Laser-induced site-selective silver seeding on polyimide for electroless copper plating

Ag particles were generated on Ag+-doped polyimide film by laser direct writing, followed by selective copper deposition using the metallic silver particles as seeds. Laser irradiation caused in situ reduction and agglomeration of silver on the polyimide film. The copper lines were less uniform and compact with higher scanning velocity and the width of the deposited copper line could reach 25 mu m. Equations of the relationship between scanning velocity and connectivity of the deposited copper patterns have been derived. The process was characterised by AFM, XPS, SEM, and semiconductor characterisation system.

Tunable wettability of polyimide films based on electrostatic self-assembly of ionic liquids

We have demonstrated that the surface wettability of negatively charged polyimide films could be turned by electrostatic self-assembly of ionic liquids. The water contact angles of the polyimide films varied in the range 27-80 degrees for 13 different ionic liquids based on imidazolium and ammonium salts. The surface morphology of the resulting surfaces was characterized using atomic force microscopy. The results revealed that the assembly of longer-substituent cations was characterized by the formation of spherical nanoparticles that were formed due to sequent aggregation of cations on those electrostatically assembled ones via hydrophobic interaction. In this case, the counteranions are present in the assembled layers and the wettability is accordingly affected. Whereas for shorter-substituent cations, no aggregates were formed due to the less hydrophobic interaction than the electrostatic repulsive interaction between the cations, and the counteranions were absent from the assembled layers. This method can also be utilized to quantify the hydrophobicity of various ionic liquids.

Superhydrophobic polyimide films with a hierarchical topography : combined replica molding and layer-by-layer assembly

Artificial superhydrophobic surfaces with a hierarchical topography were fabricated by using layer-by-layer assembly of polyelectrolytes and silica nanoparticles on microsphere-patterned polyimide precursor substrates followed with thermal and fluoroalkylsilane treatment. In this special hierarchical topography, micrometer-scale structures were provided by replica molding of polyamic acid using two-dimensional arrays of polystyrene latex spheres as templates, and nanosized silica particles were then assembled on these microspheres to construct finer structures at the nanoscale. Heat treatment was conducted to induce chemical cross-linking between polyelectrolytes and simultaneously convert polyamic acid to polyimide. After surface modification with fluoroalkylsilane, the as-prepared highly hydrophilic surface was endowed with superhydrophobicity due to the bioinspired combination of low surface energy materials and hierarchical surface structures. A superhydrophobic surface with a static water contact angle of 160 degrees and sliding angle of less than 10 degrees was obtained. Notably, the polyimide microspheres were integrated with the substrate and were mechanically stable. In addition, the chemical and mechanical stability of the polyelectrolyte/silica nanoparticle multilayers could be increased by heat-induced cross-linking between polyelectrolytes to form nylon-like films, as well as the formation of interfacial chemical bonds.

Superhydrophobic modification of polyimide films based on gold-coated porous silver nanostructures and self-assembled monolayers

We present a facile and effective method for controlling the surface hydrophobicity of polyimide films from sticky to superhydrophobic properties by tailoring their topographies. Nanostructured silver layers were produced on polyimide films by treatment with aqueous KOH and AgNO3, followed by thermal treatment at 200 degrees C or higher temperatures. Further modification of the gold-coated silver layers with n-dodecanethiol led to hydrophobic surfaces. Different morphologies of the silver layers at the micro- and nano-meter scales, which result in the variety of hydrophobicity, can be tailored by controlling the thermal treatment temperature. Surfaces prepared at 320 degrees C showed a sticky property that water drops did not slide off even when the sample was held upside down. Superhydrophobic surfaces were obtained when the temperature was above 340 degrees C. A remarkable superhydrophobicity, as evidenced by a very large water contact angle of 162 degrees and a very small sliding angle of 7 degrees, was achieved by heating the modified polyimide films at 360 degrees C. This is also the first example for superhydrophobic modification of polyimide films.

The role of unbound oligomers in the nucleation and growth of electrodeposited polypyrrole and method for preparing high strength, high conductivity films

Polypyrrole is a material with immensely useful properties suitable for a wide range of electrochemical applications, but its development has been hindered by cumbersome manufacturing processes. Here we show that a simple modification to the standard electrochemical polymerization method produces polypyrrole films of equivalently high conductivity and superior mechanical properties in one-tenth of the polymerization time. Preparing the film as a series of electrodeposited layers with thorough solvent washing between layering was found to produce excellent quality films even when layer deposition was accelerated by high current. The washing step between the sequentially polymerized layers altered the deposition mechanism, eliminating the typical dendritic growth and generating nonporous deposits. Solvent washing was shown to reduce the concentration of oligomeric species in the near-electrode region and hinder the three-dimensional growth mechanism that occurs by deposition of secondary particles from solution. As artificial muscles, the high density sequentially polymerized films produced the highest mechanical work output yet reported for polypyrrole actuators.

Identification of oligomers in polyethyleneterephthalate bottles for mineral water and fruit juice - Development and validation of a high-performance liquid chromatographic method for the determination of first series cyclic trimer

Cyclic oligomers were identified in PET bottles used for mineral water and fruit juice using MS and H-1 and C-13 NMR: a first series cyclic trimer, a first series cyclic tetramer, a first series cyclic dimmer and a second series cyclic trimer. An analytical method to determine first series cyclic trimer in these bottles was developed and validated, using HPLC. The first series cyclic trimer levels were 316-462 mg/100 g of PET bottle. (c) 2005 Elsevier B.V. All rights reserved.

The Role of Nanometer-Scaled Ligand Patterns in Polyvalent Binding by Large Mannan-Binding Lectin Oligomers

Mannan-binding lectin (MBL) is an important protein of the innate immune system and protects the body against infection through opsonization and activation of the complement system on surfaces with an appropriate presentation of carbohydrate ligands. The quaternary structure of human MBL is built from oligomerization of structural units into polydisperse complexes typically with three to eight structural units, each containing three lectin domains. Insight into the connection between the structure and ligand-binding properties of these oligomers has been lacking. In this article, we present an analysis of the binding to neoglycoprotein-coated surfaces by size-fractionated human MBL oligomers studied with small-angle x-ray scattering and surface plasmon resonance spectroscopy. The MBL oligomers bound to these surfaces mainly in two modes, with dissociation constants in the micro to nanomolar order. The binding kinetics were markedly influenced by both the density of ligands and the number of ligand-binding domains in the oligomers. These findings demonstrated that the MBL-binding kinetics are critically dependent on structural characteristics on the nanometer scale, both with regard to the dimensions of the oligomer, as well as the ligand presentation on surfaces. Therefore, our work suggested that the surface binding of MBL involves recognition of patterns with dimensions on the order of 10-20 nm. The recent understanding that the surfaces of many microbes are organized with structural features on the nanometer scale suggests that these properties of MBL ligand recognition potentially constitute an important part of the pattern-recognition ability of these polyvalent oligomers. The Journal of Immunology, 2012, 188: 1292-1306.

Characterization of Heparin-induced Glyceraldehyde-3-phosphate Dehydrogenase Early Amyloid-like Oligomers and Their Implication in alpha-Synuclein Aggregation

Lewy bodies and Lewy neurites, neuropathological hallmarks of several neurological diseases, are mainly made of filamentous assemblies of alpha-synuclein. However, other macromolecules including Tau, ubiquitin, glyceraldehyde-3-phosphate dehydrogenase, and glycosaminoglycans are routinely found associated with these amyloid deposits. Glyceraldehyde-3-phosphate dehydrogenase is a glycolytic enzyme that can form fibrillar aggregates in the presence of acidic membranes, but its role in Parkinson disease is still unknown. In this work, the ability of heparin to trigger the amyloid aggregation of this protein at physiological conditions of pH and temperature is demonstrated by infrared and fluorescence spectroscopy, dynamic light scattering, small angle x-ray scattering, circular dichroism, and fluorescence microscopy. Aggregation proceeds through the formation of short rod-like oligomers, which elongates in one dimension. Heparan sulfate was also capable of inducing glyceraldehyde-3-phosphate dehydrogenase aggregation, but chondroitin sulfates A, B, and C together with dextran sulfate had a negligible effect. Aided with molecular docking simulations, a putative binding site on the protein is proposed providing a rational explanation for the structural specificity of heparin and heparan sulfate. Finally, it is demonstrated that in vitro the early oligomers present in the glyceraldehyde-3-phosphate dehydrogenase fibrillation pathway promote alpha-synuclein aggregation. Taking into account the toxicity of alpha-synuclein prefibrillar species, the heparin-induced glyceraldehyde-3-phosphate dehydrogenase early oligomers might come in useful as a novel therapeutic strategy in Parkinson disease and other synucleinopathies.

Crystalline assemblies of folded oligomers

In this work a novel design concept for folded oligomers is presented. The concept involves the insertion of a rigid spacer, the 1,3-bis(ethynylene)benzene unit, into linear alkyl-chain oligomers. Number and position of these spacers determine the molecular conformation of the oligomers in crystalline assemblies. In this way, chain folding is induced on crystallization at the air-water interface and in bulk. The packing arrangements in the crystalline monolayers were determined by grazing inzidence X-ray diffraction.