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At least 325 records · Page 18

Pyrolyzed Parylene-N for in Vivo Electrochemical Detection of Neurotransmitters

Carbon electrodes are typically used for in vivo dopamine detection, and new types of electrodes and customized fabrication methods will facilitate new applications. Parylene is an insulator that can be deposited in a thin layer on a substrate and then pyrolyzed to carbon to enable its use as an electrode. However, pyrolyzed parylene has not been used for the real-time detection of neurochemicals by fast-scan cyclic voltammetry. In this work, we deposited thin layers of parylene-N (PN) on metal wires and then pyrolyzed them to carbon with high temperatures in a rapid thermal processor (RTP). Different masses of PN, 1, 6, and 12 g, were deposited to vary the thickness. RTP-PN (6 g) produced a 194 nm layer carbon thickness and had optimal electrochemical stability. Pyrolyzed parylene-N modified electrodes (PPNMEs) were characterized for electrochemical detection of dopamine, serotonin, and adenosine. Background-normalized currents at PPNMEs were about 2 times larger than those of carbon-fiber microelectrodes (CFMEs). Rich defect sites and oxygen functional groups promoted the neurochemical adsorption of cationic neurotransmitters. PPNMEs resisted fouling from serotonin polymer formation. PPNMEs were used in vivo to detect stimulated dopamine release and monitor spontaneous adenosine release. Pyrolyzed parylene is a sensitive and fouling-resistant thin-film carbon electrode that could be used in the future for making customized electrodes and devices.

25 ENERGY STORAGE↗

Increasing aggregate size reduces single-cell organic carbon incorporation by hydrogel-embedded wetland microbes

Abstract Microbial degradation of organic carbon in sediments is impacted by the availability of oxygen and substrates for growth. To better understand how particle size and redox zonation impact microbial organic carbon incorporation, techniques that maintain spatial information are necessary to quantify elemental cycling at the microscale. In this study, we produced hydrogel microspheres of various diameters (100, 250, and 500 μm) and inoculated them with an aerobic heterotrophic bacterium isolated from a freshwater wetland (Flavobacterium sp.), and in a second experiment with a microbial community from an urban lacustrine wetland. The hydrogel-embedded microbial populations were incubated with 13C-labeled substrates to quantify organic carbon incorporation into biomass via nanoSIMS. Additionally, luminescent nanosensors enabled spatially explicit measurements of oxygen concentrations inside the microspheres. The experimental data were then incorporated into a reactive-transport model to project long-term steady-state conditions. Smaller (100 μm) particles exhibited the highest microbial cell-specific growth per volume, but also showed higher absolute activity near the surface compared to the larger particles (250 and 500 μm). The experimental results and computational models demonstrate that organic carbon availability was not high enough to allow steep oxygen gradients and as a result, all particle sizes remained well-oxygenated. Our study provides a foundational framework for future studies investigating spatially dependent microbial activity in aggregates using isotopically labeled substrates to quantify growth.

59 BASIC BIOLOGICAL SCIENCES↗

High Purity and Reduced Defects Hard Carbon Synthesis for Sodium-Ion Batteries

Hard carbon (HC) is the state-of-the-art anode material for sodium-ion batteries; however, the high-temperature carbonization of precursors (>1100 °C) often introduces inorganic impurities, an issue that remains largely underexplored. Here, we report a simple synthesis strategy for producing high purity HC by carbonizing a cellulose-derived precursor at 1400 °C under a slightly reducing Ar–H2 atmosphere on a graphite substrate, thereby eliminating the aluminum contamination observed during conventional carbonization on an alumina substrate under Ar. In addition, the modified synthetic condition reduces surface defects and the concentration of oxygen-containing functional groups, thereby altering the interphase formation on the HC surface. At a current density of 20 mA g−1, the impurity-rich HC exhibited an initial coulombic efficiency (ICE) of 74.1% and a reversible capacity of 248.8 mAh g−1. In sharp contrast, the high purity HC delivered a significantly improved ICE of 90.1% and a reversible capacity of 345.1 mAh g−1. These results underscore the critical importance of impurity and defect control during HC synthesis and highlight the clear electrochemical advantages of high purity HC with reduced defects for sodium-ion battery anodes.

Harshita, Lohanni↗

Method of synthesizing metal doped diamond-like carbon films

A method of synthesizing metal doped carbon films by placing a substrate in a chamber with a selected amount of a metalorganic compound. An electron cyclotron resonance is applied to the chamber in order to vaporize the metalorganic compound. The resonance is applied to the chamber until a metal doped carbon film is formed. The metalorganic compound is preferably selected from the group consisting of an organic salt of ruthenium, palladium, gold or platinum.

Ueno, Mayumi↗

Permafrost Landscape History Shapes Fluvial Chemistry, Ecosystem Carbon Balance, and Potential Trajectories of Future Change

Intensifying permafrost thaw alters carbon cycling by mobilizing large amounts of terrestrial substrate into aquatic ecosystems. Yet, few studies have measured aquatic carbon fluxes and constrained drivers of ecosystem carbon balance across heterogeneous Arctic landscapes. Here, we characterized hydrochemical and landscape controls on fluvial carbon cycling, quantified fluvial carbon fluxes, and estimated fluvial contributions to ecosystem carbon balance across 33 watersheds in four ecoregions in the continuous permafrost zone of the western Canadian Arctic: unglaciated uplands, ice-rich moraine, and organic-rich lowlands and till plains. Major ions, stable isotopes, and carbon speciation and fluxes revealed patterns in carbon cycling across ecoregions defined by terrain relief and accumulation of organics. In previously unglaciated mountainous watersheds, bicarbonate dominated carbon export (70% of total) due to chemical weathering of bedrock. In lowland watersheds, where soil organic carbon stores were largest, lateral transport of dissolved organic carbon (50%) and efflux of biotic CO 2 (25%) dominated. In watersheds affected by thaw-induced mass wasting, erosion of ice-rich tills enhanced chemical weathering and increased particulate carbon fluxes by two orders of magnitude. From an ecosystem carbon balance perspective, fluvial carbon export in watersheds not affected by thaw-induced wasting was, on average, equivalent to 6–16% of estimated net ecosystem exchange (NEE). Finally, in watersheds affected by thaw-induced wasting, fluvial carbon export approached 60% of NEE. Because future intensification of thermokarst activity will amplify fluvial carbon export, determining the fate of carbon across diverse northern landscapes is a priority for constraining trajectories of permafrost region ecosystem carbon balance.

54 ENVIRONMENTAL SCIENCES↗

Evaluation of different getter substrates using two-dimensional gas chromatography with time of flight mass spectrometry

We report while understanding hydrogen uptake by organic based getters such as 1,4-bis(phenylethynyl)benzene (DEB) combined with a palladium(0)bis(dibenzylideneacetone) (Pd(dba) 2 ) catalyst is essential, another crucial element to understand is the decomposition of the DEB, Pd(dba) 2 , and/or substrate material. The breakdown of these materials may create unwanted volatiles, which may interact with and lead to deterioration of sensitive materials. Moreover, it is critical to understand if different substrates cause the getter and/or catalyst to degrade in different manners. Utilizing comprehensive two-dimensional gas chromatography (GC×GC) with time-of-flight mass spectrometry (TOFMS), the presence of volatiles located in the headspace of various DEB/Pd(dba) 2 getter substrates is examined. These samples include a getter infused silicone foam, a hydrogenated getter infused silicone foam, an activated carbon getter pellet, and a hydrogenated activated carbon getter pellet. Application of Fisher ratio (F-ratio) analyses lead to the identification of several compounds that are generated or consumed through the hydrogenation process. These include benzene derivatives such as bibenzyl, benzaldehyde, and vinyl benzoate in the activated carbon pellets and 1,5-diphenyl-3-pentanone, toluene, styrene, and 1–1'(2-pentene 1,5-diyl)bis benzene in the silicone foams, and alkane/alkene derivatives such undecane, 4-tridecene, and decane in the activated carbon pellets and 2,6-dimethyl undecane in the silicone foams. Further comparison of the different hydrogenated getter substrates (e.g. activated carbon pellet and silicone foam) indicates that the different substrates alter the decomposition products created from the degradation of the DEB and Pd(dba) 2 .

47 OTHER INSTRUMENTATION↗

Wetting Angles and Surface Tension of Ge(1-x)Si(x) Melts on Different Substrate Materials

The wetting angles and the surface tension of Ge(1-x)Si(x) melts (0.02 less than x less than 0.13) have been measured on various substrate materials using the sessile drop technique. Fused quartz, sapphire, SiC, glassy carbon, pBN, AIN, and Si3N4 have been used as substrates. The highest and most stable wetting angles were found for pBN substrates with 164 +/- 8 deg., either under forming gas with an additional carbon getter in the system or under active vacuum. The surface tension measurements resulted in a value of +2.2 x 10(exp -3) N/m.at%Si for the concentration dependence delta(gamma)/(delta)C. For the composition range measured, the temperature dependence (delt)gamma/(delta)T showed values similar to those of pure Ge, on average -0.07 x 10(exp -3) N/mK.

Croell, A.↗

Multi-layered diamond-like carbon coating for electronic components

A multi-layer coating on an outer surface of a substrate includes a first layer applied directly to the outer surface of the substrate. The first layer includes diamond-like carbon (DLC) configured to mitigate metal whisker formation. A second layer is applied on a top surface of the first layer. The second layer is a conformal coating that includes a second material configured to bind to the top surface of the first layer and fill any microfractures that may form in the first layer. Optionally, a third layer is applied on a top surface of the second layer and includes DLC configured to protect the second layer from oxidation and degradation.

Selter, Thomas Matthew↗

Carbon Nanotube Based Light Sensor

A light sensor substrate comprises a base made from a semi-conductive material and topped with a layer of an electrically non-conductive material. A first electrode and a plurality of carbon nanotube (CNT)-based conductors are positioned on the layer of electrically non-conductive material with the CNT-based conductors being distributed in a spaced apart fashion about a periphery of the first electrode. Each CNT-based conductor is coupled on one end thereof to the first electrode and extends away from the first electrode to terminate at a second free end. A second or gate electrode is positioned on the non-conductive material layer and is spaced apart from the second free end of each CNT-based conductor. Coupled to the first and second electrode is a device for detecting electron transfer along the CNT-based conductors resulting from light impinging on the CNT-based conductors.

Wincheski, russell A.↗

Ion beam sputter etching

An ion beam etching process which forms extremely high aspect ratio surface microstructures using thin sputter masks is utilized in the fabrication of integrated circuits. A carbon rich sputter mask together with unmasked portions of a substrate is bombarded with inert gas ions while simultaneous carbon deposition occurs. The arrival of the carbon deposit is adjusted to enable the sputter mask to have a near zero or even slightly positive increase in thickness with time while the unmasked portions have a high net sputter etch rate.

Banks, Bruce A.↗

Pore-scale view of microbial turnover: combining 14 C imaging, μCT, and zymography after adding soluble carbon to soil pores of specific sizes

The location of microorganisms and substrates within soil pore networks plays a crucial role for organic carbon (C) processing, its microbial utilization and turnover, and has direct consequences for C and nutrient cycling. An optimal approach to quantify responses to new C inputs from microorganisms residing in specific pores is the addition of new C to pores of target sizes in undisturbed soil cores. We used the matric potential approach to add 14 C labeled glucose to small (< 40 μm, root free) or large (60-180 μm, potentially inhabited by roots) pores of undisturbed soil cores. Localization of glucose-derived C via 14 C imaging was related to pore size distributions and connectivity, characterized via X-ray computed micro-tomography (μCT), and to β-glucosidase activity, characterized via zymography. After two-week incubations, 1.3 times more glucose was mineralized ( 14 CO 2 ) when it was added to the large pores, however more 14 C remained in microbial biomass when glucose was added to the small pores. Consequently, while utilizing the same amounts of easily available C, the microorganisms localized in the large pores had faster turnover compared to microorganisms in small pores. Stronger associations between β-glucosidase activity and glucose-derived C were observed when glucose was added to the large pores. We conclude that 1) the matric potential approach allows placing, albeit not exactly, soluble substrates into pores of target diameter range, and 2) microorganisms localized in large pores respond to new C inputs with faster turnover, greater growth, and more intensive enzyme production compared to those inhabiting the small pores.

54 ENVIRONMENTAL SCIENCES↗

Evaluation of the Effect of Silicone Contamination on Various Bond Systems and the Feasibility of Removing the Contamination

Silicone is a contaminant that can cause catastrophic failure of a bond system depending on the materials and processes used to fabricate the bond system. Unfortunately, more and more materials are fabricated using silicone. The purpose of this testing was to evaluate which bond systems are sensitive to silicone contamination and whether or not a cleaning process could be utilized to remove the silicone to bring the bond system performance back to baseline. Due to the extensive nature of the testing, attempts will be made to generalize the understanding within classes of substrates, bond systems, and surface preparation and cleaning methods. This study was done by contaminating various metal (steel, Inconel, and aluminum), phenolic (carbon-cloth phenolic [CCP] and glass-cloth phenolic [GCP]), and rubber (natural rubber, asbestos-silicone dioxide filled natural butyldiene rubber [ASNBR]; silica-filled ethylene propylenediene monomer [SFEPDM], and carbon-filled ethylene propylenediene monomer [CFEPDM]) substrates which were then bonded using various adhesives and coatings (epoxy-based adhesives, paints, ablative compounds, and Chemlok adhesives) to determine the effect silicone contamination has on a given bond system's performance. The test configurations depended on the bond system being evaluated. The study also evaluated the feasibility of removing the silicone contamination by cleaning the contaminated substrate prior to bonding. The cleaning processes also varied depending on bond system.

Stanley, Stephanie D.↗

Preparation and analysis of particulate metal deposits

Small particles and clusters of palladium were grown by deposition from the vapor phase under ultrahigh vacuum conditions. Amorphous and crystalline support films of Al2O3 and ultrathin amorphous carbon films were used as substrate materials. The growth of the metal deposit was monitored in situ by scanning transmission diffraction of energy-filtered 100 kV electrons and high resolution transmission electron microscopy (TEM) analysis was performed in a separate instrument. It was established by in situ TEM, however, that the transfer of specimens in this case did not unduly affect the size and distribution of deposit particles. It was found that the cleanness, stoichiometry, crystallinity and structural perfection of the support surface play an essential role in determining the crystalline perfection and structure of the particles. The smallest palladium clusters reproducibly prepared contained not more than six atoms but size determinations below 1 nm average particle diameter are very problematic with conventional TEM. Palladium particles grown on carbon supports feature an impurity-stabilized mosaic structure.

Poppa, H.↗

Gas Composition Sensing Using Carbon Nanotube Arrays

This innovation is a lightweight, small sensor for inert gases that consumes a relatively small amount of power and provides measurements that are as accurate as conventional approaches. The sensing approach is based on generating an electrical discharge and measuring the specific gas breakdown voltage associated with each gas present in a sample. An array of carbon nanotubes (CNTs) in a substrate is connected to a variable-pulse voltage source. The CNT tips are spaced appropriately from the second electrode maintained at a constant voltage. A sequence of voltage pulses is applied and a pulse discharge breakdown threshold voltage is estimated for one or more gas components, from an analysis of the current-voltage characteristics. Each estimated pulse discharge breakdown threshold voltage is compared with known threshold voltages for candidate gas components to estimate whether at least one candidate gas component is present in the gas. The procedure can be repeated at higher pulse voltages to estimate a pulse discharge breakdown threshold voltage for a second component present in the gas. The CNTs in the gas sensor have a sharp (low radius of curvature) tip; they are preferably multi-wall carbon nanotubes (MWCNTs) or carbon nanofibers (CNFs), to generate high-strength electrical fields adjacent to the tips for breakdown of the gas components with lower voltage application and generation of high current. The sensor system can provide a high-sensitivity, low-power-consumption tool that is very specific for identification of one or more gas components. The sensor can be multiplexed to measure current from multiple CNT arrays for simultaneous detection of several gas components.

Li, Jing↗

Pyrolyzed thin film carbon

A method of making carbon thin films comprises depositing a catalyst on a substrate, depositing a hydrocarbon in contact with the catalyst and pyrolyzing the hydrocarbon. A method of controlling a carbon thin film density comprises etching a cavity into a substrate, depositing a hydrocarbon into the cavity, and pyrolyzing the hydrocarbon while in the cavity to form a carbon thin film. Controlling a carbon thin film density is achieved by changing the volume of the cavity. Methods of making carbon containing patterned structures are also provided. Carbon thin films and carbon containing patterned structures can be used in NEMS, MEMS, liquid chromatography, and sensor devices.

Tai, Yu-Chong↗

Soil minerals affect taxon-specific bacterial growth

Abstract Secondary minerals (clays and metal oxides) are important components of the soil matrix. Clay minerals affect soil carbon persistence and cycling, and they also select for distinct microbial communities. Here we show that soil mineral assemblages—particularly short-range order minerals—affect both bacterial community composition and taxon-specific growth. Three soils with different parent material and presence of short-range order minerals were collected from ecosystems with similar vegetation and climate. These three soils were provided with 18O-labeled water and incubated with or without artificial root exudates or pine needle litter. Quantitative stable isotope probing was used to determine taxon-specific growth. We found that the growth of bacteria varied among soils of different mineral assemblages but found the trend of growth suppression in the presence of short-range order minerals. Relative growth of bacteria declined with increasing concentration of short-range order minerals between 25–36% of taxa present in all soils. Carbon addition in the form of plant litter or root exudates weakly affected relative growth of taxa (p = 0.09) compared to the soil type (p < 0.01). However, both exudate and litter carbon stimulated growth for at least 34% of families in the soils with the most and least short-range order minerals. In the intermediate short-range order soil, fresh carbon reduced growth for more bacterial families than were stimulated. These results highlight how bacterial-mineral-substrate interactions are critical to soil organic carbon processing, and how growth variation in bacterial taxa in these interactions may contribute to soil carbon persistence and loss.

59 BASIC BIOLOGICAL SCIENCES↗

Stable carbon isotope fractionation by sulfate-reducing bacteria

Biogeochemical transformations occurring in the anoxic zones of stratified sedimentary microbial communities can profoundly influence the isotopic and organic signatures preserved in the fossil record. Accordingly, we have determined carbon isotope discrimination that is associated with both heterotrophic and lithotrophic growth of pure cultures of sulfate-reducing bacteria (SRB). For heterotrophic-growth experiments, substrate consumption was monitored to completion. Sealed vessels containing SRB cultures were harvested at different time intervals, and delta(13)C values were determined for gaseous CO(2), organic substrates, and products such as biomass. For three of the four SRB, carbon isotope effects between the substrates, acetate or lactate and CO(2), and the cell biomass were small, ranging from 0 to 2 per thousand. However, for Desulfotomaculum acetoxidans, the carbon incorporated into biomass was isotopically heavier than the available substrates by 8 to 9 per thousand. SRB grown lithoautotrophically consumed less than 3% of the available CO(2) and exhibited substantial discrimination (calculated as isotope fractionation factors [alpha]), as follows: for Desulfobacterium autotrophicum, alpha values ranged from 1.0100 to 1.0123; for Desulfobacter hydrogenophilus, the alpha value was 0.0138, and for Desulfotomaculum acetoxidans, the alpha value was 1.0310. Mixotrophic growth of Desulfovibrio desulfuricans on acetate and CO(2) resulted in biomass with a delta(13)C composition intermediate to that of the substrates. The extent of fractionation depended on which enzymatic pathways were used, the direction in which the pathways operated, and the growth rate, but fractionation was not dependent on the growth phase. To the extent that environmental conditions affect the availability of organic substrates (e.g., acetate) and reducing power (e.g., H(2)), ecological forces can also influence carbon isotope discrimination by SRB.

Deltaproteobacteria/growth & development/metabolis↗

Self-Sacrificial Template Synthesis of Fe-N-C Catalysts with Dense Active Sites Deposited on A Porous Carbon Network for High Performance in PEMFC

In this study, iron-nitrogen-carbon (Fe-N-C) single-atom catalysts are promising sustainable alternatives to the costly and scarce platinum (Pt) to catalyze the oxygen reduction reactions (ORR) at the cathode of proton exchange membrane fuel cells (PEMFCs). However, Fe-N-C cathodes for PEMFC are made thicker than Pt/C ones, in order to compensate for the lower intrinsic ORR activity and site density of Fe-N-C materials. The thick electrodes are bound with mass transport issues that limit their performance at high current densities, especially in H 2 /air PEMFCs. Practical Fe-N-C electrodes must combine high intrinsic ORR activity, high site density, and fast mass transport. Herein, it has achieved an improved combination of these properties with a Fe-N-C catalyst prepared via a two-step synthesis approach, constructing first a porous zinc-nitrogen-carbon (Zn-N-C) substrate, followed by transmetallating Zn by Fe via chemical vapor deposition. A cathode comprising this Fe-N-C catalyst has exhibited a maximum power density of 0.53 W cm -2 in H 2 /air PEMFC at 80 °C. The improved power density is associated with the hierarchical porosity of the Zn-N-C substrate of this work, which is achieved by epitaxial growth of ZIF-8 onto g-C 3 N 4 , leading to a micro-mesoporous substrate.

25 ENERGY STORAGE↗