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At least 991 records · Page 55

Contribution of the graded region of a HgCdTe diode to its saturation current

Experimental results show that the contribution of the graded region to the current of Hg(1-x)Cd(x)Te diodes is not negligible, as compared to that of the p type bulk. The theoretical analysis reveals the influence of the electric field present outside the depletion region on the current generated by the graded region. The analysis shows the importance of the lifetime profile in the graded region, which is a function of the specific recombination mechanism and its dependence on the local dopant concentration. The effect of parameters such as substrate concentration, surface concentration, and junction depth on this current is discussed.

Schacham, S. E.↗

Pr-specific phytochrome phosphorylation in vitro by a protein kinase present in anti-phytochrome maize immunoprecipitates

Protein kinase activity has repeatedly been found to co-purify with the plant photoreceptor phytochrome, suggesting that light signals received by phytochrome may be transduced or modulated through protein phosphorylation. In this study immunoprecipitation techniques were used to characterize protein kinase activity associated with phytochrome from maize (Zea mays L.). A protein kinase that specifically phosphorylated phytochrome was present in washed anti-phytochrome immunoprecipitates of etiolated coleoptile proteins. No other substrate tested was phosphorylated by this kinase. Adding salts or detergents to disrupt low-affinity protein interactions reduced background phosphorylation in immunoprecipitates without affecting phytochrome phosphorylation, indicating that the protein kinase catalytic activity is either intrinsic to the phytochrome molecule or associated with it by high-affinity interactions. Red irradiation (of coleoptiles or extracts) sufficient to approach photoconversion saturation reduced phosphorylation of immunoprecipitated phytochrome. Subsequent far-red irradiation reversed the red-light effect. Phytochrome phosphorylation was stimulated about 10-fold by a co-immunoprecipitated factor. The stimulatory factor was highest in immunoprecipitates when Mg2+ was present in immunoprecipitation reactions but remained in the supernatant in the absence of Mg2+. These observations provide strong support for the hypothesis that phytochrome-associated protein kinase modulates light responses in vivo. Since only phytochrome was found to be phosphorylated, the co-immunoprecipitated protein kinase may function to regulate receptor activity.

NASA Discipline Plant Biology↗

Decoupling Thin Film CdTe Growth from Packaging: Toward Record Specific Power in Low Cost Polycrystalline PV: Preprint

There are critical material and scientific barriers to producing high efficiency, flexible, lightweight solar cells that maximize specific power in a cost-effective manner. GaAs solar cells produce the highest specific power of any photovoltaic (PV) technology due to their low weight and extremely high efficiency, but they are also among the most expensive to produce. This work explores a novel lift-off approach with thin-film solar cells, particularly CdTe, to achieve high specific power at low costs. Thin-film devices can be delaminated from their heavy, glass growth substrates post-growth by exploiting a mismatch in coefficient of thermal expansion between the two. This allows thin-film PV to be decoupled from high temperature growth requirements and repackaged using lightweight materials. Currently, the most consistent method of achieving complete delamination of CdTe films is to apply a glass handle at the back contact of the device using epoxy and submerge it in liquid nitrogen. By Tthen re-depositing a transparent front contact but be re-deposited and selectively etcheding to expose the back contact to produce, a functioning lifted-off devices have been produced. Effects of delamination and contributions to device functionality from CdCl2 and CdS layers are discussed. Reproducible delamination of high efficiency, thin-film solar cells over large areas will enable work to further improve device efficiency through passivation and reconstruction of the previously buried interface between the transparent contact and CdS.

14 SOLAR ENERGY↗

Highly durable nanoscale electrocatalyst based on core shell particles

A multimetallic nanoscale catalyst having a core portion enveloped by a shell portion and exhibiting high catalytic activity and improved catalytic durability. In various embodiments, the core/shell nanoparticles comprise a gold particle coated with a catalytically active platinum bimetallic material. The shape of the nanoparticles is substantially defined by the particle shape of the core portion. The nanoparticles may be dispersed on a high surface area substrate for use as a catalyst and is characterized by no significant loss in surface area and specific activity following extended potential cycling.

36 MATERIALS SCIENCE↗

Numerical Simulation of Nanostructure Growth

Nanoscale structures, such as nanowires and carbon nanotubes (CNTs), are often grown in gaseous or plasma environments. Successful growth of these structures is defined by achieving a specified crystallinity or chirality, size or diameter, alignment, etc., which in turn depend on gas mixture ratios. pressure, flow rate, substrate temperature, and other operating conditions. To date, there has not been a rigorous growth model that addresses the specific concerns of crystalline nanowire growth, while demonstrating the correct trends of the processing conditions on growth rates. Most crystal growth models are based on the Burton, Cabrera, and Frank (BCF) method, where adatoms are incorporated into a growing crystal at surface steps or spirals. When the supersaturation of the vapor is high, islands nucleate to form steps, and these steps subsequently spread (grow). The overall bulk growth rate is determined by solving for the evolving motion of the steps. Our approach is to use a phase field model to simulate the growth of finite sized nanowire crystals, linking the free energy equation with the diffusion equation of the adatoms. The phase field method solves for an order parameter that defines the evolving steps in a concentration field. This eliminates the need for explicit front tracking/location, or complicated shadowing routines, both of which can be computationally expensive, particularly in higher dimensions. We will present results demonstrating the effect of process conditions, such as substrate temperature, vapor supersaturation, etc. on the evolving morphologies and overall growth rates of the nanostructures.

Hwang, Helen H.↗

Local Environment and Interactions of Liquid and Solid Interfaces Revealed by Spectral Line Shape of Surface Selective Nonlinear Vibrational Probe

Vibrational spectral lineshape contains important detailed information of molecular vibration and reports its specific interactions and couplings to its local environment. In this work, recently developed sub-1 cm-1 high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) was used to measure the -C≡N stretch vibration in the 4-n-octyl-4’-cyanobiphenyl (8CB) Langmuir or Langmuir-Blodgett (LB) monolayer as a unique vibrational probe, and the spectral lineshape analysis revealed the local environment and interactions at the air/water, air/glass, air/calcium fluoride and air/-quartz interfaces for the first time. The 8CB Langmuir or LB film is uniform and the vibrational spectral lineshape of its -C≡N group has been well characterized, making it a good choice as the surface vibrational probe. Lineshape analysis of the 8CB -C≡N stretch SFG vibrational spectra suggests the coherent vibrational dynamics and the structural and dynamic inhomogeneity of the -C≡N group at each interface are uniquely different. In addition, it is also found that there are significantly different roles for water molecules in the LB films on different substrate surfaces. These results demonstrated the novel capabilities of the surface nonlinear spectroscopy in characterization and in understanding the specific structures and chemical interactions at the liquid and solid interfaces in general.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly stable and self-repairing membrane-mimetic 2D nanomaterials assembled from lipid-like peptoids

Two-dimensional (2D) materials with molecular-scale thickness have attracted increasing interest for separation, electronic, catalytic, optical, energy and biomedical applications. Although extensive research on 2D materials, such as graphene and graphene oxide, has been performed in recent years, progress is limited on self-assembly of 2D materials from sequence-specific macromolecules, especially from synthetic sequences that could exhibit lipid-like self-assembly of bilayer sheets and mimic membrane proteins for functions. The creation of such new class of materials could enable development of highly stable biomimetic membranes that exhibit cell-membrane-like molecular transport with exceptional selectively and high transport rates. Here we demonstrate self-assembly of lipid-like 12-mer peptoids into extremely stable, crystalline, flexible and free-standing 2D membrane materials. As with cell membranes, upon exposure to external stimuli, these materials exhibit changes in thickness, varying from 3.5 nm to 5.6 nm. We find that self-assembly occurs through a facile crystallization process, in which inter-peptoid hydrogen bonds and enhanced hydrophobic interactions drive the formation of a highly-ordered structure. Molecular simulation confirms this is the energetically favored structure. Displaying functional groups at arbitrary locations of membrane-forming peptoids produces membranes with similar structures. This research further shows that single-layer membranes can be coated onto substrate surfaces. Moreover, membranes with mechanically-induced defects can self-repair. Given that peptoids are sequence-specific and exhibit protein-like molecular recognition with enhanced stability, we anticipate our membranes to be a robust platform tailored to specific applications.

36 MATERIALS SCIENCE↗

Improving metal/semiconductor conductivity using AlO{sub x} interlayers on n-type and p-type Si

Thermal atomic layer deposition was used to form ultra-thin interlayers in metal/interlayer/ semiconductor Ohmic contacts on n-type and p-type Si. AlO{sub x} of thickness 1–2 nm was deposited at 120 °C on Si substrates prior to metallization, forming Ni/AlO{sub x}/Si contacts. Conductivity improved by two orders of magnitude but the contacts remained rectifying. When they were annealed at 200 °C, the conductivity increased by another order of magnitude and the samples became Ohmic. A minimum specific contact resistivity of 1.5 × 10{sup −4} Ω-cm{sup 2} was obtained for structures based on lightly doped (10{sup 15 }cm{sup −3}) Si substrates. Existing models that describe Fermi level de-pinning do not fully explain our results, which are however consistent with other experimental data in the literature.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Microfabricated Ion Traps on Sapphire for Larger Trap Areas and Higher Qubit Count

Surface ion traps are a promising platform for quantum computing due to their potential to store large numbers of ions that can be addressed by electrical and optical control signals in order to implement quantum algorithms. Increasing the power of the quantum computer requires increasing the number of ions, but this poses a significant challenge in that it leads to a non-linear increase in on-chip power dissipation. The primary contributor to this power scaling in current devices is the capacitance between the radio frequency (RF) electrode and the metal plane that shields the silicon substrate from the RF signals applied to it. Silicon has traditionally been chosen for the substrate material for compatibility with the processing required for multi-metal-level traps. In this work, we address these capacitance and fabrication challenges by replacing the commonly used silicon substrate with an insulating sapphire substrate to fabricate a multi-metal-level ion trap, while still employing common semiconductor manufacturing techniques. This change in substrate allows the design to remove the metal shielding from the device design, reducing the capacitance of the RF electrode. The electrical characteristics of these traps were measured, specifically trap impedance, capacitance, and voltage breakdown, and compared to nearly identical silicon trap devices. Finally, we used laser cutting techniques to shape a sapphire wafer into bowtie shapes matching silicon traps previously fabricated at Sandia National Labs to explore solutions for integrating sapphire substrates into non-rectangular ion trap designs.

97 MATHEMATICS AND COMPUTING↗

Bacteria Contribute to Plant Secondary Compound Degradation in a Generalist Herbivore System

Leaf-cutter ants are dominant neotropical herbivores capable of deriving energy from a wide range of plant substrates. The success of leaf-cutter ants is largely due to their external gut, composed of key microbial symbionts, specifically, the fungal mutualist L. gongylophorus and a consistent bacterial community. Both symbionts are known to have critical roles in extracting energy from plant material, yet comparatively little is known about their roles in the detoxification of plant secondary compounds. In this study, we assessed if the bacterial communities associated with leaf-cutter ant fungus gardens can degrade harmful plant chemicals. We identify plant secondary compound detoxification in leaf-cutter ant gardens as a process that depends on the degradative potential of both the bacterial community and L. gongylophorus . Our findings suggest that the fungus garden and its associated microbial community influence the generalist foraging abilities of the ants, underscoring the importance of microbial symbionts in plant substrate suitability for herbivores.

59 BASIC BIOLOGICAL SCIENCES↗

Human cytochrome P450 17A1 structures with metabolites of prostate cancer drug abiraterone reveal substrate-binding plasticity and a second binding site

Abiraterone acetate is a first-line therapy for castration-resistant prostate cancer. This prodrug is deacetylated in vivo to abiraterone, which is a potent and specific inhibitor of cytochrome P450 17A1 (CYP17A1). CYP17A1 performs two sequential steps that are required for the biosynthesis of androgens that drive prostate cancer proliferation, analogous to estrogens in breast cancer. Abiraterone can be further metabolized in vivo on the steroid A ring to multiple metabolites that also inhibit CYP17A1. Despite its design as an active-site-directed substrate analog, abiraterone and its metabolites demonstrate mixed competitive/noncompetitive inhibition. To understand their binding, we solved the X-ray structures of CYP17A1 with three primary abiraterone metabolites. Despite different conformations of the steroid A ring and substituents, all three bound in the CYP17A1 active site with the steroid core packed against the I helix and the A ring C3 keto or hydroxyl oxygen forming a hydrogen bond with N202 similar to abiraterone itself. The structure of CYP17A1 with 3-keto, 5α-abiraterone was solved to 2.0 Å, the highest resolution to date for a CYP17A1 complex. This structure had additional electron density near the F/G loop, which is likely a second molecule of the inhibitor and which may explain the noncompetitive inhibition. Mutation of the adjacent Asn52 to Tyr positions its side chain in this space, maintains enzyme activity, and prevents binding of the peripheral ligand. Collectively, our findings provide further insight into abiraterone metabolite binding and CYP17A1 function.

59 BASIC BIOLOGICAL SCIENCES↗

Electronic Tongue for Quantitation of Contaminants in Water

An assembly of sensors, denoted an electronic tongue, is undergoing development as a prototype of compact devices for use in measuring concentrations of contaminants in water. Thus far, the electronic tongue has been tested on ions of Cu, Zn, Pb, and Fe and shown to respond to concentrations as low as about 10 parts per million. This electronic tongue is expected to be capable of measuring concentrations of other metal ions and organic compounds. Potential uses for electronic tongues include monitoring the chemical quality of water in a variety of natural, industrial, and laboratory settings; detecting micro-organisms indirectly by measuring microbially influenced corrosion; and characterizing compounds of interest to the pharmaceutical and food industries. This version of the electronic tongue includes a heater, a temperature sensor, an array of ion-specific electrodes, an oxidation/ reduction sensor pair, an electrical-conductivity sensor, and an array of galvanic cells, all on one compact ceramic substrate. Special-purpose electronic excitation and readout circuitry for the sensors has also been constructed. The main advantage of the electronic tongue, relative to electrodes of this type used traditionally to assess water quality, is extreme ruggedness. The types of measurements that can be performed by use of the sensors on the electronic tongue are quite varied. The best combination of types of measurements for a given application depends on the specific contaminants that one seeks to detect. Experimental studies to identify such combinations were in progress at the time of reporting the information for this article.

Buehler, Marlin↗

Structure of Type IIL Restriction-Modification Enzyme MmeI in Complex with DNA Has Implications for Engineering New Specificities

The creation of restriction enzymes with programmable DNA-binding and -cleavage specificities has long been a goal of modern biology. The recently discovered Type IIL MmeI family of restriction-and-modification (RM) enzymes that possess a shared target recognition domain provides a framework for engineering such new specificities. However, a lack of structural information on Type IIL enzymes has limited the repertoire that can be rationally engineered. We report here a crystal structure of MmeI in complex with its DNA substrate and an S-adenosylmethionine analog (Sinefungin). The structure uncovers for the first time the interactions that underlie MmeI-DNA recognition and methylation (5’-TCCRAC-3’; R = purine) and provides a molecular basis for changing specificity at four of the six base pairs of the recognition sequence (5’-TCCRAC-3’). Surprisingly, the enzyme is resilient to specificity changes at the first position of the recognition sequence (5’-TCCRAC-3’). Collectively, the structure provides a basis for engineering further derivatives of MmeI and delineates which base pairs of the recognition sequence are more amenable to alterations than others.

59 BASIC BIOLOGICAL SCIENCES↗

Structural Basis of the Enhanced Pollutant-Degrading Capabilities of an Engineered Biphenyl Dioxygenase

Biphenyl dioxygenase, the first enzyme of the biphenyl catabolic pathway, is a major determinant of which polychlorinated biphenyl (PCB) congeners are metabolized by a given bacterial strain. Ongoing efforts aim to engineer BphAE, the oxygenase component of the enzyme, to efficiently transform a wider range of congeners. BphAE II9 , a variant of BphAE LB400 in which a seven-residue segment, 335 TFNNIRI 341 , has been replaced by the corresponding segment of BphAE B356 , 333 GINTIRT 339 , transforms a broader range of PCB congeners than does either BphAE LB400 or BphAE B356 , including 2,6-dichlorobiphenyl, 3,3'-dichlorobiphenyl, 4,4'-dichlorobiphenyl, and 2,3,4'-trichlorobiphenyl. To understand the structural basis of the enhanced activity of BphAE II9 , we have determined the three-dimensional structure of this variant in substrate-free and biphenyl-bound forms. Structural comparison with BphAE LB400 reveals a flexible active-site mouth and a relaxed substrate binding pocket in BphAE II9 that allow it to bind different congeners and which could be responsible for the enzyme's altered specificity. Biochemical experiments revealed that BphAE II9 transformed 2,3,4'-trichlorobiphenyl and 2,2',5,5'-tetrachlorobiphenyl more efficiently than did BphAE LB400 and BphAE B356 . BphAE II9 also transformed the insecticide dichlorodiphenyltrichloroethane (DDT) more efficiently than did either parental enzyme (apparent k cat /K m of 2.2 ± 0.5 mM –1 s –1 , versus 0.9 ± 0.5 mM –1 s –1 for BphAE B356 ). Studies of docking of the enzymes with these three substrates provide insight into the structural basis of the different substrate selectivities and regiospecificities of the enzymes. Biphenyl dioxygenase is the first enzyme of the biphenyl degradation pathway that is involved in the degradation of polychlorinated biphenyls. Attempts have been made to identify the residues that influence the enzyme activity for the range of substrates among various species. In this study, we have done a structural study of one variant of this enzyme that was produced by family shuffling of genes from two different species. Comparison of the structure of this variant with those of the parent enzymes provided an important insight into the molecular basis for the broader substrate preference of this enzyme. Here, the structural and functional details gained in this study can be utilized to further engineer desired enzymatic activity, producing more potent enzymes.

59 BASIC BIOLOGICAL SCIENCES↗

Thin-Film Solar Cells on Polymer Substrates for Space Power

Photovoltaic arrays have played a key role in power generation in space. The current technology will continue to evolve but is limited in the important mass specific power metric (MSP or power/weight ratio) because it is based on bulk crystal technology. Solar cells based on thin-film materials offer the promise of much higher MSP and much lower cost. However, for many space applications, a 20% or greater AM0 efficiency (eta) may be required. The leading thin-film materials, amorphous Si, CuInSe, and CdTe have seen significant advances in efficiency over the last decade but will not achieve the required efficiency in the near future. Several new technologies are herein described to maximize both device eta and MSP. We will discuss these technologies in the context of space exploration and commercialization. One novel approach involves the use of very lightweight polyimide substrates. We describe efforts to enable this advance including materials processing and device fabrication and characterization. Another approach involves stacking two cells on top of each other. These tandem devices more effectively utilize solar radiation by passing through non-absorbed longer wavelength light to a narrow-bandgap bottom cell material. Modeling of current devices in tandem format indicates that AM0 efficiencies near 20% can be achieved with potential for 25% in the near future. Several important technical issues need to be resolved to realize the benefits of lightweight technologies for solar arrays, such as: monolithic interconnects, lightweight array structures, and new ultra-light support and deployment mechanisms. Recent advances will be stressed.

Hepps, A. F.↗

Sol-gel deposited transducers characteristics: A weight percent study - 15718

Monitoring functional machinery components that operate at elevated temperatures is costly and time consuming. This work explores leave in place composite transducers for high temperature monitoring of machinery components. A theoretical model was developed utilizing software provided by NASA. This model was then compared to the experimental results. The objective is to determine the characteristics of a set of spray-on composite transducers to identify the ideal transducer for any situation where a certain specification is made: - Operating temperature; - Signal amplitude/Signal to noise ratio; - Specific material property. The transducer is fabricated through a sol-gel deposition process that utilizes spraying the transducer onto the substrate. A sol-gel solution containing bismuth titanate is mixed with a combination of bismuth titanate and lead zirconate titanate(PZT) powders to create a composite transducer. Typical sintering methods have proved to be destructive and difficult to handle for the sol-gel deposition method; however, induction sintering has proved effective. -d{sub 33} decreases with increasing weight percent of bismuth titanate -the maximum usable temperature increases with increasing weight percent bismuth titanate -signal amplitude is also higher with increasing weight percent of bismuth titanate The ideal composition for the best signal amplitude and the highest operating temperature has been shown to be pure bismuth titanate; however, if the properties of the transducer are of utmost importance including conductivity and density then PZT should be added to increase these properties. The theoretical NASA Micromechanical Analysis Code by Generalized Method of Cell model has been validated through the experimental results of these experiments. Now that the composition of the transducer has been optimized to a specific application the future work is comprised of: - Utilizing the information to evaluate wall thickness - Integrating the optimized transducer with a wireless system for remote monitoring of mechanical component - Establishing a field deposition method for the spray-on transducer.

36 MATERIALS SCIENCE↗

Non‐Conjugated Flexible Linkers in Semiconducting Polymers: A Pathway to Improved Processability without Compromising Device Performance

Semiconducting polymers, in contrast to inorganic silicon, are solution processable and can potentially be printed cost efficiently on flexible large‐area substrates. However to do so it is of paramount importance to formulate the polymeric semiconductors into inks with specific viscosities. Herein, the synthesis of a new highly soluble isoindigo monomer and its incorporation into low bandgap semiconducting polymers is presented. Non‐conjugated flexible linkers are introduced into the conjugated backbone in order to modulate the materials processability. The viscoelastic properties of the new polymers are studied in detail by means of rheometry and dynamical mechanical analysis. The solution viscosity is directly proportional to the content of non‐conjugated linkers in the polymer backbone. In organic field‐effect transistors maximum hole mobilities of 1.7 cm 2 V −1 s −1 are achieved with the new polymers. Due to the enhanced solubility all‐polymer solar cells are fabricated by solution shearing, reaching power conversion efficiency values of 3.7%.

Schroeder, Bob C.↗

Caged luciferins for bioluminescent activity-based sensing

Bioluminescence imaging is a powerful modality for in vivo imaging owing to its low background and high signal-to-noise ratio. Because bioluminescent emission occurs only upon the catalytic reaction between the luciferase enzyme and its luciferin substrate, caging luciferins with analyte-reactive triggers offers a general approach for activity-based sensing of specific biochemical processes in living systems across cell, tissue, and animal models. In this review, we summarize recent efforts in the development of synthetic caged luciferins for tracking enzyme, small molecule, and metal ion activity and their contributions to physiological and pathological processes.

59 BASIC BIOLOGICAL SCIENCES↗