Isolating the non-polar contributions to the intermolecular potential for water-alkane interactions

Intermolecular potential models for water and alkanes describe pure component properties fairly well, but fail to reproduce properties of water-alkane mixtures. Understanding interactions between water and non-polar molecules like alkanes is important not only for the hydrocarbon industry but has implications to biological processes as well. Although non-polar solutes in water have been widely studied, much less work has focused on water in non-polar solvents. In this study we calculate the solubility of water in different alkanes (methane to dodecane) at ambient conditions where the water content in alkanes is very low so that the non-polar water-alkane interactions determine solubility. Only the alkane-rich phase is simulated since the fugacity of water in the water rich phase is calculated from an accurate equation of state. Using the SPC/E model for water and TraPPE model for alkanes along with Lorentz-Berthelot mixing rules for the cross parameters produces a water solubility that is an order of magnitude lower than the experimental value. It is found that an effective water Lennard-Jones energy εW/k = 220 K is required to match the experimental water solubility in TraPPE alkanes. This number is much higher than used in most simulation water models (SPC/E—εW/k = 78.2 K). It is surprising that the interaction energy obtained here is also higher than the water-alkane interaction energy predicted by studies on solubility of alkanes in water. The reason for this high water-alkane interaction energy is not completely understood. Some factors that might contribute to the large interaction energy, such as polarizability of alkanes, octupole moment of methane, and clustering of water at low concentrations in alkanes, are examined. It is found that, though important, these factors do not completely explain the anomalously strong attraction between alkanes and water observed experimentally

MLSys: The New Frontier of Machine Learning Systems

Machine learning (ML) techniques are enjoying rapidly increasing adoption. However, designing and implementing the systems that support ML models in real-world deployments remains a significant obstacle, in large part due to the radically different development and deployment profile of modern ML methods, and the range of practical concerns that come with broader adoption. We propose to foster a new systems machine learning research community at the intersection of the traditional systems and ML communities, focused on topics such as hardware systems for ML, software systems for ML, and ML optimized for metrics beyond predictive accuracy. To do this, we describe a new conference, MLSys, that explicitly targets research at the intersection of systems and machine learning with a program committee split evenly between experts in systems and ML, and an explicit focus on topics at the intersection of the two

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Oil emulsification using surface-tunable carbon black particles

Emulsification of oil from a subsurface spill and keeping it stable in the water is an important component of the natural remediation process. Motivated by the need to find alternate dispersants for emulsifying oil following a spill, we examine particle-stabilized oil-in-water emulsions. Emulsions that remain stable for months are prepared either by adding acid or salt to carboxyl-terminated carbon black (CB) suspension in water to make the particles partially hydrophobic, adding the oil to this suspension and mixing. When naphthalene, a model potentially toxic polycyclic aromatic hydrocarbon, is added to octane and an emulsion formed, it gets adsorbed significantly by the CB particles, and its transport into the continuous water is markedly reduced. In contrast to an undesirable seawater-in-crude oil emulsion produced using a commercially used dispersant, Corexit 9500A, we demonstrate the formation of a stable crude oil-in-seawater emulsion using the CB particles (with no added acid or salt), important for natural degradation. The large specific surface area of these surface functionalized CB particles, their adsorption capability and their ability to form stable emulsions are an important combination of attributes that potentially make these particles a viable alternative or supplement to conventional dispersants for emulsifying crude oil following a spill. © 2013 American Chemical Society

Water-in-trichloroethylene emulsions stabilized by uniform carbon microspheres

Uniform hard carbon spheres (HCS), synthesized by the hydrothermal decomposition of sucrose followed by pyrolysis, are effective at stabilizing water-in-trichloroethylene (TCE) emulsions. The irreversible adsorption of carbon particles at the TCE-water interface resulting in the formation of a monolayer around the water droplet in the emulsion phase is identified as the key reason for emulsion stability. Cryogenic scanning electron microscopy was used to image the assembly of carbon particles clearly at the TCE-water interface and the formation of bilayers in regions of droplet-droplet contact. The results of this study have potential implications to the subsurface injection of carbon submicrometer particles containing zero-valent iron nanoparticles to treat pools of chlorinated hydrocarbons that are sequestered in fractured bedrock. © 2011 American Chemical Society

Molecular Insights into Glass Transition in Condensed Core Asphaltenes

Glass transition in a condensed core asphaltene model was investigated using molecular dynamics simulations performed in the isobaric–isothermal ensemble. Glass transition temperature obtained from the discontinuities in the slope of specific volume versus temperature plots was in close agreement with experimental results reported in the literature. These discontinuities also correspond to those in isothermal compressibility versus temperature plots. In this paper, we separate the contributions of aliphatic and aromatic regions of the asphaltene molecule to the glass transition behavior. We demonstrate that the aliphatic chains contribute significantly to volumetric changes and impose restrictions to the molecular orientations. Glass transition is accompanied by breaking of π–π stacking of the asphaltene molecule. Therefore, the size of the fused aromatic region in the condensed core determines the strength of intermolecular interactions and the glass transition temperature <i>T</i>_g

Attachment of a hydrophobically modified biopolymer at the oil-water interface in the treatment of oil spills

The stability of crude oil droplets formed by adding chemical dispersants can be considerably enhanced by the use of the biopolymer, hydrophobically modified chitosan. Turbidimetric analyses show that emulsions of crude oil in saline water prepared using a combination of the biopolymer and the well-studied chemical dispersant (Corexit 9500A) remain stable for extended periods in comparison to emulsions stabilized by the dispersant alone. We hypothesize that the hydrophobic residues from the polymer preferentially anchor in the oil droplets, thereby forming a layer of the polymer around the droplets. The enhanced stability of the droplets is due to the polymer layer providing an increase in electrostatic and steric repulsions and thereby a large barrier to droplet coalescence. Our results show that the addition of hydrophobically modified chitosan following the application of chemical dispersant to an oil spill can potentially reduce the use of chemical dispersants. Increasing the molecular weight of the biopolymer changes the rheological properties of the oil-in-water emulsion to that of a weak gel. The ability of the biopolymer to tether the oil droplets in a gel-like matrix has potential applications in the immobilization of surface oil spills for enhanced removal. © 2013 American Chemical Society

Growth of gold nanoparticles in human cells

Gold nanoparticles of 20-100 nm diameter were synthesized within HEK-293 (human embryonic kidney), HeLa (human cervical cancer), SiHa (human cervical cancer), and SKNSH (human neuroblastoma) cells. Incubation of 1 mM tetrachloroaurate solution, prepared in phosphate buffered saline (PBS), pH 7.4, with human cells grown to ~80% confluency yielded systematic growth of nanoparticles over a period of 96 h. The cells, stained due to nanoparticle growth, were adherent to the bottom of the wells of the tissue culture plates, with their morphology preserved, indicating that the cell membrane was intact. Transmission electron microscopy of ultrathin sections showed the presence of nanoparticles within the cytoplasm and in the nucleus, the latter being much smaller in dimension. Scanning near field microscopic images confirmed the growth of large particles within the cytoplasm. Normal cells gave UV-visible signatures of higher intensity than the cancer cells. Differences in the cellular metabolism of cancer and noncancer cells were manifested, presumably in their ability to carry out the reduction process