Self-consistent field modeling of poly(ethylene oxide) adsorption onto silica: the multiple roles of electrolytes

In technological applications, it is increasingly important to understand and predict interfacial phenomena. Using a self-consistent field model within the Scheutjens-Fleer discretization scheme, we have developed a molecularly realistic model of the adsorption of poly(ethylene oxide) (PEO) onto silica from an aqueous solution. The bulk solution consists of water, PEO, 1:1 electrolyte, protons, and hydroxyl ions. The solvent quality is good below and becomes poor above a threshold ionic strength (of around 1 M). The silica surface features a number of silanol groups that have an affinity for PEO (by means of H bonding) when these groups are not dissociated. In line with experimental data, the surface changes from adsorbing to nonadsorbing at a sufficiently high pH. Even though PEO is uncharged, there is a complex effect of the ionic strength on the interfacial characteristics. For example, we report a non-monotonic behavior of the adsorbed amount as a function of ionic strength. Going from a low to a high ionic strength at a neutral or slightly basic pH, the adsorbed amount initially decreases as the surface affinity decreases (caused by the reduction of adsorption sites when, as a result of screening, the surface is increasingly charged) but then increases as a result of a reduction in solvent quality. These results indicate that molecularly realistic models can reveal much richer interfacial behavior than anticipated from generic models. The predictions follow many experimental findings.     

Surface modification of elastomeric stamps for microcontact printing of polar inks

Chemical modification of the surface of a stamp used for microcontact printing (microCP) is interesting for controling the surface properties, such as the hydrophilicity. To print polar inks, plasma polymerization of allylamine (PPAA) was employed to render the surface of poly(dimethylsiloxane) (PDMS), polyolefin plastomers (POP), and Kraton elatomeric stamps hydrophilic for long periods of time. A thin PPAA film of about 5 nm was deposited on the stamps, which increased the hydrophilicity, and which remained stable for at least several months. These surface-modified stamps were used to transfer polar inks by microCP. The employed microCP schemes are as follows: (a) a second generation of dendritic ink having eight dialkyl sulfide end groups to fabricate patterns on gold substrates by positive microCP, (b) fluorescent guest molecules on beta-cyclodextrin (beta-CD) printboards on glass employing host-guest recognition, and (c) Lucifer Yellow ethylenediamine resulting in covalent patterning on an aldehyde-terminated glass surface. All experiments resulted in an excellent performance of all three PPAA-coated stamp materials to transfer the polar inks from the stamp surface to gold and glass substrates by microCP, even from aqueous solutions.     

Dense Near Octagons With Four Points on Each Line,I

In this paper, we start the classification of the dense near octagons of order (3, t). We shall determine all dense near octagons of order (3, t) with a big hex. In order to achieve this goal, we must also classify all spreads of symmetry of all dense near hexagons of order (3, t). Bart De Bruyn: Postdoctoral Fellow of the Research Foundation - Flanders. Received November 22, 2005     

Formation of ZSM-22 zeolite catalytic particles by fusion of elementary nanorods

An ZSM-22 aluminosilicate zeolite was synthesized using the hydrothermal gel method at 150 degrees C. Products obtained after different synthesis times were characterized using various techniques and catalytic testing. Massive formation of ZSM-22 nanocrystals occurs after only a short synthesis time, appearing as isolated rods with a cross section of 12+/-4 nm. Nanorods have aluminum enriched at their external surface. Later in the crystallization process nanorods align and fuse sideways, whereby the external surface is systematically converted into an internal micropore surface. The formation of aluminum bearing micropores by the joining of nanorod surfaces is responsible for the enhanced catalytic activity. For this, the zeolite synthesis of nanoscale crystallites is ineffective for enhancing catalytic activity.     

Mass spectrometric study of selected precursors and degradation products of chemical warfare agents

Selected precursors and degradation products of chemical warfare agents namely N,N-dialkylaminoethane-2-ols, N,N-dialkylaminoethyl-2-chlorides and some of related N-quaternary salts were studied by means of electrospray ionization-multiple tandem mass spectrometry (ESI-MS(n)). Proposed structures were confirmed with accurate mass measurement. General fragmentation patterns of these compounds are discussed in detail and suggested processes are confirmed using deuterated standards. The typical processes are elimination of alkene, hydrogen chloride, or water, respectively. Besides, elimination of ethene from propyl chain under specific conditions was observed and unambiguously confirmed using exact mass measurement and labelled standard. The potential of mass spectrometry to distinguish the positional isomers occurring among the studied compounds is reviewed in detail using two different MS instruments (i.e. ion trap and hybrid quadrupole-time of flight (Q-TOF) analyzer). A new microcolumn liquid chromatography (microLC)/MS(n) method was designed for the cases where the resolution based solely on differences in fragmentation is not sufficient. Low retention of the derivatives on reversed phase (RP) was overcome by using addition of less typical ion pairing agent (1 mM/l, 3,5-dinitrobenzoic acid) to the mobile phase (mixture water : acetonitrile).     

Wetting properties of aqueous solutions of hydrophobically modified inulin polymeric surfactant

The contact angles of aqueous solutions of a polymeric surfactant namely hydrophobically modified inulin (INUTEC®SP1) were measured on hydrophilic and hydrophobised quartz glass surfaces using the sessile drop technique. These measurements showed a large difference (>10°) between the advancing contact angle θ ₁ (that is measured immediately after placing the drop on the surface) and the constant contact angle θ ₂ (that is measured 30 minutes after placing the drop). In all the results only the contact angle θ ₂ was subsequently measured. θ versus INUTEC®SP1 concentration C _s curves were obtained at various NaCl concentrations both on hydrophilic and hydrophobic glass surfaces. On hydrophilic glass surface the θ versus C _s curves showed a maximum at a concentration range of 10^–6 to 2?×?10^–5 mol dm^-3 INUTEC®SP1. These curves were shifted to lower values as the NaCl concentration was increased. On such hydrophilic surface the INUTEC®SP1 molecule adsorbs with the polyfructose loops and tails oriented towards the surface leaving the alkyl chains in solution. Saturation adsorption with this orientation occurs at 2?×?10^–5 mol dm^-3 INUTEC®SP1. However, the contact angles remain quite small (<18°) indicating the presence of several hydrophilic glass patches uncovered by surfactant molecules. At C _s?>?2?×?10^–5 mol dm^-3 θ decreases with further increase of the INUTEC®SP1 concentration reaching 5° at the Critical Association Concentration (CAC) of the polymer. This indicates the formation of a bilayer of INUTEC®SP1 molecules with the alkyl chains hydrophobically attached to those of the first layer. On a hydrophobic glass surface, adsorption of INUTEC®SP1 occurs by multi-point attachment with the alkyl chains on the surface leaving the hydrophilic polyfructose loops and tails dangling in solution. This results in a gradual decrease of the contact angle with increase in INUTEC®SP1 concentration, reaching a plateau value (>85°) between 2?×?10^–5 and 2?×?10^–4 mol dm^-3. The large contact angles obtained on adsorption of the polymeric surfactant on a hydrophobic surface indicate the presence of several uncovered hydrophobic patches. These results give a reasonable picture of the adsorption and orientation of the INUTEC®SP1 molecules on both hydrophilic and hydrophobic solid surfaces.     

Sodium alanate nanoparticles--linking size to hydrogen storage properties

Important limitations in the application of light metal hydrides for hydrogen storage are slow kinetics and poor reversibility. To alleviate these problems doping and ball-milling are commonly applied, for NaAlH 4 leading to particle sizes down to 150 nm. By wet-chemical synthesis we have prepared carbon nanofiber-supported NaAlH 4 with discrete particle size ranges of 1-10 microm, 19-30 nm, and 2-10 nm. The hydrogen desorption temperatures and activation energies decreased from 186 degrees C and 116 kJ.mol (-1) for the largest particles to 70 degrees C and 58 kJ.mol (-1) for the smallest particles. In addition, decreasing particle sizes lowered the pressures needed for reloading. This reported size-performance correlation for NaAlH 4 may guide hydrogen storage research for a wide range of nanostructured light (metal) hydrides.     

Pd(I) phosphine carbonyl and hydride complexes implicated in the palladium-catalyzed oxo process

Reduction of compound "Pd(bcope)(OTf)2" [bcope = (c-C8H14-1,5)PCH2CH2P(c-C8H14-1,5); OTf = O3SCF3] with H2/CO yields a mixture of Pd(I) compounds [Pd2(bcope)2(CO)2](OTf)2 (1) and [Pd2(bcope)2(mu-CO)(mu-H)](OTf) (2), whereas reduction with H2 or Ph3SiH in the absence of CO leads to [Pd3(bcope)3(mu3-H)2](OTf)2 (3). Exposure of 3 to CO leads to 1 and 2. The structures of 1 and 3 have been determined by X-ray diffraction. Complex [Pd2(bcope)2(CO)2](2+) displays a metal-metal bonded structure with a square planar environment for the Pd atoms and terminally bonded CO ligands and is fluxional in solution. DFT calculations aid the interpretation of this fluxional behavior as resulting from an intramolecular exchange of the two inequivalent P atom positions via a symmetric bis-CO-bridged intermediate. A cyclic voltammetric investigation reveals a very complex redox behavior for the "Pd(bcope)(OTf)2"/CO system and suggests possible pathways leading to the formation of the various observed products, as well as their relationship with the active species of the PdL2(2+)/CO/H2-catalyzed oxo processes (L2 = diphosphine ligands).     

Carbon dioxide absorption by MEA

Biogas generally contains significant quantities of carbon dioxide in addition to methane. A bubbling column reactor operating at atmospheric pressure is proposed for cheap separation and a Mettler RC1 reaction calorimeter was used to build a simplified empirical model for measuring the molar heat of solubility of CO₂ in aqueous solutions of monoethanolamine (MEA). Determinations were performed in 12 mass% MEA solutions regenerated at atmospheric pressure and reflux temperature for 3 h. Flows of CO₂ from 174 to 917 mL min^?1 were used at a reactor temperature of 283 to 353 K.     

Chemotaxonomy of bacteria by comprehensive GC and GC-MS in electron impact and chemical ionisation mode

The analysis of the cellular lipidic fraction of bacteria is described. After hydrolysis and methylation, the fatty acid methyl esters (FAMEs) are determined by 1-D GC using the Sherlock MIDI bacteria identification system, by comprehensive GC (GC x GC) and by GC-MS in electron impact (EI) and positive chemical ionisation (PCI) mode. With GC x GC, the enhanced selectivity and group type separation provides a more complete elucidation of the fatty acids in microorganisms. GC-EI-MS and GC-PCI-MS were helpful for confirmation. The bacteria selected in this study are Brevundimonas diminuta, Chryseobacterium gleum and Stenotrophomonas maltophilia.