Phase Transfer Induced Enhanced Stability of Monolayer Protected Silver Quantum Clusters

Mercaptosuccinic acid (MSA) protected silver clusters (Ag@MSA) were synthesized and their stability was monitored both in an aqueous and in a toluene phase. In the former, the pH of the cluster solution was tuned between 3 and 10 using ammonium acetate buffer, and the cluster stability was tested. The clusters were unstable at all measured pH values, whereas in the toluene phase, by using sterically hindered counter ion (tertraoctylammonium, TOA), the stability of the clusters was improved significantly. The phase transferred clusters in the toluene phase showed very high stability over months at room temperature. Transmission electron microscopy images show an average cluster size of ~ 2.05 nm. Size exclusion chromatography and Electrospray Ionisation Mass Spectrometry (ESI–MS) measurements were employed to analyse the phase transferred clusters. Importantly, Ag₄MSA₄ ^? type stable fragments were observed in ESI–MS measurements. The [Ag₈(MSA)₈(TOA)₅]^2? was the largest cluster identified by ESI–MS.     

Topochemical activation of pulp fibres

A new concept for topochemical activation of mechanical pulp fibres was investigated. The activation concept was based on attachment of precursors of peracids onto the surface of the fibres prior to hydrogen peroxide bleaching. The activators used in this work were: tetraacetylethylenediamine (water soluble), lactose octaacetate (LOA, colloidal particles, and low water solubility) and sucrose octaacetate (partially soluble in water). LOA showed promising results for application in the surface activation concept due to attachment of colloidal particles on the outmost surface of the fibres, simultaneously contributing to a brightness increase. Surface coverage by lignin on fibres had decreased after the bleaching process with activators, which was detected by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry.     

Study of PEGylated lipid layers as a model for PEGylated liposome surfaces: molecular dynamics simulation and Langmuir monolayer studies

We have combined Langmuir monolayer film experiments and all-atom molecular dynamics (MD) simulation of a bilayer to study the surface structure of a PEGylated liposome and its interaction with the ionic environment present under physiological conditions. Lipids that form both gel and liquid-crystalline membranes have been used in our study. By varying the salt concentration in the Langmuir film experiment and including salt at the physiological level in the simulation, we have studied the effect of salt ions present in the blood plasma on the structure of the poly(ethylene glycol) (PEG) layer. We have also studied the interaction between the PEG layer and the lipid bilayer in both the liquid-crystalline and gel states. The MD simulation shows two clear results: (a) The Na(+) ions form close interactions with the PEG oxygens, with the PEG chains forming loops around them and (b) PEG penetrates the lipid core of the membrane for the case of a liquid-crystalline membrane but is excluded from the tighter structure of the gel membrane. The Langmuir monolayer results indicate that the salt concentration affects the PEGylated lipid system, and these results can be interpreted in a fashion that is in agreement with the results of our MD simulation. We conclude that the currently accepted picture of the PEG surface layer acting as a generic neutral hydrophilic polymer entirely outside the membrane, with its effect explained through steric interactions, is not sufficient. The phenomena we have observed may affect both the interaction between the liposome and bloodstream proteins and the liquid-crystalline-gel transition and is thus relevant to nanotechnological drug delivery device design.     

All-integer column generation for set partitioning: Basic principles and extensions

Column generation, combined with an appropriate integer programming technique, has shown to be a powerful tool for solving huge integer programmes arising in various applications. In these column generation approaches, the master problem is often of a set partitioning type.     

Palladium(II) chemically bonded to silica surface applied to the separation and identification of polycyclic aromatic sulfur heterocycles in heavy oil

Separation of polycyclic aromatic sulfur heterocycles among themselves and also from interferents in petrochemical matrices is a challenging task because of their low concentration, matrix complexity, and also due to the presence of polyaromatic hydrocarbons, as they present similar physico‐chemical properties. Therefore, the objective of this work was preparation, characterization, and application of a stationary phase for separation of these compounds in a heavy gas oil sample and their identification by comprehensive two‐dimensional gas chromatography. The stationary phase was prepared by grafting mercaptopropyltrimethoxisilane onto a silica surface, followed by palladium(II) chloride immobilization. Elemental analysis, thermogravimetry, nitrogen adsorption‐desorption isotherms, infrared analysis, and scanning electron microscopy were performed to characterize this solid phase. Sulfur compounds were separated in an open column packed with the stationary phase and analyzed by comprehensive two‐dimensional gas chromatography coupled to time‐of‐flight mass spectrometric detection. The number of compounds tentatively identified was 314 and their classes were thiophenes, benzotiophenes, dibenzothiophenes, naphthothiophenes, benzonaphthothiophenes, and dinaphthothiophenes. Separation among sulfur compounds and polyaromatic hydrocarbons was successful, which is a difficult goal to achieve with the traditionally employed solid phases. Some recalcitrant compounds (dibenzothiophenes with substituents of two and four carbons) were fully separated and tentatively identified.     

From localised to delocalised electronic states in free Ar, Kr and Xe clusters

We present new results for the inner valence levels of clusters of the three inert gases Ar, Kr and Xe based on photoelectron spectroscopy studies. The inner valence levels are compared to the localised core levels and to the delocalised outer valence levels. This comparison shows a gradual change from a relatively localised behaviour for Ar inner valence 3s, over the intermediate case of Kr inner valence 4s, to a more delocalised behaviour for Xe inner valence 5s. This change correlates well with the ratio between the orbital sizes and the interatomic distances. The Kr4s intermediate case is found to exhibit characteristics of both localised and delocalised behaviour.Received: 4 May 2004, Published online: 24 August 2004PACS: 36.40.-c Atomic and molecular clusters - 36.40.Wa Charged clusters - 61.46. + w Nanoscale materials: clusters, nanoparticles, nanotubes, and nanocrystalsA. Naves de Brito: On leave from Dept. of Physics, University of Brasília, 70910-900 Brasília, Brazil.     

Weighted generalized functions and hyperbolic Riesz B‐potential

The paper is devoted to the study of the fractional integral operator, which is a negative real power of the singular wave operator generated by Bessel operator using weighted generalized functions. We give conditions for this operator to be bounded in appropriate spaces, obtain formula for the Hankel transform of this operator, and get formula of connection between this operator and natural degree of singular wave operator generated by Bessel operator.     

Copper-cobalt ferrites as catalysts for methanol decomposition

Copper-cobalt ferrites with composition Cu_1?xCo_xFe₂O₄, where x= 0.2 and 0.8 were prepared by thermal treatment of co-precipitated precursor. The obtained materials were characterized by TG-DSC, XRD, Transmission and Conversion Electron Mössbauer spectroscopy and temperature programmed reduction with hydrogen. The catalytic properties of ferrites were tested in methanol decomposition to CO and hydrogen.