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At least 289 records · Page 16

Creating multifunctional synthetic lichen platforms for sustainable biosynthesis of biofuel precursors

In this project, we were creating a sustainable platform for biofuel production, utilizing carbon-fixing autotrophs to supply oxygen and organic substrates to heterotrophic partners, which in turn produce carbon dioxide to feed the autotrophs. This symbiotic lichen community could lower the input cost, optimize metabolic exchanges and improve the generation of biofuel precursors through multi-omics driven genetic engineering. The cyanobacteria Synechococcus elongatus (S. elongatus) was used as the primary autotroph to provide oxygen and organic substrates, especially sucrose, to a co-culture system. The strain with overexpression of sucrose transporter cscB demonstrated a significant increase in sucrose production under salt stress as what we expected. We also implemented 13C metabolic flux analysis on the sucrose secreting strain S. elongatus cscB-NaCl. Next, transporters proteins like glutamate exporter mscCG from Corynebacterium glutamicum was overexpressed in S. elongatus to improve metabolite exchange. We provided sucrose and glutamate to filamentous fungi to enable their growth and production of biochemicals using substrates from the cyanobacterium. Two fungi ( Aspergillus nidulans and Aspergillus niger ) and two yeast strains ( Rhodotorula toruloides and Lipomyces starkeyi ) served as heterotrophs in this system. They were co-cultured with S.elongatus under different pH condition, and growth on different carbon source to understand the symbiotic system and optimize the parameters for production. The two fungi strained grew much better at pH 7, 8 and 9 with Yeast Nitrogen Base (YNB ) supplementation. Two yeast strains grew well on pH 7 and 8 with YNB supplementation. All four species achieved the highest biomass level when utilizing sucrose as the main carbon sources, which demonstrates a great pairing with S.elongatus . In addition to investigate the metabolite exchange and growth condition of the co-culture system, we incorporated an Aspergillus strain expressing three genes (PAND, BAPAT and HPDH). Expression of these three genes enabled production of 3-hydroxypropionic acid (3HP) with a titer of 3-6 g/L regardless of pH and other nutrient conditions. Moreover, we developed a computational model with different heterotrophic fungi symbiosing with S.elongatus to evaluate the exchange of hundreds of metabolites. The accuracy and sensitivity had been optimized by high-throughput phenotyping assays. This project demonstrated ways to enhance a synthetic lichen platform’s efficiency and scalability to create a robust system for sustainable bioproduct synthesis. The project has enabled us to explore the technological and commercial potential of sustainable lichen co-culture. The project has also trained the next generation of scientists to address sustainability, carbon fixation, and design solutions to contemporary global challenges. The lichen platform represented a novel approach to sustainably producing bioproducts with a reduced carbon footprint and lower costs.

09 BIOMASS FUELS↗

Semi-tubular carbon film for stable lithium metal anodes and methods of manufacture thereof

A method of forming a battery electrode by forming, on a first substrate, a polymer template comprising interconnected polymer fibers, forming, on the polymer template, a carbon coating to form a carbon-coated polymer template, removing the carbon-coated polymer template from the first substrate, subsequent to removing the carbon-coated polymer template from the first substrate, removing the polymer template from the carbon coating, and disposing the carbon coating on a second substrate. A solid electrolyte interphase layer (SEI) comprising the carbon coating produced via the method, a battery electrode comprising such an SEI layer, and a battery comprising such a battery electrode are also provided.

Ren, Zhifeng↗

Belowground plant allocation regulates rice methane emissions from degraded peat soils

Carbon-rich peat soils have been drained and used extensively for agriculture throughout human history, leading to significant losses of their soil carbon. One solution for rewetting degraded peat is wet crop cultivation. Crops such as rice, which can grow in water-saturated conditions, could enable agricultural production to be maintained whilst reducing CO 2 and N 2 O emissions from peat. However, wet rice cultivation can release considerable methane (CH 4 ). Water table and soil management strategies may enhance rice yield and minimize CH 4 emissions, but they also influence plant biomass allocation strategies. It remains unclear how water and soil management influences rice allocation strategies and how changing plant allocation and associated traits, particularly belowground, influence CH 4 -related processes. We examined belowground biomass (BGB), aboveground biomass (AGB), belowground:aboveground ratio (BGB:ABG), and a range of root traits (root length, root diameter, root volume, root area, and specific root length) under different soil and water treatments; and evaluated plant trait linkages to CH 4 . Rice (Oryza sativa L.) was grown for six months in field mesocosms under high (saturated) or low water table treatments, and in either degraded peat soil or degraded peat covered with mineral soil. We found that BGB and BGB:AGB were lowest in water saturated conditions where mineral soil had been added to the peat, and highest in low-water table peat soils. Furthermore, CH 4 and BGB were positively related, with BGB explaining 60% of the variation in CH 4 but only under low water table conditions. Our results suggest that a mix of low water table and mineral soil addition could minimize belowground plant allocation in rice, which could further lower CH 4 likely because root-derived carbon is a key substrate for methanogenesis. Minimizing root allocation, in conjunction with water and soil management, could be explored as a strategy for lowering CH 4 emissions from wet rice cultivation in degraded peatlands.

54 ENVIRONMENTAL SCIENCES↗

Growing Aligned Carbon Nanotubes for Interconnections in ICs

A process for growing multiwalled carbon nanotubes anchored at specified locations and aligned along specified directions has been invented. Typically, one would grow a number of the nanotubes oriented perpendicularly to a silicon integrated-circuit (IC) substrate, starting from (and anchored on) patterned catalytic spots on the substrate. Such arrays of perpendicular carbon nanotubes could be used as electrical interconnections between levels of multilevel ICs. The process (see Figure 1) begins with the formation of a layer, a few hundred nanometers thick, of a compatible electrically insulating material (e.g., SiO(x) or Si(y)N(z) on the silicon substrate. A patterned film of a suitable electrical conductor (Al, Mo, Cr, Ti, Ta, Pt, Ir, or doped Si), having a thickness between 1 nm and 2 m, is deposited on the insulating layer to form the IC conductor pattern. Next, a catalytic material (usually, Ni, Fe, or Co) is deposited to a thickness between 1 and 30 nm on the spots from which it is desired to grow carbon nanotubes. The carbon nanotubes are grown by plasma-enhanced chemical vapor deposition (PECVD). Unlike the matted and tangled carbon nanotubes grown by thermal CVD, the carbon nanotubes grown by PECVD are perpendicular and freestanding because an electric field perpendicular to the substrate is used in PECVD. Next, the free space between the carbon nanotubes is filled with SiO2 by means of CVD from tetraethylorthosilicate (TEOS), thereby forming an array of carbon nanotubes embedded in SiO2. Chemical mechanical polishing (CMP) is then performed to remove excess SiO2 and form a flat-top surface in which the outer ends of the carbon nanotubes are exposed. Optionally, depending on the application, metal lines to connect selected ends of carbon nanotubes may be deposited on the top surface. The top part of Figure 2 is a scanning electron micrograph (SEM) of carbon nanotubes grown, as described above, on catalytic spots of about 100 nm diameter patterned by electron-beam lithography. These and other nanotubes were found to have lengths ranging from 2 to 10 m and diameters ranging from 30 to 200 nm, the exact values of length depending on growth times and conditions and the exact values of diameter depending on the diameters and thicknesses of the catalyst spots. The bottom part of Figure 2 is an SEM of an embedded array of carbon nanotubes after CMP.

Li, Jun↗

Creating multifunctional synthetic lichen platforms for sustainable biosynthesis of biofuel precursors

In this project, we were creating a sustainable platform for biofuel production, utilizing carbon-fixing autotrophs to supply oxygen and organic substrates to heterotrophic partners, which in turn produce carbon dioxide to feed the autotrophs. This symbiotic lichen community could lower the input cost, optimize metabolic exchanges and improve the generation of biofuel precursors through multi-omics driven genetic engineering. The cyanobacteria Synechococcus elongatus (S. elongatus) was used as the primary autotroph to provide oxygen and organic substrates, especially sucrose, to a co-culture system. The strain with overexpression of sucrose transporter cscB demonstrated a significant increase in sucrose production under salt stress as what we expected. We also implemented 13C metabolic flux analysis on the sucrose secreting strain S. elongatus cscB-NaCl. Next, transporters proteins like glutamate exporter mscCG from Corynebacterium glutamicum was overexpressed in S. elongatus to improve metabolite exchange.

Betenbaugh, Michael↗

Multicomponent Reactions Among Alkyl Isocyanides, sp Reactants, and sp 2 Carbon Cages

We explored the reactivity and substrate scope of the reactions among an alkyl isocyanide, an sp-hybridized reactant (i.e. alkyne or allene), and a carbon cage, as a new approach to functionalize fullerenes and metallofullerenes. Furthermore, this account summarizes the key findings in our recent published work, and some original data for the reaction involving an isocyanide, allenes, and metallofullerene Lu 3 N@C 80 .

36 MATERIALS SCIENCE↗

Back contacts for silicon-on-ceramic solar cells

Grooved substrate exposes back surface of photovoltaic cells, allowing dopant diffusion into surface and electrical contact. When substrate is coated successively with carbon and molten silicon, polycrystalline-silicon bridges form over grooves, but leave channels open. Best adhesion results when substrate grooves run perpendicular to direction of liquid-silicon layer and are closely spaced.

Schuller, T. L.↗

Radiation Shielding Systems Using Nanotechnology

A system for shielding personnel and/or equipment from radiation particles. In one embodiment, a first substrate is connected to a first array or perpendicularly oriented metal-like fingers, and a second, electrically conducting substrate has an array of carbon nanostructure (CNS) fingers, coated with an electro-active polymer extending toward, but spaced apart from, the first substrate fingers. An electric current and electric charge discharge and dissipation system, connected to the second substrate, receives a current and/or voltage pulse initially generated when the first substrate receives incident radiation. In another embodiment, an array of CNSs is immersed in a first layer of hydrogen-rich polymers and in a second layer of metal-like material. In another embodiment, a one- or two-dimensional assembly of fibers containing CNSs embedded in a metal-like matrix serves as a radiation-protective fabric or body covering.

Chen, Bin↗

Direct Electrolytic Deposition of Mats of Mn(x)O(y) Nanowires

Mats of free-standing manganese oxide (MnxOy) nanowires have been fabricated as experimental electrode materials for rechargeable electrochemical power cells and capacitors. Because they are free-standing, the wires in these mats are electrochemically accessible. The advantage of the mat-of-nanowires configuration, relative to other configurations of electrode materials, arises from the combination of narrowness and high areal number density of the wires. This combination offers both high surface areas for contact with electrolytes and short paths for diffusion of ions into and out of the electrodes, thereby making it possible to charge and discharge at rates higher than would otherwise be possible and, consequently, to achieve greater power densities. The nanowires are fabricated in an electrolytic process in which there is no need for an electrode binder material. Moreover, there is no need to incorporate an electrically conductive additive into the electrode material; the only electrically conductive material that must be added is a thin substrate contact film at the anchored ends of the nanowires. Hence, the mass fraction of active electrode material is close to 100 percent, as compared with about 85 percent in conventional electrodes made from a slurry of active electrode material, binder, and conductive additive pressed onto a metal foil. The locations and sizes of the nanowires are defined by holes in templates in the form of commercially available porous alumina membranes. In experiments to demonstrate the present process, alumina membranes of various pore sizes and degrees of porosity were used. First, a film of Au was sputtered onto one side of each membrane. The membranes were then attached, variously, to carbon tape or a gold substrate by use of silver or carbon paste. Once thus attached, the membranes were immersed in a plating solution comprising 0.01 M MnSO4 + 0.03 M (NH4)2SO4. The pH of the solution was kept constant at 8 by addition of H2SO4 or NH4OH as needed. Mn(x)O(y) nanowires were potentiostatically electrodeposited in the pores in the alumina templates. Depending on the anodic deposition potentials, Mn(x)O(y) was deposited in various oxidation states [divalent (Mn3O4), trivalent (Mn2O3), or tetravalent (MnO2)]. The Mn(x)O(y) wires were made free-standing (see figure) by dissolving the alumina templates, variously, in KOH or NaOH at a concentration of 20 volume percent.

Myung, Nosang↗

Partial-Single-Atom, Partial-Nanoparticle Composites Enhance Water Dissociation for Hydrogen Evolution

The development of an efficient electrocatalyst toward the hydrogen evolution reaction (HER) is of significant importance in transforming renewable electricity to pure and clean hydrogen by water splitting. However, the construction of an active electrocatalyst with multiple sites that can promote the dissociation of water molecules still remains a great challenge. Herein, a partial-single-atom, partial-nanoparticle composite consisting of nanosized ruthenium (Ru) nanoparticles (NPs) and individual Ru atoms as an energy-efficient HER catalyst in alkaline medium is reported. The formation of this unique composite mainly results from the dispersion of Ru NPs to small-size NPs and single atoms (SAs) on the Fe/N codoped carbon (Fe–N–C) substrate due to the thermodynamic stability. The optimal catalyst exhibits an outstanding HER activity with an ultralow overpotential (9 mV) at 10 mA cm -2 (η 10 ), a high turnover frequency (8.9 H 2 s -1 at 50 mV overpotential), and nearly 100% Faraday efficiency, outperforming the state-of-the-art commercial Pt/C and other reported HER electrocatalysts in alkaline condition. Both experimental and theoretical calculations reveal that the coexistence of Ru NPs and SAs can improve the hydride coupling and water dissociation kinetics, thus synergistically enhancing alkaline hydrogen evolution performance.

36 MATERIALS SCIENCE↗

The oleaginous yeast Cutaneotrichosporon oleaginosum modifies corn stover alkali lignin

The current paradigm in synthetic biology for lignin bioconversion platforms includes primarily bacteria and filamentous fungi. Yeast are notoriously understudied for their role in lignin degradation and utilization, despite their ubiquity in saprophytic microbial communities. A few publications report lignin-modifying yeasts, but investigations to date have relied on model aromatic compounds or lignin-containing substrates replete with other carbon sources. In this work, we use a suite of analytical tools to evaluate interactions between corn stover-extracted lignin and the oleaginous yeast Cutaneotrichosporon oleaginosum. Notably, 2D-NMR analysis showed a significant decrease in the H-lignin component as well as resinol (β-β) and phenylcoumaran (β-5) linkages. Using super-resolution fluorescence microscopy, we demonstrated that this yeast may uptake polymeric lignin and/or undertakes interactions at the cellular envelope. To explore mechanisms of lignin modification, transport, and aromatics catabolism, extensive secretomics and proteomics analyses were conducted. Compared to carbon-limited glucose and “No Carbon” controls, several putative laccases, quinone reductases, superoxide dismutases, and glyoxal/oxalate oxidases were upregulated in the lignin condition. Excitingly, two ferric reductases and an oxalate exchanger were only observed in the lignin condition. These results indicate that C. oleaginosum may perform extracellular quinone redox cycling to generate lignin-modifying reactive oxygen species. These findings enhance our understanding of yeast-lignin interactions and provide valuable insights for validation studies and metabolic engineering.

09 BIOMASS FUELS↗

Continuous coating of silicon-on-ceramic

Growth of sheet silicon on low-cost substrates has been demonstrated by the silicon coating with inverted meniscus (SCIM) technique. A mullite-based ceramic substrate is coated with carbon and then passed over a trough of molten silicon with a raised meniscus. Solidification occurs at the trailing edge of the downstream meniscus, producing a silicon-on-ceramic (SOC) layer. Meniscus shape and stability are controlled by varying the level of molten silicon in a reservoir connected to the trough. The thermal conditions for growth and the crystallographic texture of the SOC layers are similar to those produced by dip-coating, the original technique of meniscus-controlled growth. The thermal conditions for growth have been analyzed in some detail. The analysis correctly predicts the velocity-thickness relationship and the liquid-solid interface shape for dip-coating, and appears to be equally applicable to SCIM-coating. Solar cells made from dip-coated SOC material have demonstrated efficiencies of 10% on 4-sq cm cells and 9.9% on 10-sq cm cells.

Heaps, J. D.↗

Optical properties of hydrogenated amorphous carbon films grown from methane plasma

A 30 kHz ac glow discharge formed from methane gas was used to grow carbon films on InP substrates. Both the growth rate, and the realitive Ar ion sputtering rate at 3 keV varied monotonically with deposition power. Results from the N-15 nuclear reaction profile experiments indicated a slight drop in the hydrogen concentration as more energy was dissipated in the ac discharge. Values for the index of refraction and extinction coefficient ranged from 1.721 to 1.910 and 0 to -0.188, respectively. Optical bandgaps as high as 2.34 eV were determined.

Pouch, J. J.↗

Degradation and crosslinking of perfluoroalkyl polyethers under X-ray irradiation in ultrahigh vacuum

Degradation of three types of commercially available perfluoroalkyl polyethers (PFPE)-Demnum S200, Fomblin Z25, and Krytox 16256-by X-ray irradiation was studied by using X-ray photoemission spectroscopy (XPS) and a mass spectrometer under ultra-high-vacuum conditions. The carbons in the polymers were characterized by chemical shifts of Cls binding energies. Gaseous products containing COF2 and low-molecular-weight fluorocarbons were formed. From Fomblin Z25, which has acetal linkages (-OCF2O-), a large quantity of COF2 gas was evolved. Liquid products became tacky after a long irradiation time, and some did not dissolve in Freon. High-pressure liquid chromatography (HPLC) showed that molecular weight distribution became broader and that higher molecular weight polymers were formed from Demnum and Krytox. We concluded from these results that degradation and cross-linking took place simultaneously. Demnum crosslinked more easily than the other fluids. The time dependence of both XPS spectra of Cls and mass spectra showed that C-O-bonded carbons in PFPE'S were removed faster than other carbons. There was no substrate effect on the degradation reaction because the first-order rate constants calculated from the change of gaseous products were similar when stainless steel (440C) and gold-coated surfaces were used. Metal fluorides were formed on stainless steel during the reaction. A mechanism for the degradation of PFPE'S is discussed on the basis of their molecular structures.

Mori, Shigeyuki↗

X-ray photoelectron spectroscopy study of catalyzed aluminum carbide formation at aluminum-carbon interfaces

Aluminum carbide may form at aluminum-graphite interfaces during the high-temperature processing of graphite fiber-reinforced aluminum metal matrix composites. The chemical interactions leading to the formation of the aluminum carbide in the solid state involve the breaking of the carbon-carbon bonds within the graphite, the transport of the carbon atoms across the interface, and the reaction with the aluminum to form Al4C3. The aluminum carbide formation process has been followed using X-ray photoelectron spectroscopy of model, thin-film, reaction couples. The overall reaction is shown to be catalyzed by the presence of water vapor. Water at the interface increases reaction kinetics by apparently weakening the bonds between the surface carbon atoms and their substrate. This result is in general agreement with what is known to occur during the oxidation of graphite in air.

Rabenberg, L.↗

Multilayer Film Assembly of Carbon Nanotubes

An approach to assemble multilayers of carbon nanotubes on a substrate is presented. Chemical vapor deposition using a transition metal catalyst formulation is used to grow the nanotubes. Results show a bilayer assembly of nanotubes each with a different density of tubes.

Cassell, Alan M.↗

PECVD Growth of Carbon Nanotubes

Plasma enhanced chemical vapor deposition (PECVD), using inductively coupled plasma, has been used to grow carbon nanotubes (CNTs) and graphitic carbon fibers (GCF) on substrates sputtered with aluminum and iron catalyst. The capacitive plasma's power has been shown to cause a transition from nanotubes to nanofibers, depending on the strength of the plasma. The temperature, placement, and other factors have been shown to affect the height and density of the tube and fiber growth.

McAninch, Ian↗