Characterization of the structural and surface properties of chemically modified MCM-41 material

Mesoporous Mobil catalytic materials of number 41 (MCM-41) silica was chemically modified using both inorganic and organic precursors and characterized using the techniques, XRD, XPS, MAS NMR, FTIR, W-Vis, and physical adsorption of nitrogen, hydrocarbons (hexane, benzene, acetone, and methanol) and water vapor. Modification using organic reagents was found to result in a significant loss in porosity and a shape change of surface properties (increased hydrophobicity and decreased acidity). With inorganic modifying reagents, the decrease in porosity was also observed while the surface properties were not significantly altered as reflected by the adsorption isotherms of organics and water vapors. Chemical modifications can greatly improve the hydrothermal stability of MCM-41 material because of the enhanced surface hydrophobicity (with organic modifiers) or increased pore wall thickness (with inorganic modifiers). (C) 2000 Elsevier Science B.V. All rights reserved.

Surface reflectance properties of Antarctic moss and their relationship to plant species, pigment composition and photosynthetic function

In this study the variations in surface reflectance properties and pigment concentrations of Antarctic moss over species, sites, microtopography and with water content were investigated. It was found that species had significantly different surface reflectance properties, particularly in the region of the red edge (approximately 700 nm), but this did not correlate strongly with pigment concentrations. Surface reflectance of moss also varied in the visible region and in the characteristics of the red edge over different sites. Reflectance parameters, such as the photochemical reflectance index (PRI) and cold hard band were useful discriminators of site, microtopographic position and water content. The PRI was correlated both with the concentrations of active xanthophyll-cycle pigments and the photosynthetic light use efficiency, F-v/F-m, measured using chlorophyll fluorescence. Water content of moss strongly influenced the amplitude and position of the red-edge as well as the PRI, and may be responsible for observed differences in reflectance properties for different species and sites. All moss showed sustained high levels of photoprotective xanthophyll pigments, especially at exposed sites, indicating moss is experiencing continual high levels of photochemical stress.

Comparative surface accessibility of a pore-lining threonine residue (T6') in the glycine and GABA(A) receptors

The substituted cysteine accessibility method was used to probe the surface exposure of a pore-lining threonine residue (T6') common to both the glycine receptor (GlyR) and gamma-aminobutyric acid, type A receptor (GABAAR) chloride channels. This residue lies close to the channel activation gate, the ionic selectivity filter, and the main pore blocker binding site. Despite their high amino acid sequence homologies and common role in conducting chloride ions, recent studies have suggested that the GlyRs and GABA(A)Rs have divergent open state pore structures at the 6' position. When both the human alpha1(T6'C) homomeric GlyR and the rat alpha1(T6'C)beta1(T6'C) heteromeric GABA(A)R were expressed in human embryonic kidney 293 cells, their 6' residue surface accessibilities differed significantly in the closed state. However, when a soluble cysteine-modifying compound was applied in the presence of saturating agonist concentrations, both receptors were locked into the open state. This action was not induced by oxidizing agents in either receptor. These results provide evidence for a conserved pore opening mechanism in anion-selective members of the ligand-gated ion channel family. The results also indicate that the GABA(A)R pore structure at the 6' level may vary between different expression systems.

Comparative surface accessibility of a pore-lining threonine residue (T6') in the glycine and GABA(A) receptors

The substituted cysteine accessibility method was used to probe the surface exposure of a pore-lining threonine residue (T6’) common to both the glycine receptor (GlyR) and GABAA receptor (GABAAR) chloride channels. This residue lies close to the channel activation gate, the ionic selectivity filter and the main pore blocker binding site. Recent studies have suggested that the GlyRs and GABAARs have divergent open state pore structures at the 6’ position. When both the human a1T6’C homomeric GlyR and the rat a1T6’Cb1T6’C heteromeric GABAAR were expressed in HEK293 cells, their 6’ residue surface accessibilities differed significantly in the closed state. However, when a soluble cysteine-modifying compound was applied in the presence of saturating agonist concentrations, both receptors were locked into the open state. This action was not induced by oxidising agents in either receptor. These results provide evidence for a conserved pore opening mechanism in anion-selective members of the ligand-gated ion channel family. The results also indicate that the GABAAR pore structure at the 6’ level may vary between different expression systems.

Is cell surface calreticulin involved in phagocytosis by insect hemocytes?

The innate immune system of insects consists of humoral and cellular components involved in the recognition of and responses to intruding foreign micro- or macroorganisms. Several molecules have been identified so far that recognize molecular patterns present on microorganisms, such as lipopolysaccharides, peptidoglycans and lipoteichonic acid. These molecules, acting as opsonins, trigger immune responses such as phagocytosis, nodule formation, melanization and encapsulation. Here, we investigated the role of calreticulin (CRT) present on the surface of Pieris rapae hemocytes in phagocytosis. Comparative phagocytosis assays using yeast cells showed that hemocytes from different insects exhibit significant variation in their phagocytosing potential and relative CRT involvement. (C) 2003 Elsevier Science Ltd. All rights reserved.

Infiltration from surface and buried point sources: The average wetting water content

The assumption in analytical solutions for flow from surface and buried point sources of an average water content, (θ) over bar, behind the wetting front is examined. Some recent work has shown that this assumption fitted some field data well. Here we calculated (θ) over bar using a steady state solution based on the work by Raats [1971] and an exponential dependence of the diffusivity upon the water content. This is compared with a constant value of (θ) over bar calculated from an assumption of a hydraulic conductivity at the wetting front of 1 mm day(-1) and the water content at saturation. This comparison was made for a wide range of soils. The constant (θ) over bar generally underestimated (θ) over bar at small wetted radii and overestimated (θ) over bar at large radii. The crossover point between under and overestimation changed with both soil properties and flow rate. The largest variance occurred for coarser texture soils at low-flow rates. At high-flow rates in finer-textured soils the use of a constant (θ) over bar results in underestimation of the time for the wetting front to reach a particular radius. The value of (θ) over bar is related to the time at which the wetting front reaches a given radius. In coarse-textured soils the use of a constant value of (θ) over bar can result in an error of the time when the wetting front reaches a particular radius, as large as 80% at low-flow rates and large radii.

Surface characterization of 6H-SiC (0001) substrates in indentation and abrasive machining

Surface characterization of 6H-SiC (0001) substrates in indentation and abrasive machining was carried out to investigate microfracture, residual damage, and surface roughness associated with material removal and surface generation. Brittle versus plastic deformation was studied using Vickers indention and nano-indentation. To characterize the abrasive machining response, the 6H-SiC (0001) substrates were ground using diamond wheels with grit sizes of 25, 15 and 7 mum, and then polished with diamond suspensions of 3 and 0.05 mum. It is found that in indentation, there was a scale effect for brittle versus plastic deformation in 6H-SiC substrates. Also, in grinding, the scales of fracture and surface roughness of the substrates decreased with a decrease in diamond grit size. However, in polishing, a reduction in grit size of diamond suspensions gave no significant improvement in surface roughness. Furthermore, the results showed that fracture-free 6H-SiC (0001) surfaces were generated in polishing with the existence of the residual crystal defects, which were associated with the origin of defects in single crystal growth. (C) 2003 Elsevier Ltd. All rights reserved.

Interpretation of negative values of the interaction parameter in the adsorption equation through the effects of surface layer heterogeneity

The problem of the negative values of the interaction parameter in the equation of Frumkin has been analyzed with respect to the adsorption of nonionic molecules on energetically homogeneous surface. For this purpose, the adsorption states of a homologue series of ethoxylated nonionic surfactants on air/water interface have been determined using four different models and literature data (surface tension isotherms). The results obtained with the Frumkin adsorption isotherm imply repulsion between the adsorbed species (corresponding to negative values of the interaction parameter), while the classical lattice theory for energetically homogeneous surface (e.g., water/air) admits attraction alone. It appears that this serious contradiction can be overcome by assuming heterogeneity in the adsorption layer, that is, effects of partial condensation (formation of aggregates) on the surface. Such a phenomenon is suggested in the Fainerman-Lucassen-Reynders-Miller (FLM) 'Aggregation model'. Despite the limitations of the latter model (e.g., monodispersity of the aggregates), we have been able to estimate the sign and the order of magnitude of Frumkin's interaction parameter and the range of the aggregation numbers of the surface species. (C) 2004 Elsevier B.V All rights reserved.

Immobilisation of electroactive macrocyclic complexes within titania films

The 4-carboxyphenyl-appended macrocyclic ligand trans-6,13-dimethyl-6-((4-carboxybenzyl)amino)-1,4,8,11-tetraazacyclotetradecane-6-amine (HL10) has been synthesised and complexed with Co-III. The mononuclear complexes [Co(HL10)(CN)](2+) and [CoL10(OH)](+) have been prepared and the crystal structures of their perchlorate salts are presented, where the ligand is bound in a pentadentate mode in each case while the 4-carboxybenzyl-substituted pendent amine remains free from the metal. The cyano-bridged dinuclear complex [CoL10-mu-NC-Fe(CN)(5)](2-) was also prepared and chemisorbed on titania-coated ITO conducting glass. The adsorbed complex is electrochemically active and cyclic voltammetry of the modified ITO working electrode in both water and MeCN solution was undertaken with simultaneous optical spectroscopy. This experiment demonstrates that reversible electrochemical oxidation of the Fe-II centre is coupled with rapid changes in the optical absorbance of the film.

Surface foam film waves studied with high-speed linescan camera

Dynamic foam films have been investigated using an improved experimental set-up with a CCD high-speed linescan camera in conjunction with the Scheludko micro-interferometric cell for studying the drainage and rupture of liquid foam films. The improved experimental set-up increased the sensibility of detection of the local thickness heterogeneities and domains during the film evolution. The evolution of the foam films up to the formation of black spots was recorded in the time intervals of 50ms. The wavelengths of the propagating surface waves and their frequencies were determined experimentally. The experimental results show that the current quasi-static hydrodynamic theory does not properly describe the wave dynamics with inter-domain channels. However, the thermodynamic condition for formation of black spots in the foam films was met by the experimental results. (c) 2005 Elsevier B.V. All rights reserved.

Effect of sodium dodecylbenzene sulfonate on the motion of three-phase contact lines on the Wilhelmy plate surface

The combined approach of the molecular-kinetic and hydrodynamic theories for description of the motion of three-phase gas-liquid-solid contact lines has been examined using the Wilhelmy plate method. The whole dynamic meniscus has been divided into molecular, hydrodynamic, and static-like regions. The Young-Laplace equation and the molecular-kinetic and hydrodynamic dewetting theories have been applied to describe the meniscus profiles and contact angle. The dissipative forces accompanying the dynamic dewetting have also been investigated. The experiments with a Wilhelmy plate made from an acrylic polymer sheet were carried out using a computerized apparatus for contact angle analysis (OCA 20, DataPhysics, Germany). The extrapolated dynamic contact angle versus velocity of the three-phase contact line for Milli-Q water and 5 x 10(-4) M SDBS solution was experimentally obtained and compared with the combined MHD models with low and moderate Reynolds numbers. The models predict similar results for the extrapolated contact angle. SDBS decreases the equilibrium contact angle and increases the molecular jumping length but does not affect the molecular frequency significantly. The hydrodynamic deformation of the meniscus, viscous dissipation, and friction were also influenced by the SDBS surfactant. (c) 2005 Elsevier Inc. All rights reserved.

Superior electric double layer capacitors using ordered mesoporous carbons

This paper reports for the first time superior electric double layer capacitive properties of ordered mesoporous carbon (OMCs) with varying ordered pore symmetries and mesopore structure. Compared to commercially used activated carbon electrode, Maxsorb, these OMC carbons have superior capacitive behavior, power output and high-frequency performance in EDLCs due to the unique structure of their mesopore network, which is more favorable for fast ionic transport than the pore networks in disordered microporous carbons. As evidenced by N-2 sorption, cyclic voltammetry and frequency response measurements, OMC carbons with large mesopores, and especially with 2-D pore symmetry, show superior capacitive behaviors (exhibiting a high capacitance of over 180 F/g even at very high sweep rate of 50 mV/s, as compared to much reduced capacitance of 73 F/g for Maxsorb at the same sweep rate). OMC carbons can provide much higher power density while still maintaining good energy density. OMC carbons demonstrate excellent high-frequency performances due to its higher surface area in pores larger than 3 nm. Such ordered mesoporous carbons (OMCs) offer a great potential in EDLC capacitors, particularly for applications where high power output and good high-frequency capacitive performances are required. (C) 2005 Elsevier Ltd. All rights reserved.

Improved VDC casting of aluminium alloys through an understanding of the surface properties of the molten metal

Vertical direct chill (VDC) casting of aluminium alloys is a mature process that has evolved over many decades through gradual change to both equipment design and casting practice. Today, air-pressurised, continuous lubrication, hot top mould systems with advanced station automation are selected as the process of choice for producing extrusion billet. Specific sets of operating parameters are employed on these stations for each alloy and size combination to produce optimal billet quality. The designs and parameters are largely derived from past experience and accumulated know-how. Recent experimental work at the University of Queensland has concentrated on understanding the way in which the surface properties of liquid aluminium alloys, e.g., surface tension, wetting angle and oxide skin strength, influence the size and shape of the naturally-stab le meniscus for a given alloy, temperature and atmosphere. The wide range of alloy-and condition-dependent values measured has led to the consideration of how these properties impact the stability of the enforced molten metal meniscus within the hot top mould cavity. The actual shape and position of the enforced meniscus is controlled by parameters such as the upstream conduction distance (UCD) from sub-mould cooling and the molten metal head. The degree of deviation of this actual meniscus from the predicted stable meniscus is considered to be a key driver in surface defect formation. This paper reports on liquid alloy property results and proposes how this knowledge might be used to better design VDC mould systems and casting practices.

Gas-surface interactions in the thermal and sub-thermal regime: A molecular dynamics study

Molecular dynamics simulations are used to study the interaction of low-energy Ar atoms with the Ni(001) surface, Angular scattering distributions, in and out of the plane of incidence, are investigated as a function of incident energy, angles of incidence, crystallographic orientation of the incident beam and surface temperature. The results show a clear transition to the structure scattering regime at around 2 eV. However, at lower energies, two sub-regimes are revealed by the simulations, Far energies up to 250 meV, scattering is mainly diffuse, and significant trapping on the surface is observed, At energies above this level, lobular patterns start to form and trapping decreases with the increase in energy, Generally, there is a weak temperature dependence, but variations in the angle of incidence and/or changes in the crystallographic direction, generate significant changes in the scattering patterns.