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At least 1,603 records · Page 89

Critical Factors Driving the High Volumetric Uptake of Methane in Cu 3 (btc) 2

We report a thorough experimental and computational study has been carried out to elucidate the mechanistic reasons for the high volumetric uptake of methane in the metal–organic framework Cu 3 (btc) 2 (btc 3– = 1,3,5-benzenetricarboxylate; HKUST-1). Methane adsorption data measured at several temperatures for Cu 3 (btc) 2 , and its isostructural analogue Cr 3 (btc) 2 , show that there is little difference in volumetric adsorption capacity when the metal center is changed. In situ neutron powder diffraction data obtained for both materials were used to locate four CD 4 adsorption sites that fill sequentially. This data unequivocally shows that primary adsorption sites around, and within, the small octahedral cage in the structure are favored over the exposed Cu 2+ or Cr 2+ cations. These results are supported by an exhaustive parallel computational study, and contradict results recently reported using a time-resolved diffraction structure envelope (TRDSE) method. Moreover, the computational study reveals that strong methane binding at the open metal sites is largely due to methane–methane interactions with adjacent molecules adsorbed at the primary sites instead of an electronic interaction with the metal center. Simulated methane adsorption isotherms for Cu 3 (btc) 2 are shown to exhibit excellent agreement with experimental isotherms, allowing for additional simulations that show that modifications to the metal center, ligand, or even tuning the overall binding enthalpy would not improve the working capacity for methane storage over that measured for Cu 3 (btc) 2 itself.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unlocking Failure Mechanisms and Improvement of Practical Li–S Pouch Cells through In Operando Pressure Study

For Lithium-sulfur (Li-S) battery commercialization, the study at a pouch cell level is essential, as some problems ignored or deemed minimal at the smaller level could have a greater effect on the performance of the larger pouch cell. Herein, the failure mechanisms of Li-S pouch cells are deeply investigated via in operando pressure analysis. It is found that highly porous structures of cathodes/separators and slow electrolyte diffusion through cathodes/separators can both lead to poor initial wetting. Additionally, Li-metal anode dominates the thickness variation of the whole pouch cell, which is verified by in situ measured pressure variation. Consequently, a real-time approach that combined normalized pressure with dP/dV analysis is proposed and validated to diagnose the morphology evolution of Li-metal anode. Moreover, applied pressure and porosity/tortuosity ratio of the cathode are both identified as independent factors that influence anode performance. In addition to stabilizing anodes, high pressure is proven to improve the cathode connectivity and avoid cathode cracking over cycling, which improves the possibility of developing cathodes with high sulfur mass loading. Here, this work provides insights into Li-S pouch cell design (e.g., cathode and separator) and highlights pathways to improve cell capacity and cycling performance with applied and monitored pressure.

25 ENERGY STORAGE↗

Locus coeruleus catecholamines link neuroticism and vulnerability to tau pathology in aging

Higher neuroticism is a risk factor for Alzheimer's disease (AD), and is implicated in disordered stress responses. The locus coeruleus (LC)-catecholamine system is activated during perceived threat and is a centerpiece of developing models of the pathophysiology of AD, as it is the first brain region to develop abnormal tau. We examined relationships among the "Big 5" personality traits, LC catecholamine synthesis capacity measured with [ 18 F]Fluoro-m-tyrosine PET, and tau burden measured with [ 18 F]Flortaucipir PET in cognitively normal older adults (n = 47). β-amyloid (Aβ) status was determined using [ 11 C]Pittsburgh compound B PET (n = 14 Aβ positive). Lower LC catecholamine synthesis capacity was associated with higher neuroticism, more depressive symptoms as measured by the Geriatric Depression Scale, and higher amygdala tau-PET binding. Exploratory analyses with other personality traits revealed that low trait conscientiousness was also related to both lower LC catecholamine synthesis capacity, and more depressive symptoms. A significant indirect path linked both high neuroticism and low conscientiousness to greater amygdala tau burden via their mutual association with low LC catecholamine synthesis capacity. Together, these findings reveal LC catecholamine synthesis capacity to be a promising marker of affective health and pathology burden in aging, and identifies candidate neurobiological mechanisms for the effect of personality on increased vulnerability to dementia.

59 BASIC BIOLOGICAL SCIENCES↗

DNA-Peptide Amphiphile Nanofibers Enhance Aptamer Function

The single-stranded DNA oligonucleotides known as aptamers have the capacity to bind proteins and other molecules and offer great therapeutic potential. Further work is required to optimize their function and to diminish their susceptibility to nuclease degradation. We report here on the synthesis and supramolecular self-assembly of DNA-peptide amphiphiles that form high aspect ratio nanofibers and display aptamers for the platelet-derived growth factor. The nanofibers were found to bind the growth factor with an affinity that was 5-fold greater than the free aptamer. Additionally, we also observed that the aptamer displayed by the supramolecular nanostructures was eight times more nuclease-resistant than the free aptamer. In order to highlight the therapeutic potential of these supramolecular systems, we demonstrated the improved inhibition of proliferation when the growth factor was bound to aptamers displayed by the nanofibers.

59 BASIC BIOLOGICAL SCIENCES↗

Understanding the Role of SEI Layer in Low-Temperature Performance of Lithium-Ion Batteries

Low-temperature electrolytes (LTEs) have been considered as one of the most challenging aspects for the wide adoption of lithium-ion batteries (LIBs) since the SOA electrolytes cannot sufficiently support the redox reactions at LT resulting in dramatic performance degradation. Although many attempts have been taken by employing various noncarbonate solvent electrolytes, there was a lack of fundamental understanding of the limiting factors for low-temperature operations (e.g., -20 to -40 degrees C). Here, the crucial role of the solid-electrolyte-interface (SEI) in LIB performance at low temperature using a butyronitrile (BN)-based electrolyte was demonstrated. These results suggested that an additive formed SEI with low resistance and low charge transfer dictates the LT performance in terms of capacity and cycle life, presenting a useful guideline in designing new electrolytes to address the LT issue.

25 ENERGY STORAGE↗

Three-Dimensional Solid-State Lithium-Ion Batteries Fabricated by Conformal Vapor-Phase Chemistry

Three-dimensional thin-film solid-state batteries (3D TSSB) were proposed by Long et al. in 2004 as a structure-based approach to simultaneously increase energy and power densities. Here, we report experimental realization of fully conformal 3D TSSBs, demonstrating the simultaneous power-and-energy benefits of 3D structuring. All active battery components—electrodes, solid electrolyte, and current collectors—were deposited by atomic layer deposition (ALD) onto standard CMOS processable silicon wafers microfabricated to form arrays of deep pores with aspect ratios up to approximately 10. The cells utilize an electrochemically prelithiated LiV 2 O 5 cathode, a very thin (40–100 nm) Li 2 PO 2 N solid electrolyte, and a SnNx anode. The fabrication process occurs entirely at or below 250 °C, promising compatibility with a variety of substrates as well as integrated circuits. The multilayer battery structure enabled all-ALD solid-state cells to deliver 37 μAh/cm 2 ·μm (normalized to cathode thickness) with only 0.02% per-cycle capacity loss. Conformal fabrication of full cells over 3D substrates increased the areal discharge capacity by an order of magnitude while simulteneously improving power performance, a trend consistent with a finite element model. Furthermore, this work shows that the exceptional conformality of ALD, combined with conventional semiconductor fabrication methods, provides an avenue for the successful realization of long-sought 3D TSSBs which provide power performance scaling in regimes inaccessible to planar form factor cells.

25 ENERGY STORAGE↗

Extrapolation Domains for Aggregating Environmental Outcomes from Local to Regional Levels

Billions of dollars are invested every year to run field experiments to quantify the response of crops to new technologies and associated environmental outcomes. Given the diversity of environments where crop production occurs, conducting these research studies without a robust framework for research site selection and upscaling results to larger spatial scales is inefficient. In this project, researchers from the University of Nebraska-Lincoln used their unique Technology Extrapolation Domains framework (TED) as a tool to guide the selection of experimental sites and as basis for aggregating and validating environmental outcomes from local to regional levels. In the present project, we first used the TED framework to evaluate the current distribution and area coverage of the current SMARTFARM sites. The purpose was to showcase how it is possible to use the TED framework to guide site selection and extrapolate results over space. Additionally, the original TED framework was expanded to account for other factors influencing environmental outcomes by inclusion of three additional variables: soil organic matter, soil texture, and topographic wetness index. The resulting expanded framework (TED-E) was validated using nitrogen (N) losses from corn in the United States as a case study. To do so, we used N balance as a proxy to N losses and we evaluated the capacity of the framework to explain variation in N balance across fields and across countries. We found that the TED-E has substantially higher predictive power than the original TED framework to explain spatial variation in N balance. However, improvements in predictive power with the TED-E tool come at the expense of a higher number of TEDs needed to achieve a given crop area coverage compared with the original TED framework. We conclude that the new TED-E framework can help aggregate and extrapolate environmental outcomes from research sites to regional levels and improve the visualization of their spatial patterns across the United States. An online version of the framework is available at: https://www.toolted.org/

54 ENVIRONMENTAL SCIENCES↗

Hanford Reach Fall Chinook Salmon Productivity Analysis, Brood Years 1975–2016

Updating the Hanford Reach fall Chinook salmon productivity analysis to include seven additional years of data (BY 2010–2016), including three years of record escapements (>150,000 adults), reaffirmed the highly productive nature of this population and the positive effect of flow fluctuation constraints as implemented at Priest Rapids Dam by the VBSA and HRFCPP. The addition of several years of high escapements also revealed that competition among juveniles (and not spawning habitat limitations) is likely the mechanism driving density dependence in the Hanford Reach. The addition of the high escapement brood years also provided evidence for the high recruitment capacity of the population. As such, the WDFW may consider increasing the maximum escapement goal from 42,000 adults to 49,000 adults, which would be more in-line with SMSY as estimated from this update. Given the in-river protections that are in place as part of the HRFCPP, ocean conditions appear to be the primary factor controlling adult production. Therefore, the success of any additional management actions taken in freshwater are likely to be dependent on survival in the ocean. As such, the most effective management actions may be those that limit juvenile competition and density dependent growth effects in the Hanford Reach. Limiting competition would be expected to increase growth, resulting in larger smolts that would be less likely to suffer size-dependent mortality in the marine environment, even during years of poor ocean conditions. Increasing terminal harvest rates when high escapements are anticipated (from downstream dam counts) is one management option that could help to curtail juvenile competition.

Harnish, Ryan A.↗

Direct Nano‐Synthesis Methods Notably Benefit Mg‐Battery Cathode Performance

Abstract Rechargeable magnesium batteries are promising candidates for next‐generation electrochemical energy storage, but their development is severely hindered by sluggish solid‐state diffusion and significant desolvation penalties of the divalent cation. Studies suggest that nano‐sized electrode materials alleviate these issues by shortening diffusion lengths and increasing electrode/electrolyte interaction. Here, the effect of particle size and synthetic methodology on the electrochemical performance of four sulfide cathode materials in Mg batteries is investigated: layered TiS 2 , CuS, spinel Ti 2 S 4 , and CuCo 2 S 4 . In these sulfide hosts, the direct preparation of nano‐dimensional crystallites is critical to activate or improve electrochemistry. Even promising cathode materials can appear electrochemically inert when micron‐sized particles are investigated (e.g., CuCo 2 S 4 ), and mechanical milling leads to surface degradation of active material which severely limits performance. However, nano‐sized CuCo 2 S 4 prepared directly reaches a capacity nearly double that of ball‐milled material and delivers 350 mAh g −1 at 60 °C. This work provides synthetic considerations which may be crucial in the discovery and design of novel Mg cathode materials, so that promising candidates are not overlooked. By extension, in oxide materials where Mg 2+ diffusion is expected to be much more sluggish, this factor is anticipated to be even more important when screening for new hosts.

Blanc, Lauren E.↗

Development of manganese-rich cathodes as alternatives to nickel-rich chemistries

High-energy, inexpensive and safe electrochemistries have been the main goals of lithium-ion battery research for many years. Historically, manganese-based cathodes have long been studied for their attractive cost and safety characteristics [1]. However, due to issues related to both surface and bulk instabilities, manganese-rich electrodes have yet to find substantial success in the high-energy lithium-ion battery market. With current trends in cathode chemistries leaning heavily toward Ni-rich compositions, the factors of cost and safety are again at the forefront of research and development efforts. This paper reports the recent progress made at Argonne National Laboratory (USA) to stabilize manganese-rich cathode structures and surfaces with a specific focus on composite materials with intergrown layered and spinel components; it presents an overview of their electrochemical properties in terms of capacity, energy, and cycle-life in cells with metallic lithium, graphite, and Li 4 Ti 5 O 12 anodes. These layered-spinel cathodes show promise as alternatives to highly nickel-rich electrode compositions, which bodes well for continued advances.

25 ENERGY STORAGE↗

Lloviu virus VP24 and VP35 proteins function as innate immune antagonists in human and bat cells

Lloviu virus (LLOV) is a new member of the filovirus family that also includes Ebola virus (EBOV) and Marburg virus (MARV). LLOV has not been cultured; however, its genomic RNA sequence indicates the coding capacity to produce homologs of the EBOV and MARV VP24, VP35, and VP40 proteins. EBOV and MARV VP35 proteins inhibit interferon (IFN)-alpha/beta production and EBOV VP35 blocks activation of the antiviral kinase PKR. The EBOV VP24 and MARV VP40 proteins inhibit IFN signaling, albeit by different mechanisms. Here we demonstrate that LLOV VP35 suppresses Sendai virus induced IFN regulatory factor 3 (IRF3) phosphorylation, IFN-α/β production, and PKR phosphorylation. Additionally, LLOV VP24 blocks tyrosine phosphorylated STAT1 binding to karyopherin alpha 5 (KPNA5), STAT1 nuclear accumulation, and IFN-induced gene expression. LLOV VP40 lacks detectable IFN antagonist function. These activities parallel EBOV IFN inhibitory functions. EBOV and LLOV VP35 and VP24 proteins also inhibit IFN responses in bat cells. These data suggest that LLOV infection will block innate immune responses in a manner similar to EBOV. - Highlights: • Lloviu virus (LLOV) is a new member of the filovirus family. • LLOV VP35 blocks IRF3 phosphorylation, IFN-α/β production and PKR phosphorylation. • LLOV VP24 inhibits IFN responses by targeting phospho-STAT1 KPNA interaction. • Infection by LLOV may block innate immune responses in a manner similar to EBOV.

60 APPLIED LIFE SCIENCES↗

Capacitated arc routing problem and its extensions in waste collection

Capacitated arc routing problem (CARP) is the youngest generation of graph theory that focuses on solving the edge/arc routing for optimality. Since many years, operational research devoted to CARP counterpart, known as vehicle routing problem (VRP), which does not fit to several real cases such like waste collection problem and road maintenance. In this paper, we highlighted several extensions of capacitated arc routing problem (CARP) that represents the real-life problem of vehicle operation in waste collection. By purpose, CARP is designed to find a set of routes for vehicles that satisfies all pre-setting constraints in such that all vehicles must start and end at a depot, service a set of demands on edges (or arcs) exactly once without exceeding the capacity, thus the total fleet cost is minimized. We also addressed the differentiation between CARP and VRP in waste collection. Several issues have been discussed including stochastic demands and time window problems in order to show the complexity and importance of CARP in the related industry. A mathematical model of CARP and its new version is presented by considering several factors such like delivery cost, lateness penalty and delivery time.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Economic Analysis and Optimal Sizing for behind-the-meter Battery Storage

This paper proposes methods to estimate the potential benefits and determine the optimal energy and power capacity for behind-the-meter BSS. In the proposed method, a linear programming is first formulated only using typical load profiles, energy/demand charge rates, and a set of battery parameters to determine the maximum saving in electric energy cost. The optimization formulation is then adapted to include battery cost as a function of its power and energy capacity in order to capture the trade-off between benefits and cost, and therefore to determine the most economic battery size. Using the proposed methods, economic analysis and optimal sizing have been performed for a few commercial buildings and utility rate structures that are representative of those found in the various regions of the Continental United States. The key factors that affect the economic benefits and optimal size have been identified. The proposed methods and case study results cannot only help commercial and industrial customers or battery vendors to evaluate and size the storage system for behind-the-meter application, but can also assist utilities and policy makers to design electricity rate or subsidies to promote the development of energy storage.

Wu, Di↗

Structural and Electrochemical Characterization of Thin Film Li 2 MoO 3 Electrodes

We report that Li 2 MoO 3 is a promising structural stabilizing unit for use in composite layered-layered cathodes for Li-ion batteries. To enable the rational design of such cathodes, studies on fundamental phenomena related to the active material structure and electrode/electrolyte interface are needed. The present work details the fabrication and characterization of thin film Li 2 MoO 3 cathodes and shows that their electrochemical performance greatly depends on the nature of the cathode/electrolyte interface. The Li 2 MoO 3 thin films exhibit poor cyclability in a liquid carbonate electrolyte (e.g., initial capacity of 166 mAh/g with 40% capacity fade over 20 cycles) whereas all-solid-state Li 2 MoO 3 /Lipon/Li batteries show negligible fade during cycling. A suite of characterization methods including Raman spectroscopy and X-ray photoelectron spectroscopy are used to study the evolution of the cathode structure and cathode electrolyte interphase (CEI) layer during charge/discharge cycling. Li transport rates are another important factor which affect cathode performance. AC impedance spectroscopy studies reveal that the Li diffusion coefficient (D Li ) in Li 2 MoO 3 decreases from 4.36 × 10 -11 cm 2 /s in the fully discharged state to 4.51 × 10 -13 cm 2 /s when charged to 3.6 V vs. Li/Li + . In conclusion, the results presented herein provide insight on the fundamental phenomena which govern Li 2 MoO 3 cathode performance.

25 ENERGY STORAGE↗

Patterns of longer-term climate change effects on CO 2 efflux from biocrusted soils differ from those observed in the short term

Biological soil crusts (biocrusts) are predicted to be sensitive to the increased temperature and altered precipitation associated with climate change. We assessed the effects of these factors on soil carbon dioxide (CO 2 ) balance in biocrusted soils using a sequence of manipulations over a 9-year period. We warmed biocrusted soils by 2 and, later, by 4 °C to better capture updated forecasts of future temperature at a site on the Colorado Plateau, USA. We also watered soils to alter monsoon-season precipitation amount and frequency and had plots that received both warming and altered precipitation treatments. Within treatment plots, we used 20 automated flux chambers to monitor net soil exchange (NSE) of CO 2 hourly, first in 2006–2007 and then again in 2013–2014, for a total of 39 months. Net CO 2 efflux from biocrusted soils in the warming treatment increased a year after the experiment began (2006–2007). However, after 9 years and even greater warming (4 °C), results were more mixed, with a reversal of the increase in 2013 (i.e., controls showed higher net CO 2 efflux than treatment plots) and with similarly high rates in all treatments during 2014, a wet year. Over the longer term, we saw evidence of reduced photosynthetic capacity of the biocrusts in response to both the temperature and altered precipitation treatments. Patterns in biocrusted soil CO 2 exchange under experimentally altered climate suggest that (1) warming stimulation of CO 2 efflux was diminished later in the experiment, even in the face of greater warming; and (2) treatment effects on CO 2 flux patterns were likely driven by changes in biocrust species composition and by changes in root respiration due to vascular plant responses.

54 ENVIRONMENTAL SCIENCES↗

EV Charging Infrastructure Energization An Overview of Approaches for Simplifying and Accelerating Timelines to Processing EV Charging Load Service Requests

The United States has seen significant growth in electric vehicle (EV) adoption, leading to increased demand for EV charging infrastructure. Over the past decade, EV charging infrastructure site developers, site hosts, and electric distribution utilities have navigated the process to integrate chargers onto the electric grid. Site developers and site hosts have raised the alarm that the integration process for high-powered EV charging projects does not meet the needs of the EV market for timeliness or cost. High-powered charging stations typically require a load service request or an agreement with the local utility to connect to the grid. The process of energizing a new high-powered charging site can be complex and time-consuming, often taking up to 2 years. This timeline is the result of current utility energization processes having been designed for construction projects that take longer to build (i.e., buildings). The specific challenges stem from various factors, including compartmentalization in application processes, the integration of EV charging process approvals with other distributed energy resources (DERs), and the need to ensure grid reliability. The energization process needs to evolve to meet the growing demand for high-powered EV charging. This white paper compiles information gathered through various conversations with key stakeholders, including utilities, utility regulators, EV charging operators, site developers, and authorities having jurisdiction (AHJ) as well as through an extensive literature review. This document identifies the challenges and provides potential solutions to streamline the process of connecting EV charging infrastructure to the power grid in the United States, serving as a starting point for future conversations around these solutions. The solutions noted in this white paper require collaborative efforts among utilities, regulators, and EV charging infrastructure developers to streamline the grid connection process for EV charging infrastructure. They are broadly organized into four areas: 1. Increase data access and transparency: Develop automated load service request tools, integrate hosting capacity and load service request analyses, incorporate EV adoption forecasts, and provide transparency on the processing queue. 2. Improve energization processes and timing: Create fast-track options based on prescreening criteria, provide flexibility or phased approvals in the load service request/interconnection process, build internal knowledge within utilities about EV charging technologies, and provide standardized workforce training. 3. Promote economic efficiency: Right size distribution components to accurately reflect the load requirements of EV charging infrastructure, make proactive investments in grid infrastructure based on EV adoption forecasts and growth projections, and consider energy equity and environmental justice factors such as equitable access to EV charging when planning infrastructure. 4. Improve grid reliability and resilience: Use load management/power control systems (PCS) at EV charging stations, adopt and implement harmonized standards for communication protocols and information models between the EV charging and grid control infrastructure, and address cybersecurity considerations by implementing robust security measures and standards for EV charging infrastructure—with particular emphasis on clarifying the security requirements for the interface to the grid. The objective of the solutions proposed in this white paper is to accelerate the timeline and decrease costs associated with connecting EV charging infrastructure to the grid. Electric utilities, utility regulators, EV charging infrastructure developers, and site hosts will first need to understand which solutions are available in their service territory, and if warranted, which combination of solutions would support their specific needs. Through the successful implementations of solutions at scale detailed here, industry will demonstrate a new and innovative ecosystem where timely deployment and energization of EV charging infrastructure with greater grid resiliency and reliability is a reality.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Substance P enhances proliferation and paracrine potential of adipose-derived stem cells in vitro

Stem cells have tremendous promise to treat intractable diseases. Notably, adipose-derived stem cells (ADSCs) are actively being investigated because of ease of sampling and high repopulation capacity in vitro. ADSCs can exert a therapeutic effect through differentiation and paracrine potential, and these actions have been proven in many diseases, including cutaneous and inflammatory diseases. Transplantation of ADSCs necessitates therapeutic quantities and thus, long term ex vivo culture of ADSCs. However, this procedure can impair the activity of ADSCs and provoke cellular senescence, leading to low efficacy in vivo. Accordingly, strategies to restore cellular activity and inhibit senescence of stem cells during ex vivo culture are needed for stem cell-based therapies. This study evaluated a potential supplementary role of Substance P (SP) in ADSC ex vivo culture. After confirming that the ADSC cell cycle was damaged by passage 6 (p6), ADSCs at p6 were cultured with SP, and their proliferation rates, cumulative cell numbers, cytokine profiles, and impact on T/endothelial cells were assessed. Long-term culture weakened proliferation ability and secretion of the cytokines, transforming growth factor-beta 1 (TGF-beta1), vascular endothelial growth factor (VEGF), and stromal cell derived factor-1 alpha (SDF-1alpha) in ADSCs. However, SP treatment reduced the population doubling time (PDT), enabling gain of a sufficient number of ADSCs at early passages. In addition, SP restored cytokine secretion, enhancing the ADSC-mediated paracrine effect on T cell and human umbilical vein endothelial cells (HUVECs). Taken together, these results suggest that SP can retain the therapeutic effect of ADSCs by elevating their proliferative and paracrine potential in ex vivo culture. - Highlights: • Long-term culture of ADSCs leads to cell senescence. • Paracrine potential of ADSC decreases as passage number increases. • SP enhances the weakened proliferation capacity of ADSCs. • SP stimulates cytokine secretion from ADSC with impaired paracrine potential.

60 APPLIED LIFE SCIENCES↗

Kaolinite-catalyzed air oxidation of hydrazine: Consideration of several compositional, structural and energetic factors in surface activation

Clay minerals have been shown to have numerous, curious, energetic properties by virtue of ultra-violet light release which can be triggered by gentle environmental changes such as wetting and dewetting by a variety of liquids, unique among them water and hydrazine. Since both water and hydrazine play multiple key roles in the air-oxidation of hydrazine on kaolinite surfaces, this reaction would seem to have prime potential for studying interrelationships of energy storage, release and chemical reactivity of clay surfaces, capacities basic to either the Bernal or Cairns-Smith roles of minerals in the origin of life. Establishment of the capacity for stored electronic energy to significantly alter surface chemistry is important, regardless of the reaction chosen to demonstrate it. Hydrazine air oxidation is overawingly complex, given the possibilities for step-wise control and monitoring of parameters. In the light of recently extended characterization of the kaolinite and model sheet catalysts we used to study hydrazine oxidation and gamma-irradiated silica, previous studies of hydrazine air-oxidation on aluminosilicate surfaces have been reevaluated. Our former conclusion remains intact that, whereas trace structural and surface contaminants do play some role in the catalysis of oxidation, they are not the only, nor even the dominant, catalytic centers. Initial intermediates in the oxidation can now be proposed which are consistent with production via O(-)-centers as well as ferric iron centers. The greater than square dependence of the initial reaction rate on the weight of the clay is discussed in the light of these various mechanistic possibilities.

Coyne, L. M.↗