Hexagonal → cholesteric phase transition of DNA molecules in liquid-crystalline dispersion particles

To assess the character of packing of double-stranded (ds) DNA molecules in liquid-crystalline dispersion particles formed by phase exclusion of DNA molecules from aqueous salt solutions of poly(ethylene glycol), the circular dichroism spectra of these dispersions at different temperatures have been compared. It has been shown for the first time that heating dispersion particles with the hexagonal packing of ds-DNA molecules is accompanied by the hexagonal → cholesteric phase transition. This result can be described using the notion of quasi-nematic layers composed of orientationally ordered adjacent ds-DNA molecules in the structure of dispersion particles; these layers can be packed in two ways dictating their hexagonal or cholesteric spatial structure.     

Influence of interface structure on mass transport in phase boundaries between different ionic materials Experimental studies and formal considerations

Abstract  

Internal and external interfaces in solids exhibit completely different transport properties compared to the bulk. Transport parallel to grain or phase boundaries is usually strongly enhanced. Transport perpendicular to an interface is usually blocked, i.e., transport across an interface is often much slower. Due to the high density of interfaces in modern micro- and nanoscaled devices, a severe influence on the total transport properties can be expected. In contrast to diffusion in metal grain boundaries, transport phenomena in boundaries of ionic materials are still less understood. The specific transport properties along metal grain boundaries are explained by structural factors like packing densities or dislocation densities in the interface region. In most studies dealing with ionic materials, the interfacial transport properties are merely explained by the influence of space charge regions. In this study the influence of the interface structure on the interfacial transport properties of ionic materials is discussed in analogy to metallic materials. A qualitative model based on the density of misfit dislocations and on interfacial strain is introduced for (untilted and untwisted) phase boundaries. For experimental verification, the interfacial ionic conductivity of different multilayer systems consisting of stabilised ZrO₂ and an insulating oxide is investigated as a funtion of structural mismatch. As predicted by the model, the interfacial conductivity increases when the lattice mismatch is increased.     

十六烷基甲苯磺酸钠的界面性能研究

用自制的3种十六烷基甲苯磺酸钠,研究了其正构烷烃/水体系的界面性能。分别考察了磺酸盐支化程度及浓度等内部因素以及外加助剂脂肪醇类型和无机盐浓度等外界因素对磺酸盐最小烷烃碳数n_min以及界面张力值的影响。结果表明,磺酸盐支化程度增加,其n_min变大,最低界面张力值变小;而随着磺酸盐浓度的增加,界面张力值先下降后上升;随着助剂脂肪醇碳链长度的增加,其n_min逐渐变大;无机盐的影响则表现为随着盐浓度的增加界面张力值先下降后上升,超低界面张力值出现在一个适宜的盐浓度范围内。     

Controlling the interparticle spacing of Au-salt loaded micelles and Au nanoparticles on flat surfaces

The self-organization of diblock copolymers into micellar structures in an appropriate solvent allows the deposition of well ordered arrays of pure metal and alloy nanoparticles on flat surfaces with narrow distributions in particle size and interparticle spacing. Here we investigated the influence of the materials (substrate and polymer) and deposition parameters (temperature and emersion velocity) on the deposition of metal salt loaded micelles by dip-coating from solution and on the order and inter-particle spacing of the micellar deposits and thus of the metal nanoparticle arrays resulting after plasma removal of the polymer shell. For identical substrate and polymer, variation of the process parameters temperature and emersion velocity enables the controlled modification of the interparticle distance within a certain length regime. Moreover, also the degree of hexagonal order of the final array depends sensitively on these parameters.     

Heterogeneous nucleation of poly(ethylene terephthalate)

The effect of various metal salts as nucleating additives for poly(ethylene terephthalate) (PET) has been investigated. In the case of sodium benzoate and probably for all other effective nucleating additives, the nucleation process can be divided into a “heterogeneous particle nucleation” performed by the unreacted salt and a “homogeneous nucleation” due to the polymer–sodium (metal) salt formed during the extrusion. This polymer–sodium (metal) salt is the major nucleating agent in these systems. We have also shown the fundamental difference between the concept of a nucleating additive and that of a nucleating agent.     

Improved thermal stability of Langmuir-Blodgett films through an intermolecular hydrogen bond and metal complex

Langmuir-Blodgett (LB) films of N-octadecanoyl-L-alanine and its silver and zinc complexes have been investigated by variable-temperature Fourier transform infrared transmission spectroscopy. The thermal stability of LB films is improved through an intermolecular hydrogen bond and metal complex. The intermolecular hydrogen-bonding interaction between hydrophilic head groups in the same monolayers and the metal complex between one head group and another in the neighboring monolayers considerably increase the interaction between the corresponding hydrophobic alkyl chains. It is shown that the transformation of the triclinic subcell packing of the molecules in the LB films prior to and after the silver complex into hexagonal packing occurs before the phase transition accompanied with a change in molecular orientation. The phase transition behavior of the LB films is varied from a small temperature interval to large one depending on the hydrogen bond and metal complex.     

The influence of pH on phosphatidylcholine monolayer at the air/aqueous solution interface

The measurements of the interfacial tension at the air/aqueous subphase interface as the function of pH were performed. The interfacial tension of the air–aqueous subphase interface was divided into contributions of individuals. A simple model of the influence of pH on the phosphatidylcholine monolayer at the air/hydrophobic chains of phosphatidylcholine is presented. The contributions of additive phosphatidylcholine forms (both interfacial tension values and molecular area values) depend on pH. The interfacial tension values and the molecular areas values for LH⁺, LOH⁻ forms of phosphatidylcholine were calculated. The assumed model was verified experimentally.     

Ordered packing of soft discoidal system

A novel mesoscopic simulation method is adopted to study the ordered packing of the anisotropic disklike particles with a soft repulsive interaction, which possesses a modified anisotropic conservative force type used in dissipative particle dynamics. We examine the influence of the shape of the particles, the angular width of the repulsion, and the strength of the repulsion on the packing structures. Specifically, an ordered hexagonal columnar structure is obtained in our simulations. Our study demonstrates that an anisotropic repulsive potential between soft discoidal particles is sufficient to produce a relatively ordered hexagonal columnar structure.     

Templating behavior of a long-chain ionic liquid in the hydrothermal synthesis of mesoporous silica

The long-chain ionic liquid (IL) 1-hexadecyl-3-methylimidazolium chloride (C(16)mimCl) was used as a template to prepare porous silica with a two-dimensional hexagonal p6mm mesopore structure (MCM-41-type) as well as with a cubic Ia3d (gyroid, MCM-48-type structure) framework in basic synthesis medium via a hydrothermal synthesis procedure. A systematic study was carried out addressing the influence of the relative concentration of the IL and the pH on the mesostructure. As a main result, the IL template shows a broad range of conditions that allow the synthesis of the gyroid mesostructure with improved reproducibility. Unexpectedly, the formation of the hexagonal phase is less favorable, as the latter is quite sensitive to variations in parameters. This preference for the bicontinuous structure can be attributed to the special headgroup packing of ILs containing imidazolium groups.     

Monolayer characteristics of a long-chain N,O-diacyl substituted ethanolamine at the air/water interface

The N- and/or O-acylation of amphiphilic ethanolamine attracts particular attention because of its interesting biological, pharmaceutical, and medicinal properties. Tetradecanoic acid-2-[(1-oxotetradecyl)amino]ethyl ester (TAOAE) as the selected N,O-diacyl derivative of ethanolamine has been synthesized in order to obtain first information about its main interfacial characteristics, such as the surface pressure-area (π-A) isotherms, the morphology of the condensed phase domains, the lattice structure of the condensed phase, and information about the existence of interfacial hydrogen bonds (-NH···O═C-). The π-A isotherms of TAOAE, similar to those of the most usual monolayers of amphiphiles, show a sharp break point (A(c)) indicating the first-order phase transition from the fluid (liquid-expanded (LE), gaseous (G)) to the condensed (liquid-condensed (LC)) phase. On the mesoscopic scale, the dendritic domains homogeneously reflecting suggest an orientation of the alkyl chains perpendicular to the aqueous surface. The grazing incidence X-ray diffraction (GIXD) studies reveal hexagonal packing of the TAOAE molecules oriented perpendicular to the surface in an LS phase. The existence of a hydrogen-bonding network in the monolayer is supported by infrared reflection absorption spectroscopy (IRRAS) experiments.     

Poly(ammonioalkanesulfonate) Blends with Polar Organic Species and Alkali Metal Salts: Structure,Glass Transition and Ionic Conductivity

Because the dipole moment of its zwitterionic side group is very high (μ∼23 D), poly[3-(N,N-diethyl-N-(5-methacryloyoxy-3-oxopentyl)-ammonio) propanesulfonate] affords a unique polar host matrix possessing a strong solvation power towards a variety of polar or ionic guest species. Water, glycerol, liquid ethylammonium nitrate, triethylammoniopropanesulfonate are all good plasticizers with a fairly similar efficiency of ΔT_g∼−2°C/mol% of additive, while a dizwitterion behaves as a weak antiplasticizer. The stoichiometric blends of the polyzwitterion with alkali metal salts of low enough lattice energy such as thiocyanates, trifuoromethanesulfonates, iodides, perchlorates, tetrafluoro or tetraphenylborates, are amorphous systems showing a single glass transition, with plasticization or antiplasticization effects depending on the salt nature. Microphase separation systematically occurs in these binary systems but long-range order is observed only in some cases, with development of lamellar (I⁻) or hexagonal (SCN⁻) structures. Conductivity increases and the dielectric constant of the material decreases as salt is added. The activation energies of the conductivity are not strongly affected either by the state of the material, glassy or viscoelastic, or by the salt nature. © 1997 John Wiley & Sons, Ltd.     

胶体晶体中的两种排列方式及堆积模式

由单分散的有机或无机粒子制备三维有序的胶体晶体越来越受到人们的关注 [1～ 3 ] ,单分散颗粒如何排布和堆积是形成三维有序胶体晶体的关键 .自然界中的蛋白石 (Opal)是由单分散 Si O2 粒子的三维有序堆积中渗入水溶性的硅酸盐固化而成的 .仿照自然界的模式由单分散的有机或无机粒子制备三维有序的胶体晶体是对当今科学技术的一个挑战 [4 ] .以胶体晶体为模板制备有机、无机、金属和陶瓷等的多孔材料在催化、吸附以及光子晶体等方面具有重要的应用前景 [5～ 9] .本文研究了以单分散的聚苯乙烯 -甲基丙烯酸甲酯 -丙烯酸 [P(St- MMA- AA)…     

Equilibrium structure and dynamics of (2R, 3R)-(+)-bis(decyloxy)succinic acid at the air-water interface

A twin-tailed, twin-chiral fatty acid, (2R,3R)-(+)-bis(decyloxy)succinic acid was synthesized and its two dimensional behavior at the air-water interface was examined. The pH of the subphase had a profound effect on the monolayer formation. On acidic subphase, stable monolayers with increased area per molecule due to hydrogen bonding and bilayers at collapse pressures were observed. Highly compressible films were formed at 40 degrees C, while stable monolayers with increased area were observed at sub-room temperatures. Langmuir monolayers formed on subphases containing 1 mM ZnCl2 and CaCl2 revealed two dimensional metal complex formation with Zn2+ forming a chelate-type complex, while Ca2+ formed an ionic-type complex. Monolayers transferred from the condensed phase onto hydrophilic Si(100) and quartz substrates revealed the formation of bilayers through transfer-induced monolayer buckling. Compression induced crystallites in 2D from monolayers and vesicle-like supramolecular structures from multilayers were the noted LB film characteristics, adopting optical imaging and electron microscopy. The interfacial monolayer structure studied through molecular dynamics simulation revealed the order and packing at a molecular level; monolayers adsorbed at various simulated specific areas of the molecule corroborated the (pi-A) isotherm and the formation of a hexagonal lattice at the air-water interface.     

Branched non-ionic oligo-oxyethylene Y-amphiphiles Effect of molecular geometry on the micellar shape 1

A homologous series of branched, non-ionic surfactants with the general formula C_nG(E_mM)₂, where C_n denotes an alkyl chain, G = glycerol and E_mM = oligo-oxyethylene mono-methyl ether, has been prepared from alkyl bromides (n = 10-16) and several monodisperse 1,3-di(methoxyoligo-oxyethylene) ethers of glycerol (m = 3-5). The branched hydrophilic chain is introduced to modify the interfacial area compared to corresponding linear oligo-oxyethylene surfactants (I-amphiphiles) without essentially changing the hydrophilic-lipophilic balance. The phase behaviour of these Y-surfactants in aqueous solution reveals that according to established packing models the branched hydrophilic group strongly stabilizes the cubic and hexagonal mesophases, while a lamellar phase is not observed.     

Effect of the type of the oil phase on stability of highly concentrated water-in-oil emulsions

The water-in-oil high internal phase emulsions were the subject of the study. The emulsions consisted of a super-cooled aqueous solution of inorganic salt as a dispersed phase and industrial grade oil as a continuous phase. The influence of the industrial grade oil type on a water-in-oil high internal phase emulsion stability was investigated. The stability of emulsions was considered in terms of the crystallization of the dispersed phase droplets (that are super-cooled aqueous salt solution) during ageing. The oils were divided into groups: one that highlighted the effect of oil/aqueous phase interfacial tension and another that investigated the effect of oil viscosity on the emulsion rheological properties and shelf-life. For a given set of experimental conditions the influence of oil viscosity for the emulsion stability as well as the oil/aqueous interfacial tension plays an important role. Within the frames of our experiment it was found that there are oil types characterized by optimal parameters: oil/aqueous phase interfacial tension being in the region of 19–24 mN/m and viscosity close to 3 mPa s; such oils produced the most stable high internal phase emulsions. It was assumed that the oil with optimal parameters kept the critical micelle concentration and surfactant diffusion rate at optimal levels allowing the formation of a strong emulsifier layer at the interface and at the same time creating enough emulsifier micelles in the inter-droplet layer to prevent the droplet crystallization.     

Quantitative SAXS analysis of the P123/water/ethanol ternary phase diagram

The ternary phase diagram of the amphiphilic triblock copolymer PEO-PPO-PEO ((EO)(20)(PO)(70)(EO)(20) commercialized under the generic name P123), water, and ethanol has been investigated at constant temperature (T = 23 degrees C) by small-angle X-ray scattering (SAXS). The microstructure resulting from the self-assembly of the PEO-PPO-PEO block copolymer varies from micelles in solution to various types of liquid crystalline phases such as cubic, 3D hexagonal close packed spheres (HCPS), 2D hexagonal, and lamellar when the concentration of the polymer is increased. In the isotropic liquid phase, the micellar structural parameters are obtained as a function of the water-ethanol ratio and block copolymer concentration by fitting the scattering data to a model involving core-shell form factor and a hard sphere structure factor of interaction. The micellar core, the aggregation number, and the hard sphere interaction radius decrease when increasing the ethanol/water ratio in the mixed solvent. We show that the fraction of ethanol present in the core is responsible for the swelling of the PPO blocks. In the different liquid crystalline phases, structural parameters such as lattice spacing, interfacial area of PEO block, and aggregation number are also evaluated. In addition to classical phases such as lamellar, 2D hexagonal, and liquid isotropic phases, we have observed a two-phase region in which cubic Fm3m and P6(3)mmc (hexagonally close packing of spheres (HCPS)) phases coexist. This appears at 30% (w/w) of P123 in pure water and with 5% (w/w) of ethanol. At 10% (w/w) ethanol, only the HCPS phase remains present.     

Theory of nanoparticle diffusion in unentangled and entangled polymer melts

We propose a statistical dynamical theory for the violation of the hydrodynamic Stokes-Einstein (SE) diffusion law for a spherical nanoparticle in entangled and unentangled polymer melts based on a combination of mode coupling, Brownian motion, and polymer physics ideas. The non-hydrodynamic friction coefficient is related to microscopic equilibrium structure and the length-scale-dependent polymer melt collective density fluctuation relaxation time. When local packing correlations are neglected, analytic scaling laws (with numerical prefactors) in various regimes are derived for the non-hydrodynamic diffusivity as a function of particle size, polymer radius-of-gyration, tube diameter, degree of entanglement, melt density, and temperature. Entanglement effects are the origin of large SE violations (orders of magnitude mobility enhancement) which smoothly increase as the ratio of particle radius to tube diameter decreases. Various crossover conditions for the recovery of the SE law are derived, which are qualitatively distinct for unentangled and entangled melts. The dynamical influence of packing correlations due to both repulsive and interfacial attractive forces is investigated. A central finding is that melt packing fraction, temperature, and interfacial attraction strength all influence the SE violation in qualitatively different directions depending on whether the polymers are entangled or not. Entangled systems exhibit seemingly anomalous trends as a function of these variables as a consequence of the non-diffusive nature of collective density fluctuation relaxation and the different response of polymer-particle structural correlations to adsorption on the mesoscopic entanglement length scale. The theory is in surprisingly good agreement with recent melt experiments, and new parametric studies are suggested.     

油/水界面张力的影响因素及无机盐对油水铺展的影响

讨论不同有机相与水形成的油/水界面处水/气、油/气及油/水3个界面张力的影响因素及相对大小。重点讨论了加入无机盐对作用于透镜状油滴上的3个界面张力的影响,总结出基本的规律并进行了实验验证。     

Influence of cationic composition and pH on the formation of metal stearates at oil-water interfaces

We study the formation of layers of metal stearates at the interface between a decane solution of stearic acid and aqueous salt solutions of variable composition and pH by monitoring the evolution of their mechanical, optical, and chemical properties as a function of time after formation of the interface. For values of the pH below the pK(a) of stearic acid hardly any interfacial activity is observed. For pH > pK(a), stearic acid deprotonates at the interface and forms metal stearates, eventually leading to the formation of macroscopic solid layers. Dynamic interfacial tension measurements reveal that the process takes place in several stages, which we attribute to the successive formation of dilute and dense monolayers followed by three-dimensional growth. In the presence of divalent ions, the solid layers display a significant increase in the dilatational storage modulus. Experiments performed with an aqueous phase containing multiple cation species (artificial seawater) give rise to particularly pronounced growth of solid layers, which preferentially incorporate Ca(2+) as revealed by X-ray photoelectron and infrared spectroscopy. Our results highlight in particular the importance of the complex synergistic effects of simultaneously present monovalent and divalent cation species on the interfacial adsorption.     

Dendrite‐Free Nanocrystalline Zinc Electrodeposition from an Ionic Liquid Containing Nickel Triflate for Rechargeable Zn‐Based Batteries

Metallic zinc is a promising anode material for rechargeable Zn‐based batteries. However, the dendritic growth of zinc has prevented practical applications. Herein it is demonstrated that dendrite‐free zinc deposits with a nanocrystalline structure can be obtained by using nickel triflate as an additive in a zinc triflate containing ionic liquid. The formation of a thin layer of Zn–Ni alloy (η‐ and γ‐phases) on the surface and in the initial stages of deposition along with the formation of an interfacial layer on the electrode strongly affect the nucleation and growth of zinc. A well‐defined and uniform nanocrystalline zinc deposit with particle sizes of about 25 nm was obtained in the presence of Ni^II. Further, it is shown that the nanocrystalline Zn exhibits a high cycling stability even after 50 deposition/stripping cycles. This strategy of introducing an inorganic metal salt in ionic liquid electrolytes can be considered as an efficient way to obtain dendrite‐free zinc.