of the heat capacity has been carried out in the context of the theory of smeared (Λ-shaped) first-order phase transitions.     

CH基团与金刚石(111)面的碰撞反应及其对碳膜生长的影响

等离子体增强化学气相沉积技术中的碳膜选择性自组装机理是高性能碳膜制备过程中的挑战性基础课题.采用经典分子动力学方法,模拟了不同能量(1.625-65 eV)的CH基团在清洁金刚石和吸氢金刚石(111)面上的轰击行为,获得了吸附、反弹、反应等各类事件的发生概率,并据此探讨了含氢碳膜制备过程中CH基团的贡献.结果表明,随着入射能量的增加,CH基团对薄膜生长的贡献由单纯的吸附、反弹机理向反应、吸附混合机理转变,其中最主要的反应过程是释放一个或两个氢原子的反应,而释放氢分子的反应则很少发生.这些反应不仅使薄膜生长过程更均匀、薄膜表面更平整,还降低了薄膜的氢含量.生长机理的转变导致低能量条件下所成薄膜中的多数碳原子都包含一个氢原子作为配位原子,而高能量条件下的薄膜中的碳原子则很少有氢原子作为配位原子.另外,通过分析sp~3-C和sp~2-C数目的变化,研究了CH基团对金刚石基底的破坏作用.     

Interface electronic properties of oligothiophenes: the effect of chain length and chemical substituents

We present a comparison of the energy levels at interfaces between different thiophene based organic semiconductors and gold. The thiophene materials are comprised of oligomers with different length and with additional saturated side chains. Our results demonstrate that the interface dipole at these interfaces is independent of the molecule length as well as of the substitution. In addition, the position of the Fermi level in the gap of the organic semiconductors indicates that these interfaces are not free from interactions.