Surface-acoustic-wave counterflow micropumps for on-chip liquid motion control in two-dimensional microchannel arrays

Fully controlled liquid injection and flow in hydrophobic polydimethylsiloxane (PDMS) two-dimensional microchannel arrays based on on-chip integrated, low-voltage-driven micropumps are demonstrated. Our architecture exploits the surface-acoustic-wave (SAW) induced counterflow mechanism and the effect of nebulization anisotropies at crossing areas owing to lateral propagating SAWs. We show that by selectively exciting single or multiple SAWs, fluids can be drawn from their reservoirs and moved towards selected positions of a microchannel grid. Splitting of the main liquid flow is also demonstrated by exploiting multiple SAW beams. As a demonstrator, we show simultaneous filling of two orthogonal microchannels. The present results show that SAW micropumps are good candidates for truly integrated on-chip fluidic networks allowing liquid control in arbitrarily shaped two-dimensional microchannel arrays.

Investigation of the Potential Energy Surface for the First Step in the Alkaline Hydrolysis of Methyl Acetate

The potential energy surface for the first step of the alkaline hydrolysis of methyl acetate was explored by a variety of methods. The conformational search routine within SPARTAN was used to determine the lowest energy am1 and pm3 structures for the anionic tetrahedral intermediate. Ab initio single point and geometry optimization calculations were performed to determine the lowest energy conformer, and the linear synchronous transition (lst) method was used to provide an initial structure for transition state optimization. Transition states were obtained at the am1, pm3, 3-21G, and 3-21 + G levels of theory. These transition states were compared with the anionic tetrahedral intermediates to examine the assumption that the intermediate is a good model for the transition state. In addition, the Cramer/Truhlar sm3 solvation model was used at the semiempirical level to compare gas phase and aqueous alkaline hydrolysis of methyl acetate.

Electrochemical scanning tunnelling spectroscopy of a ferrocene-modified n-Si(111)-surface: electrolyte gating and ambipolar FET behaviour

As revealed for the first time by in situ scanning tunnelling spectroscopy (STS), ferrocene-modified Si(111) substrates show ambipolar field effect transistor (FET) behaviour upon electrolyte gating.

Effects of drilling and stress release on hydraulic properties and porewater chemistry of crystalline rocks

The experimental verification of matrix diffusion in crystalline rocks largely relies on indirect methods performed in the laboratory. Such methods are prone to perturbations of the rock samples by collection and preparation and therefore the laboratory-derived transport properties and fluid composition might not represent in situ conditions. We investigated the effects induced by the drilling process and natural rock stress release by mass balance considerations and sensitivity analysis of analytical out-diffusion data obtained from originally saturated, large-sized drillcore material from two locations drilled using traced drilling fluid. For in situ stress-released drillcores of quartz-monzodiorite composition from the Aspo HRL, Sweden, tracer mass balance considerations and 1D and 2D diffusion modelling consistently indicated a contamination of <1% of the original pore water. This chemically disturbed zone extends to a maximum of 0.1 mm into the drillcore (61.8 mm x 180.1 mm) corresponding to about 0.66% of the total pore volume (0.77 vol.%). In contrast, the combined effects of stress release and the drilling process, which have influenced granodioritic drillcore material from 560 m below surface at Forsmark. Sweden, resulted in a maximum contamination of the derived porewater Cl(-) concentration of about 8%. The mechanically disturbed zone with modified diffusion properties covers the outermost similar to 6 mm of the drillcore (50 mm x 189 mm), whereas the chemically disturbed zone extends to a maximum of 0.3 mm based on mass balance considerations, and to 0.15 mm to 0.2 mm into the drillcore based on fitting the observed tracer data. This corresponds to a maximum of 2.4% of the total pore volume (0.62 vol.%) being affected by the drilling-fluid contamination. The proportion of rock volume affected initially by drilling fluid or subsequently with experiment water during the laboratory diffusion and re-saturation experiments depends on the size of the drillcore material and will become larger the smaller the sample used for the experiment. The results are further in support of matrix diffusion taking place in the undisturbed matrix of crystalline rocks at least in the cm range.

Synthesis and Surface Modification of CdSe and CdS Quantum Dots Exhibiting High Quantum Yield

The thesis investigates the effect of surface treatment with various reducing and oxidizing agents on the quantum yield (QY) of CdSe and CdS quantum dots (QDs). The QDs, as synthesized by the organometallic method, contained defect sites on their surface that trapped photons and prevented their radiative recombination, therefore resulting in adecreased QY. To passivate these defect sites and enhance the QY, the QDs were treated with various reducing and oxidizing agents, including: sodium borohydride (NaBH4), calcium hydride (CaH2), hydrazine (N2H4), benzoyl peroxide (C14H10O4), and tert-butylhydroperoxide (C4H10O2). It was hypothesized that the reducing/oxidizing agents reduced the ligands on the QD surface, causing them to detach, thereby allowing oxygen from atmospheric air to bind to the exposed cadmium. This cadmium oxdide (CdO) layeraround the QD surface satisfied the defect sites and resulted in an increased QY. To correlate what effect the reducing and oxidizing agents were having on the optical properties of the QDs, we investigated these treatments on the following factors:chalcogenide (Se vs. S), ligand (oleylamine vs. OA), coordinating solvent (ODE vs.TOA), and dispersant solvent (chloroform vs. toluene) on the overall optical properties of the QDs. The QY of each sample was calculated before and after the various surface treatments from ultra-violet visible spectroscopy (UV-Vis) and fluorescence spectroscopy data to determine if the treatment was successful.From our results, we found that sodium borohydride was the most effective surface treatment, with 10 of the 12 treatments resulting in an increased QY. Hydrazine, on the other hand, was the least effective treatments, as it quenched the QD fluorescence in every case. From these observations, we hypothesize that the effectiveness of the QD surface treatments was dependent on reaction rate. More specifically, when the surface treatment reaction happened too quickly, we hypothesize that the QDs began to aggregate, resulting in a quenched fluorescence. Furthermore, we believe that the reactionrate is dependent on concentration of the reducing/oxidizing agents, solubility of the agents in each solvent, and reactivity of the agents with water. The quantum yield of the QDs can therefore be maximized by slowing the reaction rate of each surface treatment toa rate that allows for the proper passivation of defect sites.

Wetting and spreading of a surfactant film on solid particles: influence of sharp edges and surface irregularities

In addition to particle size and surface chemistry, the shape of particles plays an important role in their wetting and displacement by the surfactant film in the lung. The role of particle shape was the subject of our investigations using a model system consisting of a modified Langmuir-Wilhelmy surface balance. We measured the influence of sharp edges (lines) and other highly curved surfaces, including sharp corners or spikes, of different particles on the spreading of a dipalmitoylphosphatidyl (DPPC) film. The edges of cylindrical sapphire plates (circular curved edges, 1.65 mm radius) were wetted at a surface tension of 10.7 mJ/m2 (standard error (SE) = 0.45, n = 20) compared with that of 13.8 mJ/m2 (SE = 0.20, n = 20) for cubic sapphire plates (straight linear edges, edge length 3 mm) (p < 0.05). The top surfaces of the sapphire plates (cubic and cylindrical) were wetted at 8.4 mJ/m2 (SE = 0.54, n = 20) and 9.1 mJ/m2 (SE = 0.50, n = 20), respectively, but the difference was not significant (p > 0.05). The surfaces of the plates showed significantly higher resistance to spreading compared to that of the edges, as substantially lower surface tensions were required to initiate wetting (p < 0.05). Similar results were found for talc particles, were the edges of macro- and microcrystalline particles were wetted at 7.2 mJ/m2 (SE = 0.52, n = 20) and 8.2 mJ/m2 (SE = 0.30, n = 20) (p > 0.05), respectively, whereas the surfaces were wetted at 3.8 mJ/m2 (SE = 0.89, n = 20) and 5.8 mJ/m2 (SE = 0.52, n = 20) (p < 0.05), respectively. Further experiments with pollen of malvaceae and maize (spiky and fine knobbly surfaces) were wetted at 10.0 mJ/m2 (SE = 0.52, n = 10) and 22.75 mJ/m2 (SE = 0.81, n = 10), respectively (p < 0.05). These results show that resistance to spreading of a DPPC film on various surfaces is dependent on the extent these surfaces are curved. This is seen with cubic sapphire plates which have at their corners a radius of curvature of about 0.75 microm, spiky malvaceae pollen with an even smaller radius on top of their spikes, or talc with various highly curved surfaces. These highly curved surfaces resisted wetting by the DPPC film to a higher degree than more moderately curved surfaces such as those of cylindrical sapphire plates, maize pollens, or polystyrene spheres, which have a surface free energy similar to that of talc but a smooth surface. The macroscopic plane surfaces of the particles demonstrated the greatest resistance to spreading. This was explained by the extremely fine grooves in the nanometer range, as revealed by electron microscopy. In summary, to understand the effects of airborne particles retained on the surfaces of the respiratory tract, and ultimately their pathological potential, not only the particle size and surface chemistry but also the particle shape should be taken in consideration.

Understanding the chemistry of dental erosion

The mineral in our teeth is composed of a calcium-deficient carbonated hydroxyapatite (Ca10-xNax(PO4)6-y(CO3)z(OH)2-uFu). These substitutions in the mineral crystal lattice, especially carbonate, renders tooth mineral more acid soluble than hydroxyapatite. During erosion by acid and/or chelators, these agents interact with the surface of the mineral crystals, but only after they diffuse through the plaque, the pellicle, and the protein/lipid coating of the individual crystals themselves. The effect of direct attack by the hydrogen ion is to combine with the carbonate and/or phosphate releasing all of the ions from that region of the crystal surface leading to direct surface etching. Acids such as citric acid have a more complex interaction. In water they exist as a mixture of hydrogen ions, acid anions (e.g. citrate) and undissociated acid molecules, with the amounts of each determined by the acid dissociation constant (pKa) and the pH of the solution. Above the effect of the hydrogen ion, the citrate ion can complex with calcium also removing it from the crystal surface and/or from saliva. Values of the strength of acid (pKa) and for the anion-calcium interaction and the mechanisms of interaction with the tooth mineral on the surface and underneath are described in detail.

Potential of chemically modified hydrophilic surface characteristics to support tissue integration of titanium dental implants

In the past, several modifications of specific surface properties such as topography, structure, chemistry, surface charge, and wettability have been investigated to predictably improve the osseointegration of titanium implants. The aim of the present review was to evaluate, based on the currently available evidence, the impact of hydrophilic surface modifications of titanium for dental implants. A surface treatment was performed to produce hydroxylated/hydrated titanium surfaces with identical microstructure to either acid-etched, or sand-blasted, large grit and acid-etched substrates, but with hydrophilic character. Preliminary in vitro studies have indicated that the specific properties noted for hydrophilic titanium surfaces have a significant influence on cell differentiation and growth factor production. Animal experiments have pointed out that hydrophilic surfaces improve early stages of soft tissue and hard tissue integration of either nonsubmerged or submerged titanium implants. This data was also corroborated by the results from preliminary clinical studies. In conclusion, the present review has pointed to a potential of hydrophilic surface modifications to support tissue integration of titanium dental implants.

The Role of Water Chemistry in the Concentration of Hematite Ore

Selective flocculation and dispersion processes rely on differences in the surface chemistry of fine mineral particles (<25 >ìm) to allow for the concentration of specific minerals from an ore body. The effectiveness of selective flocculation and dispersion processes for the concentration of hematite (Fe2O3) ore are strongly dependent on the ionic content of the process water. The goal of this research was to analyze the ionic content of an operating selective flocculation and dispersion type hematite ore concentrator and determine how carbon dioxide affects the filtration of the final product. A detailed water chemistry analysis of the entire process was determined to show concentration profiles throughout the process. This information was used to explain process phenomena and promote future research into this subject. A subsequent laboratory study was conducted to show how carbon dioxide affects filtration rate and relate this effect to the zeta potential of the constituents of the concentrated hematite ore.

Geochemistry and Stable Isotopes of Surface Water and Groundwater in the Continental Pit in Butte, Montana, USA

The Continental porphyry Cu‐Mo mine, located 2 km east of the famous Berkeley Pit lake of Butte, Montana, contains two small lakes that vary in size depending on mining activity. In contrast to the acidic Berkeley Pit lake, the Continental Pit waters have near-neutral pH and relatively low metal concentrations. The main reason is geological: whereas the Berkeley Pit mined highly‐altered granite rich in pyrite with no neutralizing potential, the Continental Pit is mining weakly‐altered granite with lower pyrite concentrations and up to 1‐2% hydrothermal calcite. The purpose of this study was to gather and interpret information that bears on the chemistry of surface water and groundwater in the active Continental Pit. Pre‐existing chemistry data from sampling of the Continental Pit were compiled from the Montana Bureau of Mines and Geology and Montana Department of Environmental Quality records. In addition, in March of 2013, new water samples were collected from the mine’s main dewatering well, the Sarsfield well, and a nearby acidic seep (Pavilion Seep) and analyzed for trace metals and several stable isotopes, including dD and d18O of water, d13C of dissolved inorganic carbon, and d34S of dissolved sulfate. In December 2013, several soil samples were collected from the shore of the frozen pit lake and surrounding area. The soil samples were analyzed using X‐ray diffraction to determine mineral content. Based on Visual Minteq modeling, water in the Continental Pit lake is near equilibrium with a number of carbonate, sulfate, and molybdate minerals, including calcite, dolomite, rhodochrosite (MnCO3), brochantite (CuSO4·3Cu(OH)2), malachite (Cu2CO3(OH)2), hydrozincite (Zn5(CO3)2(OH)6), gypsum, and powellite (CaMoO4). The fact that these minerals are close to equilibrium suggests that they are present on the weathered mine walls and/or in the sediment of the surface water ponds. X‐Ray Diffraction (XRD) analysis of the pond “beach” sample failed to show any discrete metal‐bearing phases. One of the soil samples collected higher in the mine, near an area of active weathering of chalcocite‐rich ore, contained over 50% chalcanthite (CuSO4·5H2O). This water‐soluble copper salt is easily dissolved in water, and is probably a major source of copper to the pond and underlying groundwater system. However, concentrations of copper in the latter are probably controlled by other, less‐soluble minerals, such as brochantite or malachite. Although the acidity of the Pavilion Seep is high (~ 11 meq/L), the flow is much less than the Sarsfield Well at the current time. Thus, the pH, major and minor element chemistry in the Continental Pit lakes are buffered by calcite and other carbonate minerals. For the Continental Pit waters to become acidic, the influx of acidic seepage (e.g., Pavilion Seep) would need to increase substantially over its present volume.

Molecular Surface Features in Modeling the HIV-1 RT Inhibitory Activity of 2-(2,6-Disubstituted phenyl)-3-(substituted pyrimidin-2-yl)-thiazolidin-4-ones

The human immunodeficiency virus-1 reverse transcriptase inhibitory activity of 2-(2,6-disubstituted phenyl)-3-(substituted pyrimidin-2-yl)-thiazolidin-4-ones have been analyzed using combinatorial protocol in multiple linear regression (CP-MLR) with several electronic and molecular surface area features of the compounds obtained from Molecular Operating Environment (MOE) software. The study has indicated the role of different charged molecular surface areas in modeling the inhibitory activity of the compounds. The derived models collectively suggested that the compounds should be compact without bulky substitutions on its peripheries for better HIV-1 RT inhibitory activity. It also emphasized the necessity of hydrophobicity and compact structural features for their activity. The scope of the descriptors identified for these analogues have been verified by extending the dataset with different 2-(disubstituted phenyl)-3-(substituted pyridin-2-yl)-thiazolidin-4-ones. The joint analysis of extended dataset highlighted the information content of identified descriptors in modeling the HIV-1 RT inhibitory activity of the compounds.