Development of a diesel surrogate for improved autoignition prediction: Methodology and detailed chemical kinetic modeling

While the surrogate fuel approach has been successfully applied to the simulation of the combustion behaviors of complex gasoline and jet fuels, its application to diesel fuels has been challenging. One of the main challenges derives from the large molecular size of the representative surrogate components necessary to simulate diesel blends, as the development of detailed chemical kinetic models and their validation becomes more complex. In this study, a new surrogate mixture that emulates the chemical and physical properties of a well-characterized diesel fuel is proposed. An optimization procedure was used to select surrogate components that can match both the physical and chemical properties of the target diesel fuel comprehensively. The surrogate fuel mixture composition was designed to have fuel properties (e.g., boiling point, cloud point, etc.) that enable its use in future diesel engine experiments. A detailed kinetic model for the surrogate fuel mixture was developed by combining well-validated sub-mechanisms of each surrogate component from Lawrence Livermore National Laboratory. The ability of the surrogate mixture and kinetic model to emulate ignition delay times was assessed by comparing the simulated results with measurements for the target diesel fuel. Comparison of the experimental and simulated ignition delay times shows that the current surrogate mixture and kinetic model well capture the autoignition response of the target diesel fuel at varying conditions of pressure, temperature, oxygen concentration, and fuel concentration. The current study is one of the first to demonstrate the efficacy of detailed chemical kinetics for diesel range fuels by assembling validated sub-mechanisms for palette compounds and successfully simulating the autoignition characteristics of a target diesel fuel. The experimental ignition delay times of diesel measured with a rapid compression machine, the surrogate mixture, and the kinetic model developed shall aid in progress of understanding diesel ignition under engine relevant conditions

Bacterial imprinting at Pickering emulsion interfaces

We demonstrate that the tendency of bacteria to assemble at oil-water interface can be utilized to create microbial recognition sites on the surface of polymer beads. In this work, two different groups of bacteria were first treated with acryloyl-functionalized chitosan, and then used to stabilize an oil-in-water emulsion composed of crosslinking monomer dispersed in aqueous buffer. Polymerization of the oil phase followed by removal of the bacterial template resulted in well-defined polymer beads bearing bacterial imprints. Chemical passivation of chitosan and cell displacement assays indicate that the bacterial recognition on the polymer beads was dependent on the nature of the pre-polymer and the target bacteria. The functional materials for microbial recognition show great potential for constructing cell-cell communication networks, biosensors, and new platforms for testing antibiotic drugs

Graphene Layer Growth: Collision of Migrating Five-Member Rings

A reaction pathway is explored in which two cyclopenta groups combine on the zigzag edge of a graphene layer. The process is initiated by H addition to a five-membered ring, followed by opening of that ring and the formation of a six-membered ring adjacent to another five-membered ring. The elementary steps of the migration pathway are analyzed using density functional theory to examine the region of the potential energy surface associated with the pathway. The calculations are performed on a substrate modeled by the zigzag edge of tetracene. Based on the obtained energetics, the dynamics of the system are analyzed by solving the energy transfer master equations. The results indicate energetic and reaction-rate similarity between the cyclopenta combination and migration reactions. Also examined in the present study are desorption rates of migrating cyclopenta rings which are found to be comparable to cyclopenta ring migration

Transistors Formed from a Single Lithography Step Using Information Encoded in Topography

This paper describes a strategy for the fabrication of functional electronic components (transistors, capacitors, resistors, conductors, and logic gates but not, at present, inductors) that combines a single layer of lithography with angle-dependent physical vapor deposition; this approach is named topographically encoded microlithography (abbreviated as TEMIL). This strategy extends the simple concept of ‘shadow evaporation’ to reduce the number and complexity of the steps required to produce isolated devices and arrays of devices, and eliminates the need for registration (the sequential stacking of patterns with correct alignment) entirely. The defining advantage of this strategy is that it extracts information from the 3D topography of features in photoresist, and combines this information with the 3D information from the angle-dependent deposition (the angle and orientation used for deposition from a collimated source of material), to create ‘shadowed’ and ‘illuminated’ regions on the underlying substrate. It also takes advantage of the ability of replica molding techniques to produce 3D topography in polymeric resists. A single layer of patterned resist can thus direct the fabrication of a nearly unlimited number of possible shapes, composed of layers of any materials that can be deposited by vapor deposition. The sequential deposition of various shapes (by changing orientation and material source) makes it possible to fabricate complex structures—including interconnected transistors—using a single layer of topography. The complexity of structures that can be fabricated using simple lithographic features distinguishes this procedure from other techniques based on shadow evaporation.Chemistry and Chemical BiologyEngineering and Applied Science

Rapid Acquisition of X-Ray Scattering Data from Droplet-Encapsulated Protein Systems

Encapsulating reacting biological or chemical samples in microfluidic droplets has the great advantage over single-phase flows of providing separate reaction compartments. These compartments can be filled in a combinatoric way and prevent the sample from adsorbing to the channel walls. In recent years, small-angle X-ray scattering (SAXS) in combination with microfluidics has evolved as a nanoscale method of such systems. Here, we approach two major challenges associated with combining droplet microfluidics and SAXS. First, we present a simple, versatile, and reliable device, which is both suitable for stable droplet formation and compatible with in situ X-ray measurements. Second, we solve the problem of “diluting” the sample signal by the signal from the oil separating the emulsion droplets by multiple fast acquisitions per droplet and data thresholding. We show that using our method, even the weakly scattering protein vimentin provides high signal-to-noise ratio data