Monte Carlo simulation of water-tetrahydrofuran mixtures

Monte Carlo simulations of water-tetrahydrofuran (THF) mixtures were performed in the isothermal-isobaric ensemble (NPT) at T = 298 K and p = 1 atm. The interaction energy was calculated using the TIP4P model for water and a five-site united atom representation for the THF molecule. The potential energy surfaces for water-THF interactions were obtained by using combining rules and the original potential functions used for pure liquids. Theoretical values obtained for the average interaction energy as a function of concentration are in good agreement with available experimental data. Results from the partitioning of the total interaction energy into water-water, water-THF and THF-THF contributions are presented. These results are useful to distinguish between the quantitative contributions of these molecular interactions to the energetic behavior of the water-THF mixing process. The radial distribution functions for HW-OTHF and OW-OTHF site-site interactions show the salient features of hydrogen-bonded liquids. Comparison of the average number of water-water complexes interacting through hydrogen bonding in water-THF and water-methanol mixtures shows an enhancement of the water-water coordination number in a THF rich environment. © 1995.

Effect of whitening and desensitizing dentifrices on composite surfaces treated with surface sealants

This study evaluated the effect of different dentifrices on the microhardness and surface roughness of composite surfaces covered by surface sealants. Samples of Filtek P60 were made and divided into groups, in accordance with surface treatments: G1 - Fortify; G2 - Fortify Plus; G3 - control (none). For Knoop microhardness evaluation, the specimens were placed in a microdurometer, under a load of 50 g for 15 sec. The analyses of surface roughness were carried out individually in a profilometer. The specimens were submitted to toothbrushing using dentifrices: Colgate Maximum Protection Anti-caries, Colgate Whitening or Sensodyne, diluted in distilled water (1:3) for 30 000 cycles. The results showed that the control group (G3) presented the highest microhardness values. The control group presented, before toothbrushing, the lowest surface roughness values, and after toothbrushing there were no differences among the experimental groups. The maintenance of the lowest values of microhardness demonstrated the effectiveness of these sealant materials to support the abrasive wear.

Environmental effects in kelvin force microscopy of modified diamond surfaces

We have explored the effects of atmospheric environment on Kelvin force microscopy (KFM) measurements of potential difference between different regions of test polycrystalline diamond surfaces. The diamond films were deposited by microwave plasma-assisted chemical vapor deposition, which naturally produces hydrogen terminations on the surface of the films formed. Selected regions were patterned by electron-beam lithography and chemical terminations of oxygen or fluorine were created by exposure to an oxygen or fluorine plasma source. For KFM imaging, the samples were mounted in a hood with a constant flow of helium gas. Successive images were taken over a 5-h period showing the effect of the environment on KFM imaging. We conclude that the helium flow removes water molecules adsorbed on the surface of the samples, resulting in differences in surface potential between adjacent regions. The degree of water removal is different for surfaces with different terminations. The results highlight the importance of taking into account the atmospheric environment when carrying out KFM analysis. (C) 2012 Wiley Periodicals, Inc.

Water-in-Oil Micro-Emulsion Enhances the Secondary Structure of a Protein by Confinement

A scheme is presented in which an organic solvent environment in combination with surfactants is used to confine a natively unfolded protein inside an inverse microemulsion droplet. This type of confinement allows a study that provides unique insight into the dynamic structure of an unfolded, flexible protein which is still solvated and thus under near-physiological conditions. In a model system, the protein osteopontin (OPN) is used. It is a highly phosphorylated glycoprotein that is expressed in a wide range of cells and tissues for which limited structural analysis exists due to the high degree of flexibility and large number of post-translational modifications. OPN is implicated in tissue functions, such as inflammation and mineralisation. It also has a key function in tumour metastasis and progression. Circular dichroism measurements show that confinement enhances the secondary structural features of the protein. Small-angle X-ray scattering and dynamic light scattering show that OPN changes from being a flexible protein in aqueous solution to adopting a less flexible and more compact structure inside the microemulsion droplets. This novel approach for confining proteins while they are still hydrated may aid in studying the structure of a wide range of natively unfolded proteins.

Resistance of Cyanobacterial Fouling on Architectural Paint Films to Cleaning by Water Jet

Mortar panels painted with three different white acrylic coatings were exposed to the environment in urban (So Paulo) and rural (Pirassununga) sites in Brazil for 7 years. After this time, all panels were almost equally discoloured, and paint detachment was observed to only a small degree. The biofilms were composed mainly of cyanobacteria and filamentous fungi, principal genera being Gloeocapsa and Chroococcidiopsis of the cyanobacteria, and Cladosporium and Alternaria of the fungi. Two of the three paints in Pirassununga became covered by a pink film that contained red-encapsulated Gloeocapsa and clay particles. The third, an 800% elastomeric matt formulation, became discoloured with a grey, only slightly pink, film, although the same cyanobacteria were present. The levels of paint detachments from all films in both locations were low, with rating range of 0-1 of a maximum 5 (100% detachment). After high-pressure water jetting, paint detachments increased at both locations, up to 2 in Pirassununga and 3 in So Paulo. Discoloration decreased; L*A*B* analysis of surface discoloration showed that Delta E (alteration in colour from the original paint film) changed from 28-39 before cleaning to 13-16 afterwards. The pink coloration was not entirely removed from Pirassununga samples, suggesting that cyanobacterial cells are difficult to detach, and microscopic analysis of the biofilms confirmed that Gloeocapsa was still present as the principal contaminant on all surfaces, with Chroococcidiopsis being present as the second most common. Almost no fungi were detected after water jet application.

WATER VAPOR CONDUCTANCE OF THE LOWER CRETACEOUS DINOSAURIAN EGGS FROM SANAGASTA, LA RIOJA, ARGENTINA: PALEOBIOLOGICAL AND PALEOECOLOGICAL IMPLICATIONS FOR SOUTH AMERICAN FAVEOLOOLITHID AND MEGALOOLITHID EGGS

The water vapor conductance (G(H20)) of the neosauropod eggs from the Lower Cretaceous Sanagasta nesting site in La Rioja Province, Argentina, was examined and compared with other Cretaceous Argentinean oological material. The 2900 mgH(2)O/day.Torr G(H2O) of the Sanagasta eggshells confirms an extremely moist nesting environment and supports field observations of dug-out nests in a geothermal setting. The observed thinning of the outer eggshell surface during incubation increases gas conductance and concomitantly decreases eggshell mechanical resistance during the late ontogenetic stages, thus facilitating embryonic development and hatching. The Sanagasta and Entre Rios Province faveoloolithid eggs display the highest and comparable 61120 values and share several morphological and diagenetic characters, indicating comparable nesting strategy in geothermal settings. However, the faveoloolithid Yamintie and La Pampa Province specimens cluster together with lower G(H20) values closer to the megaloolithid eggs. The Gnu) of the megaloolithid egg Megaloolithus patagonicus was reconsidered and new results are now congruent with other reported megaloolithid GH2O values. Additionally, we hypothesize that V-shaped pore canals of M. patagonicus, which upper sections reach only the top third or half eggshell thickness and, a wider section in the middle would not compromise the overall egg mechanical resistance like vertical pores connecting directly the outer to the inner eggshell surfaces. Such pore spatial arrangement and geometry would enhance, as the eggshell thins during incubation, a greater G(H2O), G(O2) and G(CO2) and facilitate embryonic development in high moisture nesting contents. Overall, data suggests that neosauropod nesting and brooding behaviors were dependent on elevated moisture nesting environments.

Influence of Ozone Gas and Ozonated Water Application to Dentin and Bonded Interfaces on Resin-Dentin Bond Strength

Purpose: To assess the influence of ozone gas and ozonated water application to prepared cavity and bonded interfaces on the resin/dentin bond strength of two-step etch-and-rinse adhesive systems (Adper Single Bond 2 [SB2] and XP-Bond [XP]). Materials and Methods: Sixty extracted human third molars were sectioned perpendicularly to their long axes to expose flat occlusal dentin surfaces. In experiment 1, dentin was treated with ozone before the bonding procedure, while in experiment 2, ozone was applied to resin/dentin bonded interfaces. In experiment 1, dentin surfaces were treated either with ozone gas (2100 ppm), ozonated water (3.5 ppm), or distilled water for 120 s, and then bonded with SB2 or XP according to manufacturers' instructions. Hybrid composite buildups were incrementally constructed and the teeth were sectioned into resin-dentin sticks (0.8 mm(2)). In experiment 2, dentin surfaces were first bonded with SB2 or XP, composite buildups were constructed, and bonded sticks obtained. The sticks were treated with ozone as previously described. Bonded sticks were tested under tensile stress at 1 mm/min. Silver nitrate impregnation along the resin/dentin interfaces was also evaluated under SEM. Results: Two-way ANOVA (adhesive and ozone treatment) detected no significant effect for the cross-product interaction and the main factors in the two experiments (p > 0.05), which was confirmed by the photomicrographs. Conclusion: Ozone gas and ozonated water used before the bonding procedure or on resin/dentin bonded interfaces have no deleterious effects on the bond strengths and interfaces.

Ultrasonic sensor for the presence of oily contaminants in water

The determination of the complex reflection coefficient of ultrasonic shear-waves at the solid-liquid interface is a technique employed for the measurement of the viscoelastic properties of liquids. An interesting property of the measurement technique is the very small penetration depth of the shear-waves into the liquid sample, which permits measurements with liquid films of some micrometers thick. This property, along with the adhesion of oily substances to surfaces, can be used for the detection of oily contaminants in water. In this work, the employment of the ultrasonic shear-wave reflection technique to the detection of oily contaminants in water is proposed and the theoretical and experimental concepts involved are discussed. Preliminary experimental results show the measurement technique can detect SAE 40 automotive oil in water in volume proportions less than 0.5%.

Temperature changes on the root surfaces of mandibular incisors after an 810-nm high-intensity intracanal diode laser irradiation

Temperature changes caused by laser irradiation can promote damage to the surrounding dental tissues. In this study, we evaluated the temperature changes of recently extracted human mandibular incisors during intracanal irradiation with an 810-nm diode laser at different settings. Fifty mandibular incisors were enlarged up to an apical size of ISO No. 40 file. After the final rinse with 17% ethylenediaminetetraacetic acid, 0.2% lauryl sodium sulfate biologic detergent, and sterile water, samples were irradiated with circular movements from apex to crown through five different settings of output power (1.5, 2.0, 2.5, 3.0, and 3.5 W) in continuous mode. The temperature changes were measured on both sides of the apical and middle root thirds using two thermopar devices. A temperature increase of 7 degrees C was considered acceptable as a safe threshold when applying the diode laser. Results: The results showed that only 3.5-W output power increased the outer surface temperature above the critical value. Conclusion: The recommended output power can be stipulated as equal to or less than 3 W to avoid overheating during diode laser irradiation on thin dentin walls. (c) 2012 Society of Photo-Optical Instrumentation Engineers (SPIE). [DOI: 10.1117/1.JBO.17.1.015006]

Triboelectricity: Macroscopic Charge Patterns Formed by Self-Arraying Ions on Polymer Surfaces

Tribocharged polymers display macroscopically patterned positive and negative domains, verifying the fractal geometry of electrostatic mosaics previously detected by electric probe microscopy. Excess charge on contacting polyethylene (PE) and polytetrafluoroethylene (PTFE) follows the triboelectric series but with one caveat: net charge is the arithmetic sum of patterned positive and negative charges, as opposed to the usual assumption of uniform but opposite signal charging on each surface. Extraction with n-hexane preferentially removes positive charges from PTFE, while 1,1-difluoroethane and ethanol largely remove both positive and negative charges. Using suitable analytical techniques (electron energy-loss spectral imaging, infrared microspectrophotometry and carbonization/colorimetry) and theoretical calculations, the positive species were identified as hydrocarbocations and the negative species were identified as fluorocarbanions. A comprehensive model is presented for PTFE tribocharging with PE: mechanochemical chain homolytic rupture is followed by electron transfer from hydrocarbon free radicals to the more electronegative fluorocarbon radicals. Polymer ions self-assemble according to Flory-Huggins theory, thus forming the experimentally observed macroscopic patterns. These results show that tribocharging can only be understood by considering the complex chemical events triggered by mechanical action, coupled to well-established physicochemical concepts. Patterned polymers can be cut and mounted to make macroscopic electrets and multipoles.

Identification of bacteria in drinking and purified water during the monitoring of a typical water purification system

Abstract Background A typical purification system that provides purified water which meets ionic and organic chemical standards, must be protected from microbial proliferation to minimize cross-contamination for use in cleaning and preparations in pharmaceutical industries and in health environments. Methodology Samples of water were taken directly from the public distribution water tank at twelve different stages of a typical purification system were analyzed for the identification of isolated bacteria. Two miniature kits were used: (i) identification system (api 20 NE, Bio-Mérieux) for non-enteric and non-fermenting gram-negative rods; and (ii) identification system (BBL crystal, Becton and Dickson) for enteric and non-fermenting gram-negative rods. The efficiency of the chemical sanitizers used in the stages of the system, over the isolated and identified bacteria in the sampling water, was evaluated by the minimum inhibitory concentration (MIC) method. Results The 78 isolated colonies were identified as the following bacteria genera: Pseudomonas, Flavobacterium and Acinetobacter. According to the miniature kits used in the identification, there was a prevalence of isolation of P. aeruginosa 32.05%, P. picketti (Ralstonia picketti) 23.08%, P. vesiculares 12.82%,P. diminuta 11.54%, F. aureum 6.42%, P. fluorescens 5.13%, A. lwoffi 2.56%, P. putida 2.56%, P. alcaligenes 1.28%, P. paucimobilis 1.28%, and F. multivorum 1.28%. Conclusions We found that research was required for the identification of gram-negative non-fermenting bacteria, which were isolated from drinking water and water purification systems, since Pseudomonas genera represents opportunistic pathogens which disperse and adhere easily to surfaces, forming a biofilm which interferes with the cleaning and disinfection procedures in hospital and industrial environments.

Atomistic Study of Water Confined in Silica.

In this work, we have used a combined of atomistic simulation methods to explore the effects of confinement of water molecules between silica surfaces. Firstly, the mechanical properties of water severe confined (~3A) between two silica alpha-quartz was determined based on first principles calculations within the density functional theory (DFT). Simulated annealing methods were employed due to the complex potential energry surface, and the difficulties to avoid local minima. Our results suggest that much of the stiffness of the material (46%) remains, even after the insertion of a water monolayer in the silica. Secondly, in order to access typical time scales for confined systems, classical molecular dynamics was used to determine the dynamical properties of water confined in silica cylindrical pores, with diameters varying from 10 to 40A. in this case we have varied the passivation of the silica surface, from 13% to 100% of SiOH, and the other terminations being SiOH2 and SiOH3, the distribution of the different terminations was obtained with a Monte Carlo simulation. The simulations indicates a lowering of the diffusion coefficientes as the diameter decreases, due to the structuration of hydrogen bonds of water molecules; we have also obtained the density profiles of the confined water and the interfacial tension.

Synthesis and characterisation of photoreactive silanes for the self-assembly on functionalised silica surfaces

The aim of this thesis was to investigate novel techniques to create complex hierarchical chemical patterns on silica surfaces with micro to nanometer sized features. These surfaces were used for a site-selective assembly of colloidal particles and oligonucleotides. To do so, functionalised alkoxysilanes (commercial and synthesised ones) were deposited onto planar silica surfaces. The functional groups can form reversible attractive interactions with the complementary surface layers of the opposing objects that need to be assembled. These interactions determine the final location and density of the objects onto the surface. Photolithographically patterned silica surfaces were modified with commercial silanes, in order to create hydrophilic and hydrophobic regions on the surface. Assembly of hydrophobic silica particles onto these surfaces was investigated and finally, pH and charge effects on the colloidal assembly were analysed. In the second part of this thesis the concept of novel, "smart" alkoxysilanes is introduced that allows parallel surface activation and patterning in a one-step irradiation process. These novel species bear a photoreactive head-group in a protected form. Surface layers made from these molecules can be irradiated through a mask to remove the protecting group from selected regions and thus generate lateral chemical patterns of active and inert regions on the substrate. The synthesis of an azide-reactive alkoxysilane was successfully accomplished. Silanisation conditions were carefully optimised as to guarantee a smooth surface layer, without formation of micellar clusters. NMR and DLS experiments corroborated the absence of clusters when using neither water nor NaOH as catalysts during hydrolysis, but only the organic solvent itself. Upon irradiation of the azide layer, the resulting nitrene may undergo a variety of reactions depending on the irradiation conditions. Contact angle measurements demonstrated that the irradiated surfaces were more hydrophilic than the non-irradiated azide layer and therefore the formation of an amine upon irradiation was postulated. Successful photoactivation could be demonstrated using condensation patterns, which showed a change in wettability on the wafer surface upon irradiation. Colloidal deposition with COOH functionalised particles further underlined the formation of more hydrophilic species. Orthogonal photoreactive silanes are described in the third part of this thesis. The advantage of orthogonal photosensitive silanes is the possibility of having a coexistence of chemical functionalities homogeneously distributed in the same layer, by using appropriate protecting groups. For this purpose, a 3',5'-dimethoxybenzoin protected carboxylic acid silane was successfully synthesised and the kinetics of its hydrolysis and condensation in solution were analysed in order to optimise the silanisation conditions. This compound was used together with a nitroveratryl protected amino silane to obtain bicomponent surface layers. The optimum conditions for an orthogonal deprotection of surfaces modified with this two groups were determined. A 2-step deprotection process through a mask generated a complex pattern on the substrate by activating two different chemistries at different sites. This was demonstrated by colloidal adsorption and fluorescence labelling of the resulting substrates. Moreover, two different single stranded oligodeoxynucleotides were immobilised onto the two different activated areas and then hybrid captured with their respective complementary, fluorescent labelled strand. Selective hybridisation could be shown, although non-selective adsorption issues need to be resolved, making this technique attractive for possible DNA microarrays.

Core-shell particles and their application for superhydrophobic surfaces

During the last years great effort has been devoted to the fabrication of superhydrophobic surfaces because of their self-cleaning properties. A water drop on a superhydrophobic surface rolls off even at inclinations of only a few degrees while taking up contaminants encountered on its way. rnSuperhydrophobic, self-cleaning coatings are desirable for convenient and cost-effective maintenance of a variety of surfaces. Ideally, such coatings should be easy to make and apply, mechanically resistant, and long-term stable. None of the existing methods have yet mastered the challenge of meeting all of these criteria.rnSuperhydrophobicity is associated with surface roughness. The lotus leave, with its dual scale roughness, is one of the most efficient examples of superhydrophobic surface. This thesis work proposes a novel technique to prepare superhydrophobic surfaces that introduces the two length scale roughness by growing silica particles (~100 nm in diameter) onto micrometer-sized polystyrene particles using the well-established Stöber synthesis. Mechanical resistance is conferred to the resulting “raspberries” by the synthesis of a thin silica shell on their surface. Besides of being easy to make and handle, these particles offer the possibility for improving suitability or technical applications: since they disperse in water, multi-layers can be prepared on substrates by simple drop casting even on surfaces with grooves and slots. The solution of the main problem – stabilizing the multilayer – also lies in the design of the particles: the shells – although mechanically stable – are porous enough to allow for leakage of polystyrene from the core. Under tetrahydrofuran vapor polystyrene bridges form between the particles that render the multilayer-film stable. rnMulti-layers are good candidate to design surfaces whose roughness is preserved after scratch. If the top-most layer is removed, the roughness can still be ensured by the underlying layer.rnAfter hydrophobization by chemical vapor deposition (CVD) of a semi-fluorinated silane, the surfaces are superhydrophobic with a tilting angle of a few degrees. rnrnrn

Drainage of thin aqueous films between solid surfaces measured with the colloidal probe technique

Understanding liquid flow at the vicinity of solid surfaces is crucial to the developmentrnof technologies to reduce drag. One possibility to infer flow properties at the liquid-solid interface is to compare the experimental results to solutions of the Navier-Stokes equations assuming the no-slip boundary condition (BC) or the slip BC. There is no consensus in the literature about which BC should be used to model the flow of aqueous solutions over hydrophilic surfaces. Here, the colloidal probe technique is used to systematically address this issue, measuring forces acting during drainage of water over a surface. Results show that experimental variables, especially the cantilever spring constant, lead to the discrepancy observed in the literature. Two different parameters, calculated from experimental variables, could be used to separate the data obtained in this work and those reported in the literature in two groups: one explained with the no-slip BC, and another with the slip BC. The observed residual slippage is a function of instrumental variables, showing a trend incompatible with the available physical justifications. As a result, the no-slip is the more appropriate BC. The parameters can be used to avoid situations where the no-slip BC is not satisfied.