A method to construct polyelectrolyte multilayers film containing gold nanoparticles

Gold nanoparticles in polyelectrolyte multilayers film can be easily prepared by repeating immersion of a substrate in poly(diallyl dimethylammonium) chloride (PDDA)-AuCl₄⁻ complexes solution followed by reduction Au³⁺ through heating. UV-vis spectroscopy, cyclic voltammetry (CV) and tapping-mode atomic force microscopy (AFM) are used to confirm the successful construction of the polyelectrolyte multilayers film and the formation of gold nanoparticles. The multilayers film shows electrocatalytic activity to dioxygen reduction.     

Structure and properties of plasma-polymerized thin films of polyaniline

Plasma polymerization of aniline and in-situ doping of polvaniline with iodine was carried out using radio frequency glow discharge. Thin films of polyaniline were deposited on platinum and glass. The infrared spectrum shows that the aromatic ring is retained under the plasma conditions. The electrical conductivity measurements indicate that the conductivity increases by more than seven orders of magnitude when the polyaniline is doped by iodine. The scanning electron microscopic studies reveal the formation of irregular pentagons on glass substrate while on platinum, polvaniline forms a fibrillar network. In both the cases a continuous film is obtained.     

A quantitative method for dual‐pass electrostatic force microscopy phase measurements

Electrostatic force microscopy (EFM) has become a powerful tool for investigating charges on surfaces. The use of phase measurement in EFM is a direct and fast way to detect electrostatic force gradients, but only qualitatively. With the dual‐pass scheme, the phase signal at lifted height is often assumed to exclude any influences from the topography, but it does not. We report the collection of both topography and phase data by EFM on charged, micron‐sized metal wires. In order to quantify the electrostatic force, a cone model and finite element analysis are provided to integrate the force gradient from the phase signal. Copyright © 2007 John Wiley & Sons, Ltd.     

高聚物球晶偏光织态研究中的厚度性消光与补偿机理

以两维聚环氧乙烷（ＰＥＯ）球晶为对象，探讨了偏光显微法的消光机理，尤其是其中的厚度性消光机理，并对于补偿片的作用原理作了细致的理论分析，运用上述手段对ＰＥＯ球晶的形态进行了研究。     

Nioboxidfluoride mit Blockstrukturen — Elektronenmikroskopische Durchstrahlungsaufnahmen und ihre Simulation

Niobiumoxidefluorides Nb₅₉O₁₄₇F, Nb₃₁O₇₇F, Nb₆₅O₁₆₁F₃ and Nb₃₄O₈₄F₂ were prepared by reaction of Nb₂O₅ and Nb₃O₇F at 1 270°C. These niobiumoxidefluorides have blockstructures which were examined by high resolution electron microscopy. The observed images of the crystal structures were compared with computer simulated images.

     

Two‐ and Three‐Dimensional Molecular Organization of Schiff‐Base Derivatives

We have designed and synthesized a series of Schiff base derivatives, and studied their structural features in two‐dimensional (2D) and three‐dimensional (3D) states by combining scanning tunneling microscopy (STM) and X‐ray diffraction experiments. The Schiff‐base derivatives with short alkyl chains crystallize easily, which allows a detailed structural analysis by X‐ray diffraction. Due to the strong adsorbate–substrate interactions, those bases with long alkyl chains easily form 2D assemblies on highly oriented pyrolytic graphite (HOPG). The STM images indicate also that the introduction of two methoxy groups into the molecule can change the structure of these 2D assemblies as a result of the increased steric hindrances, for example: the Schiff‐base derivative, bearing both methoxy groups and C₁₆H₃₃ tails, forms 2D Moiré patterns, and an alignment of pairing Schiff‐base molecules may be easily resolved. Conversely, the Schiff base derivative, bearing solely C₁₆H₃₃ tails, forms 2D non‐Moiré patterns. It is demonstrated that the 3D structural features result from the compromise of intermolecular interactions of different molecular moieties. However, there is one more factor, which also governs the 2D structure: the adsorbate‐substrate interaction. The 3D crystal structure may thus help to understand many factors involved in the formation of 2D structures, and would be helpful for designing new molecular assemblies with tailoring functions.     

Synthesis and characterization of polystyrene‐b‐poly (1,2‐isoprene‐ran‐3,4‐isoprene) block copolymers with azobenzene side groups

Polystyrene‐b‐poly(1,2‐isoprene‐ran‐3,4‐isoprene) block copolymers with azobenzene side groups were synthesized by the esterification of azobenzene acid chloride with polystyrene‐b‐hydroxylated poly(1,2‐isoprene‐ran‐3,4‐isopenre) block copolymers for creating new photochromic materials. The resulting block copolymers with azobenzene side groups were characterized for structural, thermal, and morphological properties. IR and NMR spectroscopies confirmed that the polymers obtained had the expected structures. Differential scanning calorimetric measurements by heating runs clearly showed the glass transitions of polystyrene and polyisoprene main chains and two distinct first‐order transitions at temperatures of azobenzene side groups around 48 and 83 °C. The microstructure of these block copolymer films was investigated using both transmission electron microscopy (TEM) and near‐field optical microscopy (NOM). TEM images revealed typical microphase‐separated morphologies such as sphere, cylinder, and lamellar structures. The domain spacing of microphase‐separated cylindrical morphology in the NOM image agreed with that of the TEM results. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2406–2414, 2002     

Poly(butylene terephthalate)/poly(ε-caprolactone) blends: Influence of PCL molecular mass on PBT melting and crystallization behavior

The isothermal crystallization kinetics and melting behavior of poly(butylene terephthalate) (PBT) in binary blends with poly(ε-caprolactone) (PCL) was investigated as a function of PCL molecular mass by differential scanning calorimetry and optical microscopy. The components are miscible in the melt when oligomeric PCL (M_w = 1250) is blended with PBT, whereas only partial miscibility was found in mixtures with higher molecular mass (M_w = 10,000 and 50,000). The equilibrium melting point of PBT in the homopolymer and in blends with PCL was determined through a non-linear extrapolation of the T_m = f(T_c) curve. The PBT spherulitic growth rate and bulk crystallization rate were found to increase with respect to plain PBT in blends with PCL1250 and PCL10000, whereas addition of PCL50000 causes a reduction of PBT solidification rate. The crystallization induction times were determined by differential scanning calorimetry for all the mixtures through a blank subtraction procedure that allows precise estimation of the crystallization kinetics of fast crystallizing polymers. The results have been discussed on the basis of the Hoffman-Lauritzen crystallization theory and considerations on both the transport of chains towards the crystalline growth front and the energy barrier for the formation of critical nuclei in miscible and partially miscible PBT/PCL mixtures are widely debated.     

Energy Landscape of Aptamer/Protein Complexes Studied by Single‐Molecule Force Spectroscopy

Aptamers are single‐stranded nucleic acid molecules selected in vitro to bind to a variety of target molecules. Aptamers bound to proteins are emerging as a new class of molecules that rival commonly used antibodies in both therapeutic and diagnostic applications. With the increasing application of aptamers as molecular probes for protein recognition, it is important to understand the molecular mechanism of aptamer–protein interaction. Recently, we developed a method of using atomic force microscopy (AFM) to study the single‐molecule rupture force of aptamer/protein complexes. In this work, we investigate further the unbinding dynamics of aptamer/protein complexes and their dissociation‐energy landscape by AFM. The dependence of single‐molecule force on the AFM loading rate was plotted for three aptamer/protein complexes and their dissociation rate constants, and other parameters characterizing their dissociation pathways were obtained. Furthermore, the single‐molecule force spectra of three aptamer/protein complexes were compared to those of the corresponding antibody/protein complexes in the same loading‐rate range. The results revealed two activation barriers and one intermediate state in the unbinding process of aptamer/protein complexes, which is different from the energy landscape of antibody/protein complexes. The results provide new information for the study of aptamer–protein interaction at the molecular level.     

Oxidation products of the niobium tungsten oxide Nb4W13O47: A high-resolution scanning transmission electron microscopy study

Nb₄W₁₃O₄₇, a member of the solid solution series Nb_8−nW_9+nO₄₇ (0?n?5), crystallizes in a threefold superstructure of the tetragonal tungsten bronze structure. While the oxidation of this reduced phase at T_OX=1200 °C leads to a separation into the thermodynamically stable phases, lower oxidation temperatures result in products that comprise new structural elements and ordering variants. The characterization of the oxidation products obtained at T_OX=1000 °C was performed by scanning transmission electron microscopy applying a high-angle annular dark field detector. At the selected imaging conditions (Z contrast), not only the metal positions are revealed by this technique but valuable additional information about the elemental distribution can be obtained simultaneously.