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At least 343 records · Page 19

Grain engineering: How nanoscale inhomogeneities can control charge collection in solar cells

Statistical and correlative analysis are increasingly important in the design and study of new materials, from semiconductors to metals. Non-destructive measurement techniques, with high spatial resolution, capable of correlating composition and/or structure with device properties, are few and far between. For the case of polycrystalline and inhomogeneous materials, the added challenge is that nanoscale resolution is in general not compatible with the large sampling areas necessary to have a statistical representation of the specimen under study. For the study of grain cores and grain boundaries in polycrystalline solar absorbers this is of particular importance since their dissimilar behavior and variability throughout the samples makes it difficult to draw conclusions and ultimately optimize the material. In this study, we present a nanoscale in-operando approach based on the multimodal utilization of synchrotron nano x-ray fluorescence and x-ray beam induced current collected for grain core and grain boundary areas and correlated pixel-by-pixel in fully operational Cu(In(1-x)Gax)Se2Cu(In(1-x)Gax)Se2 solar cells. We observe that low gallium cells have grain boundaries that over perform compared to the grain cores and high gallium cells have boundaries that under perform. These results demonstrate how nanoscale correlative X-ray microscopy can guide research pathways towards grain engineering low cost, high efficiency solar cells.

14 SOLAR ENERGY↗

Genome-scale engineering of Saccharomyces cerevisiae with single-nucleotide precision

Here, we developed a CRISPR/Cas9 and homology-directed-repair assisted genome-scale engineering method named CHAnGE that can rapidly output tens of thousands of specific genetic variants in yeast. More than 98% of target sequences were efficiently edited with an average frequency of 82%. We validate the single-nucleotide resolution genome-editing capability of this technology by creating a genome-wide gene disruption collection and apply our method to improve tolerance to growth inhibitors.

59 BASIC BIOLOGICAL SCIENCES↗

Reversible S-nitrosylation in an engineered azurin

S-Nitrosothiols are known as reagents for NO storage and transportation and as regulators in many physiological processes. Although the S-nitrosylation catalysed by haem proteins is well known, no direct evidence of S-nitrosylation in copper proteins has been reported. Here, we report reversible insertion of NO into a copper–thiolate bond in an engineered copper centre in Pseudomonas aeruginosa azurin by rational design of the primary coordination sphere and tuning its reduction potential by deleting a hydrogen bond in the secondary coordination sphere. The results not only provide the first direct evidence of S-nitrosylation of Cu(II)-bound cysteine in metalloproteins, but also shed light on the reaction mechanism and structural features responsible for stabilizing the elusive Cu(I)–S(Cys)NO species. The fast, efficient and reversible S-nitrosylation reaction is used to demonstrate its ability to prevent NO inhibition of cytochrome bo3 oxidase activity by competing for NO binding with the native enzyme under physiologically relevant conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlled synthesis of highly-branched plasmonic gold nanoparticles through peptoid engineering

Inspired by peptide- and protein-controlled formation of hierarchical inorganic nanostructures in nature, herein we report the design of sequence-defined peptoids for biomimetic synthesis of flower-like gold nanosuperstruc-tures. We demonstrate that the peptoid-induced morphosyn-thesis of gold nanoflowers is sequence-dependent. By varying the hydrophobicity, number of carboxylate and amino groups, and side-chain positions of peptoids, we develop a rule of thumb for designing peptoids that yield gold nanoflowers. Through a combination of hyperspectral UV-Vis absorption micro-spectroscopy (H-UVVIS-AMS) and three-photon photoemission electron microscopy (TP-PEEM), we measured the plasmonic properties of individual nanoflowers. Whereas H-UVVIS-AMS experiments revealed well-defined plasmon resonances centered at ~528 nm, TP-PEEM measurements showed an unprecedented plasmonic enhancement as high as 105 for a single nanoflower. A com-bination of the unique plasmonic property and the high sta-bility endows the peptoid-engineered nanoflowers with po-tential applications in chemical and biological imaging. FY, YC, HJ and C-LC acknowledge support by the Materials Synthesis and Simulation Across Scales (MS3) Initiative, through the Laboratory Directed Research & Development (LDRD) fund at Pacific Northwest National Laboratory (PNNL). FY was also partially supported by fellowships from Shandong Provincial Education Association for International Exchanges. YG was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. PZE acknowledges support from the Laboratory Directed Research and Development Program through a Linus Pauling Fellowship at PNNL. PNNL is multi-program national laboratory operated for the Department of Energy by Battelle under Contracts No. DE-AC05-76RL01830. The authors are most grateful to Alan Joly and Wayne Hess (PNNL) for their support with the PEEM measurements and several useful discussions.

Yan, Feng↗

A microbial sensor for organophosphate hydrolysis exploiting an engineered specificity switch in a transcription factor

A whole-cell biosensor utilizing a transcription factor (TF) is an effective tool for sensitive and selective detection of specialty chemicals or anthropogenic molecules, but requires access to an expanded repertoire of TFs. Using homology modeling and ligand docking for binding pocket identification, assisted by conservative mutations in the pocket, we engineered a novel specificity in an Acinetobacter TF, PobR, to ‘sense’ a chemical p-nitrophenol (pNP) and measured the response via a fluorescent protein reporter expressed from a PobR promoter. Out of 107 variants of PobR, four were active when dosed with pNP, with two mutants showing a specificity switch from the native effector 4-hydroxybenzoate (4HB). One of the mutants, pNPmut1 was then used to create a smart microbial cell responding to pNP production from hydrolysis of an insecticide, paraoxon, in a coupled assay involving phosphotriesterase (PTE) enzyme expressed from a separate promoter. We show the fluorescence of the cells correlated with the catalytic efficiency of the PTE variant expressed in each cell. High selectivity between similar molecules (4HB versus pNP), high sensitivity for pNP detection (~2 μM) and agreement of apo- and holo-structures of PobR scaffold with predetermined computational models are other significant results presented in this work.

Jha, Ramesh K.↗

Increased Photochemical Efficiency in Cyanobacteria via an Engineered Sucrose Sink

In plants, a limited capacity to In plants, a limited capacity to utilize or export the end-products of the Calvin–Benson cycle (CB) from photosynthetically active source cells to non-photosynthetic sink cells can result in reduced carbon capture and photosynthetic electron transport (PET), and lowered photochemical efficiency. The down-regulation of photosynthesis caused by reduced capacity to utilize photosynthate has been termed ‘sink limitation’. Recently, several cyanobacterial and algal strains engineered to overproduce target metabolites have exhibited increased photochemistry, suggesting that possible source–sink regulatory mechanisms may be involved. Here, we directly examined photochemical properties following induction of a heterologous sucrose ‘sink’ in the unicellular cyanobacterium Synechococcus elongatus PCC 7942. We show that total photochemistry increases proportionally to the experimentally controlled rate of sucrose export. Importantly, the quantum yield of PSII (ΦII) increases in response to sucrose export while the PET chain becomes more oxidized from less PSI acceptor-side limitation, suggesting increased CB activity and a decrease in sink limitation. Enhanced photosynthetic activity and linear electron flow are detectable within hours of induction of the heterologous sink and are independent of pigmentation alterations or the ionic/osmotic effects of the induction system. These observations provide direct evidence that secretion of heterologous carbon bioproducts can be used as an alternative approach to improve photosynthetic efficiency, presumably by by-passing sink limitation. Our results also suggest that engineered microalgal production strains are valuable alternative models for examining photosynthetic sink limitation because they enable greater control and monitoring of metabolite fluxes relative to plants.

59 BASIC BIOLOGICAL SCIENCES↗

Numerical Analysis of Detonability Assessment in a Natural Gas-Air Fueled Rotating Detonation Engine

Rotating Detonation Engines (RDE) offer an alternative combustion strategy to replace conventional constant pressure combustion with a process that could produce a pressure gain without the use of a mechanical compressor. Recent numerical and experimental publications that consider air as the oxidizer have primarily focused on the ability of these annular combustors to sustain a stable continuous detonation wave when fueled by hydrogen. However, for this to be a viable consideration for the land-based power generation it is necessary to explore the ability to detonate natural gas and air within the confines of the annular geometry of an RDE. Previous studies on confined detonations have expressed the importance of permitting detonation cells to fully form within the combustor in order to achieve stability. This poses a challenge for natural gas–air fueled processes as their detonation cell size can be quite large even at moderate pressures. Despite the practical importance, only a few studies are available on natural gas detonations for air-breathing RDE applications. Moreover, the extreme thermodynamic condition (high temperature inside the combustor) allows limited accessibility inside the combustor for detailed experimental instrumentations, providing mostly single-point data. Recent experimental studies at the National Energy Technology Laboratory (NETL) have reported detonation failure at higher methane concentration in an air-breathing RDE fueled by natural gas-hydrogen fuel blends. This encourages to perform a detailed numerical investigation on the wave characteristics of detonation in a natural gas-air fueled RDE to understand the various aspects of instability associated with the natural gas-air detonation.This study is a numerical consideration of a methane-air fueled RDE with varying operating conditions to ascertain the ability to achieve a stable, continuous detonation wave. The simulations have been performed in a 2D unwrapped RDE geometry using the open-source CFD library “OpenFOAM” employing an unsteady pressure-based compressible reactive flow solver with a <em>k</em>–<em>ε</em> turbulence model in a structured rectangular grid system. Both reduced and detailed chemical kinetic models have been used to assess the effect of the chemistry on the detonation wave characteristics and the underlying flow features. A systematic grid sensitivity study has been conducted with various grid sizes to quantify the weakly stable overdriven detonation on a coarse mesh and oscillating features at fine mesh resolutions.The main focus of the current study is to investigate the effects of operating injection pressure on detonation wave characteristics of an air-breathing Rotating Detonation Engine (RDE) fueled with natural gas-hydrogen fuel blends. Wave speeds, peak pressures and temperatures, and dominant frequencies have been computed from the time histories. The flow structures were then visualized using 2D contours of temperature and species concentration.

Saha, Pankaj↗