Small-angle-neutron-scattering from giant water-in-oil microemulsion droplets. II. Polymer-decorated droplets in a quaternary system

Amphiphilic block copolymers of the type poly(ethylenepropylene)-co-poly(ethyleneoxide) dramatically enhance the solubilisation efficiency of non-ionic surfactants in microemulsions that contain equal volumes of water in oil. Consequently, the length scale of the microstructure of such bicontinuous microemulsions is dramatically increased up to the order of a few 100 nm. In this paper, we show that this so-called efficiency boosting effect can also be applied to water-in-oil microemulsions with droplet microstructure. Such giant water-in-oil microemulsions would provide confined compartments in which chemical reactions of biological macromolecules can be performed on a single molecule level. With this motivation we investigated the phase behavior and the microstructure of oil-rich microemulsions containing D(2)O, n-decane(d22), C(10)E(4) and the amphiphilic block copolymer PEP5-PEO5 [poly(ethylenepropylene)-co-poly(ethyleneoxide), weight per block of 5000 g/ mol]. We found that 15 wt % of water can be solubilised by 5 wt % of surfactant and block copolymer when about 6 wt % of surfactant is replaced by the block copolymer. Small-angle-neutron-scattering experiments were performed to determine the length scales and microstructure topologies of the oil-rich microemulsions. To analyze the scattering data, we derived a novel form factor that also takes into account the scattering contribution of the hydrophobic part of the block copolymer molecules that reside in the surfactant shell. The quantitative analysis of the scattering data with this form factor shows that the radius of the largest droplets amounts up to 30 nm. The novel form factor also yielded qualitative information on the stretching of the polymer chains in dependence on the polymer surface density and the droplet radius.     

Pulse radiolytic investigation of perfluorinated surfactants in aqueous solutions

Pulse radiolysis studies were performed for aqueous solutions of ammonium perfluorooctanoate, tetraethylammonium perfluorooctyl sulfonate, and an ammonium salt of a carboxylic perfluoropolyether derivative. The protiated system of sodium octanoate was also examined for comparison. The rate constants of hydrated electron (e⁻ _aq) and ^·OH radical reactions with these amphiphiles, and absorption spectra of the intermediate products are reported for the first time. It is demonstrated that the critical micellar concentrations (CMC) can be determined from the kinetic data. The observed differences in e⁻ _aq reactivity towards fluorinated amphiphiles above CMC are rationalized in terms of different charge density at the micellar interface.     

Pulse radiolytic investigation of the reaction of hydroxyl radicals with gentamycin

Hydroxyl radicals were generated radiolytically in N₂O-saturated aqueous solutions of the aminoglycoside antibiotic, gentamycin. Using the pulse radiolysis technique, the rate constant of OH radicals with gentamycin determined was 1.2·10⁹ dm³·mol⁻¹·s⁻¹. Upon^.OH attack a transient species with an absorption maximum at 270 nm is observed which decays by second-order kinetics within the solute concentration range of 3.2·10⁻⁵ to 1·10⁻³mol·dm⁻³. Transient species undergoes transformation to a permanent product absorbing between 260 and 340 nm with maximum absorption at 300 nm. Rate constant of the reaction of bimolecular decay of gentamycin radicals, k (Gen^.+Gen^.) was found to be ≈ 1.4·10⁷ dm³·mol⁻¹·s⁻¹.     

High-resolution NMR studies on radiolytic reactions in polyethylene

High-resolution NMR spectra was obtained for linear polyethylene powder irradiated by ⁶⁰Co γ-rays in vacuo or in air. For the sample irradiated in vacuo, the spectra consist of two components having different line width. The narrow component was assigned to soluble molecules and the broad one to gel. When samples are irradiated in air, their spectra show no broad component. The GPC curves obtained for the samples irradiated in air shift to high elution counts (low molecular weight) upon increase of the irradiation dose. It is concluded that oxidative degradation is the predominant reaction in the sample irradiated in air.     

Pulse radiolytic study of the triplet excited state of naphthalene in mixed solvents

The triplet excited state of naphthalene (³N^*) has been produced by irradiating solutions of naphthalene in mixtures of isopropanol-formamide, acetonitrile-formamide and N,N-dimethylformamide — formamide mixtures with 2 microsecond electron pulses. The yield and decay kinetics of the triplet have been studied over a wide range of compositions of the mixtures. An attempt has been made to explain the variation in the yields and decay rate constants on the basis of the micro properties of the solvent mixtures.     

Reactions of halogenated organic peroxyl radicals with some biologically important compounds in a quaternary microemulsion

Reactions of various halogenated peroxyl radicals with guanine, uric acid, xanthine, hypoxanthine and ascorbic acid in a quaternary microemulsion consisting of sodium lauryl sulfate/water/1-pentanol/cyclohexane have been studied using the technique of pulse radiolysis. For all purine derivatives and ascorbic acid, formation of the respective radical cations have been observed. Variation in biomolecular rate constant values for the reactions of peroxyl radicals with the above-mentioned compounds has been discussed in terms of diffusion of radicals.     

1/f -noise in metallic clusters

Zeitschrift für Physik D Atoms,Molecules and Clusters - When the cluster excitation energy is such that the hopping between different isomers becomes energetically allowed, the power spectrum...     

Distribution of interatomic distances in large metallic clusters

Spherically averaged pseudopotential (SAPS) calculations have been done for Mg _n clusters, withn up to 250 within the framework of density functional theory. The electronic structure is computed resorting to the Thomas-Fermi-Dirac-Weizsäcker (TFDW) approximation for the kinetic energy. The equilibrium geometries have been obtained by minimizing the total cluster energy with respect to the atomic positions using the steepest-descent method. The ground state geometries obtained in this way are formed by spherical atomic shells, the number of them increasing with cluster size, up to a number of four for the biggest sizes considered here. An analysis of the distribution of the interatomic distances shows that the more internal is the shell, the more contracted are the interatomic distances. This effect diminishes progressively with increasing cluster size. For the purpose of comparison, similar calculations have been done with Cs _n clusters in the same size range, allowing us to reproduce previous results obtained using a more elaborated density functional technique (Kohn-Sham method). The inhomogeneous contraction of interatomic distances then appears as a general fact for simple metallic clusters and not only for alkaline ones.     

Ionic vibrational breathing mode of metallic clusters

The energy of the vibrational mode with spherical symmetry, in which the ionic cores oscillate in the radial direction around the equilibrium geometry (ionic breathing mode) is calculated for trivalent (Al_N, 2≤N≤50) and monovalent (Na_N, 2≤N≤73; Cs_N, 2≤N≤74) metallic clusters. The ground-state total energy is calculated using density functional theory, with a spherically averaged pseudopotential to describe the ion–electron interaction and optimizing the geometry by the simulated annealing technique. The energy of the ionic mode is calculated by diagonalization of the dynamical matrix including the electronic relaxation in the linear response approximation. The compressibility and bulk modulus of the metallic cluster are obtained from the energies of the monopole oscillations. These energies present a linear behavior on the inverse of the cluster radius, which is analyzed using a semiclassical liquid drop mass formula for the total energy of the clusters and a scaling model. The values of the vibrational frequencies present electronic shell closing effects for the three metals.©1997 John Wiley & Sons, Inc.     

Molecular clusters as models of metallic catalysts

A critical view of the use of molecular clusters as models of metallic catalysts and as means of modelling chemistry at the surface is presented. The major problems that still exist in the identification of surface adsorbed species and the bonding modes they adopt on reaction with the variety of different metal faces available on the surface of close-packed metal arrays are identified. Limitations have been placed on any direct comparisons because of the relatively small size of clusters under examination and the non-planar characteristics. The use of molecular clusters in this way has led to a much clearer understanding of the bonding mode adopted by a variety of chemisorbed species and can provide answers to long-standing problems.     

Pulse radiolysis investigations on the reactions of primary radiolytic species of water with atropine

On pulse radiolysis of N₂O saturated aqueous solutions of atropine, an optical absorption band (_max at 320 nm,e=2.81·10³ dm³·mol^–1·cm^–1) was observed, which is assigned to the product of reaction of OH radicals with the solute. This absorption decayed following second order kinetics with a rate constant of 4.5·10⁸ dm³·mol^–1·s^–1. The rate constant for the reaction of OH radicals with atropine as estimated by following the build-up kinetics is 2.7·10⁹ dm³·mol^–1·s^–1. The H atoms also reacted with this compound to produce a transient absorption band behaving similarly to the one observed in the case of reaction with OH radicals. The transient species formed in both cases is assigned to a radical derived by H atom abstraction by H/OH radicals from the parent compound. This radical was unreactive towards 2-mercaptoethanol. e _aq ^– was found to react with atropine forming a transient band with _max at 310 nm (=3.55·10³ dm³·mol^–1). Its decay was also second order with a rate constant of 1.64·10⁹ dm³·mol^–1·s^–1. The bimolecular rate constant for the reaction of e _aq ^– with atropine as estimated from the decay of e _aq ^– absorption at 720 nm is 3.9·10⁹ dm³·mol^–1·s^–1. Specific one-electron oxidizing and reducing agents (such as Cl ₂ ^– , Tl²⁺, SO ₄ ^– and (CH₃)₂COH, CO ₂ ^– , respectively) failed to oxidize or reduce this compound in aqoues solutions. The radical anion of atropine formed by its reaction with e _aq ^– was found to reduce thionine and methyl viologen with bimolecular rate constant of 3.8·10⁹ and 3.2·10⁹ dm³·mol^–1·s^–1, respectively.     

Electronic shells and shells of atoms in metallic clusters

Intensity anomalies (magic numbers) have been observed in the mass spectra of sodium clusters containing up to 22 000 atoms. For small clusters (Na _n ,n≤1500) the anomalies appear to be due to the filling of electronic shells (groups of subshells having the same energy). The shells can be characterized rather well by a pseudoquantum-number, indicating the possible existence of a symmetry higher than spherical. The mass spectra of larger clusters (1500≤n≤22 000) are well explained by the completion of icosahedral or cuboctahedral shells of atoms. The fact that the two types of shells (electron and atom) occur in distinct and non-overlapping size intervals might indicate the existence of a “liquid” to “solid” transition in going from small to large clusters.     

Synthesis and pulse radiolytic studies of mono- and polyfluorinated biphenyls

The polyfluorinated biphenyls investigated were synthesized by reaction of fluorinated anilines with excess benzene and characterized by spectroscopic methods. Upon pulse radiolysis of the polyfluorinated biphenyls in dichloroethane radical cations are formed. By comparison with unsubstituted biphenyl the fluoro-substitution does not exert a strong effect on the optical absorption spectra or the first half-lives of the biphenyl radical cations.     

Large fullerenes stabilized by encapsulation of metallic clusters

Structures are proposed for six endohedral metallofullerenes with large carbon cages (from C(92) to C(100)) on the basis of sizeable (LUMO-4)-(LUMO-3) gap and the formal transfer of six electrons to the cages.     

Shell structure and level spacing distribution in metallic clusters

The lattice gas Monte Carlo and tight binding method is used to study the electronic shell structure in large metallic clusters. The average density of states of a large ensemble of deformed clusters shows the same shell structure as the most spherical geometry. The level spacing distribution at the Fermi level is a Wigner distribution.     

.OH诱导氧化磷酰化甲硫氨酸机理的脉冲辐解研究

采用脉冲辐解动态吸收光谱研究了.OH自由基诱导N-二异丙基磷酰化甲硫氨酸(NDM)水溶液的氧化过程, 结果表明.OH主要进攻NDM中硫原子, 并形成含硫三电子键NDM2^+[S], 其在480nm处有最大吸收峰, 形成和衰变均呈一级反应, 推导了反应机理,并与.OH自由基诱导氧化甲硫氨酸水溶液机理进行了比较。     

Optical properties of fractal clusters of small metallic particles

In this paper we describe a method to calculate the optical properties of deterministic fractal clusters. Our method takes advantage of the fact that deterministic fractals can be constructed by an iterative rule. We calculate first the optical properties of a small cluster that describes one stage in the iteration. The optical properties of this cluster are then assigned to an “effective particle”. A small number of these produce the next stage in the fractal construction. We performed the calculations for metallic particles with dielectric functions described by the hydrodynamic model. Results in the dipolar and quadrupolar approximations for a cluster at the second fractal stage shows the double extinction peak often seen in experimental studies.     

高硅煤中Si-Al-Fe-Ca四元体系碳热反应研究

研究了不同温度条件下高硅煤中矿物组成比例下的Si-Al-Fe-Ca多元体系的碳热反应以及其影响因素。通过XRD和FESEM-EDS技术对各还原产物进行分析。结果表明,Fe_2O_3对含硅矿物的碳热反应起促进作用,Fe可以有效提高Si反应活性。CaO在较低温度时与灰中的Al_2O_3和SiO_2反应形成致密的Ca-Al-Si相共熔体CaAl_2Si_2O_8,阻碍含硅矿物碳热反应的进行。随着温度的升高,继续反应生成SiC、CaAl_4O_7和CaSiO_3。热力学模拟计算与实验结果基本吻合。     

Mechanical properties of one-phase microemulsion system

A theoretical approach for free Gibbs energy of microemulsion ternary systems water-oil-non-ionic surfactant of arbitrary size and shape is presented. We consider the Gibbs energy for three different geometries (flat, spherical and cylindrical) to estimate the free energy of surfactant-oil-water microemulsion. We also used a lattice-based self-consistent field (SCF) theory to calculate the free energy and the mechanical properties (the mean bending modulus k _c , and the spontaneous curvature J ₀, and the saddlesplay modulus $\bar k$ ) of such system. The values obtained by our theoretical approach were compared qualitatively with those predicted by SCF theory. The results of theoretical approach were in a good agreement with those of SCF in the region where the values of free energy approach zero for the flat geometry. We demonstrated that the parameters k _c, J ₀ and $\bar k$ strongly depend on the surfactant concentration.