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166 records · Page 10

Biophysical and biochemical evidence for the role of acetate kinases (AckAs) in an acetogenic pathway in pathogenic spirochetes

Unraveling the metabolism of Treponema pallidum is a key component to understanding the pathogenesis of the human disease that it causes, syphilis. For decades, it was assumed that glucose was the sole carbon/energy source for this parasitic spirochete. But the lack of citric-acid-cycle enzymes suggested that alternative sources could be utilized, especially in microaerophilic host environments where glycolysis should not be robust. Recent bioinformatic, biophysical, and biochemical evidence supports the existence of an acetogenic energy-conservation pathway in T . pallidum and related treponemal species. In this hypothetical pathway, exogenous D-lactate can be utilized by the bacterium as an alternative energy source. Herein, we examined the final enzyme in this pathway, acetate kinase (named TP0476), which ostensibly catalyzes the generation of ATP from ADP and acetyl-phosphate. We found that TP0476 was able to carry out this reaction, but the protein was not suitable for biophysical and structural characterization. We thus performed additional studies on the homologous enzyme (75% amino-acid sequence identity) from the oral pathogen Treponema vincentii , TV0924. This protein also exhibited acetate kinase activity, and it was amenable to structural and biophysical studies. We established that the enzyme exists as a dimer in solution, and then determined its crystal structure at a resolution of 1.36 Å, showing that the protein has a similar fold to other known acetate kinases. Mutation of residues in the putative active site drastically altered its enzymatic activity. A second crystal structure of TV0924 in the presence of AMP (at 1.3 Å resolution) provided insight into the binding of one of the enzyme’s substrates. On balance, this evidence strongly supported the roles of TP0476 and TV0924 as acetate kinases, reinforcing the hypothesis of an acetogenic pathway in pathogenic treponemes.

Deka, Ranjit K.↗

Solid oxidized fuel cells seals leakage setup and testing

As the world s reserves of fossil fuels are depleted, the U.S. Government, as well as other countries and private industries, is researching solutions for obtaining power, answers that would be more efficient and environmentally friendly. For a long time engineers have been trying to obtain the benefits of clean electric power without heavy batteries or pollution-producing engines. While some of the inventions proved to be effective (i.e. solar panels or windmills) their applications are limited due to dependency on the energy source (i.e. sun or wind). Currently, as energy concerns increase, research is being carried out on the development of a Solid Oxide Fuel Cell (SOFC). The United States government is taking a proactive role in expanding the technology through the Solid State Energy Conversion Alliance (SECA) Program, which is coordinated by the Department of Energy. into an electrical energy. This occurs by the means of natural tendency of oxygen and hydrogen to chemically react. While controlling the process, it is possible to harvest the energy given off by the reaction. SOFCs use currently available fossil fuels and convert a variety of those fuels with very high efficiency (about 40% more efficient than modem thermal power plants). At the same time they are almost entirely nonpolluting and due to their size they can be placed in remote areas. The main fields where the application of the fuel cells appears to be the most useful for are stationary energy sources, transportation, and military applications. structure and materials must be resolved. All the components must be operational in harsh environments including temperatures reaching 800 C and cyclic thermal- mechanical loading. Under these conditions, the main concern is the requirement for hermetic seals to: (1) prevent mixing of the fuel and oxidant within the stack, (2) prevent parasitic leakage of the fuel from the stack, (3) prevent contamination of the anode by air leaking into the stack, (4) electrically isolate the individual cells within the stack, and (5) mechanically bond the cell components. The sealing challenges are aggravated by the need to maintain hermetic boundaries between the different flow paths within the fuel cell throughout cycled operation. Within the timeframe of my tenure, the main objective is to assist in building a state-of-art test facility.

Bastrzyk, Marta B.↗

Probing Sensitivity of Discharge Characteristics to Model Selection using Uncertainty Quantification in an aprotic Li-Oxygen Battery

Currently, there are several models in the literature, such as kinetic models, microstructural models, and mass transport models that describe a Li-air battery's discharge behavior. Many of these models are calibrated and tested at low current densities and cannot be easily transferred to high current densities. Even at low current densities, there is no quantitative method for a researcher to choose a reaction kinetic model such as classical Butler-Volmer and its derivatives, and modified Marcus-Hush-Chidsey, a resistance model for lithium peroxide such as electron transport via tunneling or linear resistivity, a surface coverage model (lithium peroxide growth) such as partial coverage or full coverage, and mass transport model (discussed in Ref. [1]). Also, it is time-consuming to test different models at high current density (1C) due to a lack of well-tested models and well-calibrated model parameters. For this presentation, we will develop an analytical model, which acts as a surrogate model for a sophisticated finite element model to predict discharge time and discharge voltage. Next, we use an uncertainty quantifying technique called reduced-order stochastic optimization [2, 3] to determine the uncertainty in model parameters for rate kinetics, lithium peroxide resistivity, and parasitic resistance. Finally, a finite element simulation is performed to determine the error introduced by the surrogate model and its influence on the uncertainty in the model parameters.

M Mehta↗

Electrochemical Reduction Pathways from Goethite to Green Iron in Alkaline Solution with Silicate Additive

Energy-efficient and low-temperature iron electrolysis in alkaline solutions is a low-cost and sustainable ironmaking process with zero-carbon emissions when renewable electrical sources are involved. However, its implementation is hindered by electrochemically inert Fe 3 O 4 and parasitic H 2 gas formation during the electrochemical reduction process, resulting in the low energy efficiency of iron electrolysis. Here, we further explore the potential of electrochemical reduction of goethite (FeOOH) by employing a low concentration of silicate additive in an alkaline solution to mitigate Fe 3 O 4 accumulation and H 2 generation. Electrochemical measurements coupled with operando X-ray diffraction and X-ray absorption spectroscopy suggested FeOOH → Fe 3 O 4 → Fe(OH) 2 → Fe reduction pathways. Interestingly, a poorly crystalline or amorphous Fe(OH) 2 phase formed in the NaOH/silicate mixed electrolyte, possibly due to the inhibitive effect of silicate on water and ion transport, which eventually contributed to the improved reduction of Fe 3 O 4 , also supported by atomistic simulations. This work demonstrates the potential for silicate as a low-cost and effective electrolyte additive to improve room-temperature green iron formation via electrolysis.

36 MATERIALS SCIENCE↗