Diffusion coefficients in a lamellar lyotropic phase: evidence for defects connecting the surfactant structure

We measure diffusion coefficients in the lamellar phase of the nonionic binary system C(12)EO(6)/H(2)O using fluorescence recovery after photobleaching. The diffusion coefficient across the lamellae shows an abrupt increase upon approaching the lamellar-isotropic phase transition. We interpret this feature in terms of defects connecting the surfactant structure. An estimation of the defect density and of the variation in defect energy close to the transition is given in terms of a simple model.     

Nano-control of self-assembled biomolecular structures

We have controlled the structure of self-assembled systems by introducing charges (charge effect) and polymeric tails (steric effects) on a spherical–cylindrical shape of nonionic surfactant micelles. In detail, we studied the effects of a phospholipid (DL-α-phosphatidycholine dimyristol: DMPC) on the shape of nonionic surfactant micelles (penta-ethyleneglycol mono-n-dodecyl ether: C₁₂E₅), which has been studied in terms of an aggregation number, critical micellization concentration (CMC), second virial coefficient (A₂), and hydrodynamic diameter (D_H) by laser light scattering. DMPC, DOPC (DL-α-phosphatidylcholine dioleoyl), and DMPE (DL-α-phosphoethanolamin dimyristol) molecules added in C₁₂E₅ micelle solutions decrease the spontaneous curvatures, leading to an increase of the end-cap energy E_c that favors micellar growth. Based on the CMC values, the total free energy per micelle of C₁₂E₅/DMPC mixtures is estimated. The free energy per micelle of C₁₂E₅/DMPC mixtures decreases as DMPC is added. This is consistent with the decrease of A₂ and the strong hydrophobicity of DMPC compared with C₁₂E₅. The average contour length, the diffusion coefficient, and the end-cap energy of mixed micelles are estimated based on the CMC and molecular specific volumes of the moiety. The end-cap energy of the mixed micelles and the average contour length increase as DMPC is added, which is also reasonable considering the molecular structure of DMPC. Furthermore, the diffusion coefficients obtained from dynamic laser light scattering are in excellent agreement with the estimated diffusion coefficients obtained from a one-dimensional growth model based on static light scattering measurements.Charged lipid (1,2-dioleoyl-3-trimethylammonium-propane) and polymer lipid (1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine-[poly(ethylene glycol)]) increase the spontaneous curvatures, resulting in breaking micelles into small size. When the lipids are added, the hydrodynamic diameter of the micelles of C₁₂E₅/lipids is nearly temperature independent due to the strong charge or steric repulsion.     

Quantum percolation in granular metals

Theory of quantum corrections to conductivity of granular metal films is developed for the realistic case of large randomly distributed tunnel conductances. Quantum fluctuations of intergrain voltages (at energies E much below the bare charging energy scale E(C)) suppress the mean conductance g (E) much more strongly than its standard deviation sigma(E). At sufficiently low energies E(*) any distribution becomes broad, with sigma(E(*)) approximately g (E(*)), leading to strong local fluctuations of the tunneling density of states. The percolative nature of the metal-insulator transition is established by a combination of analytic and numerical analysis of the matrix renormalization group equations.     

Role of dislocation loops on the elastic constants of lyotropic lamellar phases

We study the role of dislocation loops defects on the elasticity of lamellar phases by investigating the variation of the lamellar elastic constants, ˉ and K, induced by the proliferation of these defects. We focus our interest on one particular lamellar phase made up of a mixture of C₁₂E₅ and DMPC in water, which is already well-characterised. This lamellar phase undergoes a second-order (or weakly first-order) lamellar-to-nematic phase transition at about 19^°C and dislocation loops are seen to proliferate within the lamellar structure when temperature is decreased below 30^°C. The values of both elastic constants of this given lamellar phase are measured as a function of temperature, approaching the lamellar-to-nematic transition, with the help of Quasi-Elastic Light Scattering (QELS) on oriented lamellar phases. Very surprisingly we observe a strong and rapid increase in both ˉ and K as the lamellar-to-nematic transition temperature is approached. These increases are seen to start as soon as dislocation loops can be observed in the lamellar phase. We interpret our results as being the consequence of the appearance and proliferation of dislocation loops within the lamellar structure. According to a simple model we developped we show that ˉ and K are proportional to the density of dislocation loops in the lamellar phase.     

Lamellar-to-nematic phase transition in a lipid-surfactant mixture

A lyotropic system, consisting of a lecithin (DMPC) and a non-ionic surfactant (C₁₂E₅) in water was studied. The system exhibits a lamellar-to-nematic phase transition. The nematic phase appears as the temperature is decreased and only exists in a very limited temperature and concentration range, for specific lipid-to-surfactant ratios. While a lamellar phase is found at higher temperatures in both mixed and pure C₁₂E₅ systems, the transition to the nematic phase at lower temperatures coincides with a micellar phase in the pure C₁₂E₅ system. The transition appears to be driven by the strong temperature dependence of the surfactant film spontaneous curvature. The structural properties of the lamellar phase close to the lamellar-to-nematic boundary have been studied by polarised light microscopy and small-angle neutron and X-ray scattering experiments. The signature of a helical defect with Burgers vector of magnitude 2 is apparent in our data, close to the lamellar-to-nematic phase transition. The proliferation of screw dislocations in the lamellar phase might be a plausible mechanism for driving this transition. Received 6 July 1999 and Received in final form 17 April 2000     

Pressure-induced structural transition of nonionic micelles

We report dynamic light scattering and small angle neutron scattering studies of the pressure-induced structural transition of nonionic micelles of surfactant polyoxyethylene 10 lauryl ether (C12E10) in the pressure range 0 to 2000 bar. Measurements have been performed on 1 wt% C12E10 in aqueous solution with and without the addition of KF. Micelles undergo sphere to lamellar structural transitions as the pressure is increased. On addition of KF, rod-like micelles exist at ambient pressure, which results in rod-like to lamellar structural transition at a much lower pressure in the presence of KF. Micellar structural transitions have been observed to be reversible.      

Measurement of the cascade transition via the first excited state of 16O in the 12C(alpha,gamma)16O reaction, and its S factor in stellar helium burning

Radiative alpha-particle capture into the first excited, J(pi)=0+ state of 16O at 6.049 MeV excitation energy has rarely been discussed as contributing to the 12C(alpha,gamma)16O reaction cross section due to experimental difficulties in observing this transition. We report here measurements of this radiative capture in 12C(alpha,gamma)16O for center-of-mass energies of E=2.22 MeV to 5.42 MeV at the DRAGON recoil separator. To determine cross sections, the acceptance of the recoil separator has been simulated in GEANT as well as measured directly. The transition strength between resonances has been identified in R-matrix fits as resulting both from E2 contributions as well as E1 radiative capture. Details of the extrapolation of the total cross section to low energies are then discussed [S6.0(300)=25(-15)(+16) keV b] showing that this transition is likely the most important cascade contribution for 12C(alpha,gamma)16O.     

Solving topological defects via fusion

Integrable defects in two-dimensional integrable models are purely transmitting thus topological. By fusing them to integrable boundaries new integrable boundary conditions can be generated, and, from the comparison of the two solved boundary theories, explicit solutions of defect models can be extracted. This idea is used to determine the transmission factors and defect energies of topological defects in sinh-Gordon and Lee–Yang models. The transmission factors are checked in Lagrangian perturbation theory in the sinh-Gordon case, while the defect energies are checked against defect thermodynamic Bethe ansatz equations derived to describe the ground-state energy of diagonal defect systems on a cylinder. Defect bootstrap equations are also analyzed and are closed by determining the spectrum of defect bound-states in the Lee–Yang model.     

Deffect free energies in lattice gauge theories with matter fields

We introduce and analyze different defect free energies in lattice gauge theories with matter fields. We investigate in which way the behaviour of these defect free energies characterizes different phase (and different regimes not separated by bulk phase boundaries) of such theories. Our main analytical results concern the ₂ model, but some of our concepts and method extend to a fairly general class of models, including non-abelian lattice gauge theories.We also estimate masses of topological solitons (vortices and magnetic monopoles) in terms of defect free energies of line defects.     

Giant dielectric permittivity observed in Li and Ti doped NiO

A giant low-frequency dielectric constant ( epsilon 0 approximately 10(5)) near room temperature was observed in Li,Ti co-doped NiO ceramics. Unlike currently best-known high epsilon 0 ferroelectric-related materials, the doped oxide is a nonperovskite, lead-free, and nonferroelectric material. It is suggested that the giant dielectric constant response of the doped NiO could be enhanced by a grain boundary-layer mechanism as found in boundary-layer capacitors. In addition, there is about a one-hundred-fold drop in the dielectric constant at low temperature. This anomaly is attributed to a thermally excited relaxation process rather than a thermally driven phase transition, as for that yielding ferroelectrics.     

Optical transition energies for carbon nanotubes from resonant Raman spectroscopy: environment and temperature effects

This Letter reports the laser energy dependence of the Stokes and anti-Stokes Raman spectra of carbon nanotubes dispersed in aqueous solution and within solid bundles, in the energy range 1.52-2.71 eV. The electronic transition energies (E(ii)) and the radial breathing mode frequencies (omega(RBM)) are obtained for 46 different (18 metallic and 28 semiconducting) nanotubes, and the (n,m) assignment is discussed based on the observation of geometrical patterns for E(ii) versus omega(RBM) graphs. Only the low energy component of the E(M)(11) value is observed from each metallic nanotube. For a given nanotube, the resonant window is broadened and down-shifted for single wall carbon nanotube (SWNT) bundles compared to SWNTs in solution, while by increasing the temperature, the E(S)(22) energies are redshifted for S1 [(2n+m) mod 3=1] nanotubes and blueshifted for S2 [(2n+m) mod 3=2] nanotubes.     

Triple α-particle resonances in the decay of hot nuclear systems

The Efimov(Thomas) trimers in excited ~(12) C nuclei, for which no observation exists yet, are discussed by means of analyzing the experimental data of ~(70(64))Zn(~(64) Ni) + ~(70(64))Zn(~(64) Ni) reactions at the beam energy of E/A = 35 MeV/nucleon. In heavy ion collisions, a-particles interact with each other and can form complex systems such as ~8 Be and ~(12) C. For the 3 a-particle systems,multi-resonance processes give rise to excited levels of ~(12) C. The interaction between any two of the 3 a-particles provides events with one, two or three ~8 Be. Their interfering levels are clearly seen in the minimum relative energy distributions. Events with the three a-particle relative energies consistent with the ground state of ~8 Be are observed with the decrease of the instrumental error for the reconstructed 7.458 MeV excitation level in ~(12) C, which was suggested as the Efimov(Thomas) state.     

X-ray scattering and volumetric <Emphasis Type="Italic">P-V-T</Emphasis> studies of the dimyristoylphosphatidylcholine-water system

The results of a study of the temperature and pressure dependence of isothermal compressibility of dimyristoylphosphatidylcholine (DMPC) are presented. The data were obtained using a small-angle X-ray scattering instrument in the Institute of Synthetic Polymer Materials (Moscow, Russia) and a device designed in the Laboratory of Neutron Physics, Joint Institute for Nuclear Research (Dubna, Russia), for studying the liquid systems by a volumetric P-V-T method. The minute baric investigation of the region of the main phase transition (transition from the gel phase into the liquid crystalline phase) was carried out. The points of the main phase transition were determined, and the phase diagram of DMPC was plotted over the pressure range of 1–800 bar at temperature from 24 to 35°C.     

Novel surface tension isotherm for surfactants based on local density functional theory

In this Letter we report a new general method for calculating of surface tension isotherms in the presence of surfactants, based on a local density functional. We illustrate this method by deriving the interfacial tension isotherm for nonionic surfactants at an air-water or oil-water interface by using the self-consistent field theory of polymer brushes. We consider a particular case of local density functional to calculate explicitly how the interfacial tension and the surfactant adsorption depend on the surfactant bulk concentration. Experimental data for the surface tension and the surfactant adsorption isotherm for nonionic surfactants were interpreted with the help of the new isotherm. Very good agreement between the adsorption of n-dodecyl pentaoxyethylene glycol ether (C12E5) at an air-water interface, calculated from the surface tension isotherm and small-angle neutron-scattering is obtained.     

Small angle neutron scattering study of temperature-independent formulation of mixed micellar structures

SANS measurements have been performed on mixed systems of ionic surfactant sodium dodecyl sulphate (SDS) and nonionic surfactant polyoxyethylene 10 lauryl ether (C12E10). The total concentration of the mixed system was kept fixed (10 wt%) and the ionic to nonionic surfactant ratio varied in the range 0 to 1. The temperature effect on the structures of mixed micelles has been studied for temperatures between 30 and 75°C. Micelles of pure ionic and nonionic surfactants show opposite trends when the temperature is increased. Sizes of pure ionic micelles decrease and those of nonionic micelles increase with increase in temperature. We show a formulation balancing these two effects which is temperature-independent and consists of about 25% of ionic surfactants in the mixed system. Contrast variation SANS measurements by contrast matching one of the surfactant components to the solvent suggest homogeneous single mixed micelles of the two components in the mixed systems.      

Line defect dynamics around a colloidal particle

We study experimentally the dynamics of a topological defect located around a colloidal particle suspended in a thermotropic nematic liquid crystal. The considered defect consists of a disclination loop encircling the particle at the equator. Under specific conditions, it is shown that this disclination continuously shrinks to a hedgehog defect located in the immediate vicinity of the particle. This phenomenon corresponds to a transition between an elastic quadrupolar configuration and an elastic dipolar configuration. We performed a basic numerical calculation to get an estimate of the dissipated energy during the transition; we compare the results with theoretical predictions that describe the elastic energy of particles surrounded by defects. Received 21 December 2001     

戊二烯基与氧分子反应的理论研究

用G3B3//B3LYP/6-311G(d,p)方法计算了戊二烯基与氧分子反应的势能面．计算结果显示，反应的第一步为戊二烯基与氧分子结合形成两种过氧化加成物，过氧基分别连结在末端C1位置和中间C3位置．在反应的第二步，两种过氧化加成物分别发生一系列氢转移异构化反应和成环异构化反应．最后，这些氢转移异构体和环化异构体分别经过单分子分解通道，生成不饱和醛酮和羟基．共计算了20个稳定态和14个过渡态的结构和能量，通过比较各反应通道的能垒和反应热，提出以C2H3O和C3H4O为最终产物的通道可能是整个反应的主要通道．此外，计算结果还表明一些过C5H7O2自由基可能作为反应体系的长寿命中间体而存在，这与Zils等人的实验观测结果一致．     

Ab initio calculations for large dielectric matrices of confined systems

Calculations for optical excitations in confined systems require knowledge of the inverse screening dielectric function epsilon(-1)(r,r(')), which plays a crucial role in determining exciton binding energies. We present a new efficient real-space method of inverting and storing large ab initio dielectric matrices of confined systems, which relies on the separability of epsilon matrix in r and r('). The method has allowed, for the first time, full ab initio calculation of epsilon(-1)(r,r(')) of dimension N approximately 270 000, and for quantum dots as large as Si35H36. The effective screening in Si quantum dots up to 1.1 nm in diameter is found to be very ineffective with average dielectric constants ranging from 1.1 to 1.4.     

钪与氧空位共掺杂锐钛矿相TiO2的形成能与电子结构的第一性原理研究

采用基于密度泛函理论的第一性原理研究了钪(Sc)、氧空位(O_V)单/共掺杂锐钛矿相TiO₂,对晶体结构、形成能以及电子结构进行了对比分析.研究结果表明,Sc-TiO₂在富氧环境下缺陷形成能为负值,富钛环境下缺陷形成能为正值,表明Sc-TiO₂只能在富氧环境下制备;O_V-TiO₂、Sc-O_V-TiO₂在富氧或富钛环境下缺陷形成能均为负值,但富氧环境下形成能更低;O_V-TiO₂的0/1-缺陷电荷转变能级为深能级,而Sc-TiO₂的0/1-缺陷电荷转变能级则属于相对较浅能级;与纯锐钛矿相TiO₂相比,Sc-TiO₂的禁带宽度略有减小,但O_V-TiO₂、Sc-O_V-TiO₂禁带宽度变宽.     

Buckling induced by a topological defect in a chain

The chain buckling induced by a topological defect (anti-kink) is investigated using a generalized Frenkel–Kontorova model. Instead of a single-peak appeared in the classical Euler instability, the buckling shape induced by the topological defect is a Sine-like pattern (two-peaks) that is antisymmetric regarding the point of the maximum stress. Evolution of the unstable buckling mode is clearly characterized by two time scales: one is the lifetime of the unstable phase, the other is the growth rate of the new phase. The phase transition curve of the buckling is a linear function of the chain length.