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At least 685 records · Page 38

Amphiphilic Co-Solvents Modulate the Structure of Membrane Domains

Biofuels are an increasing part of the sustainable energy picture. This makes it a societal and economic imperative to optimize biofuel production. Mitigating the toxic effects of amphiphilic co-solvents is one way to improve the efficiency of biofuel production. Amphiphiles partition into cellular membranes, leading to membrane thinning, destabilization, loss of membrane potential, and, ultimately, cell death. However, this picture of solvent toxicity misses the disruptive impact of co-solvents on lateral membrane organization, which is increasingly recognized as critical for membrane protein sorting and oligomerization. The alteration or disruption of membrane domains has deleterious effects on cellular processes. Here, in this work, we pursue the hypothesis that membrane lateral organization is disrupted by the presence of co-solvents at concentrations lower than those which lead to full membrane destabilization. The disruption occurs due to an increasing interfacial tension between the co-existing phases, resulting in conformational changes to minimize the interfacial length-to-area ratio. This represents an unrecognized mode of solvent-induced stress and a new target for interventions to improve fermentation yields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Permafrost and Subsurface Ice in the Solar System

The properties and behavior of planetary permafrost are discussed with reference to the ability of such surfaces to sustain loads characteristics of spacecraft landing and planetary bases. In most occurrences, water ice is in close proximity to, or in contact with, finely divided silicate mineral matter. When ice contacts silicate mineral surfaces, a liquid-like, transition zone is created. Its thickness ranges from several hundred Angstron units at temperatures near 0 degrees C to about three Angstrom units at -150 degrees C. When soluble substances are present, the resulting brine enlarges the interfacial zone. When clays are involved, although the interfacial zone may be small, its extent is large. The unfrozen, interfacial water may amount to 100% or more weight at a temperature of -5 degrees C. The presence of this interfacial unfrozen water acts to confer plasticity to permafrost, enabling it to exhibit creep at all imposed levels of stress. Nucleation processes and load-bearing capacity are examined.

Anderson, D. M.↗

Optimizing Deep Geothermal Drilling for Energy Sustainability in the Appalachian Basin

This study investigates the geological and geomechanical characteristics of the MIP 1S geothermal well in the Appalachian Basin to optimize drilling and address the wellbore stability issues encountered. Data from well logs, sidewall core analysis, and injection tests were used to derive elastic and rock strength properties, as well as stress and pore pressure profiles. A robust 1D-geomechanical model was developed and validated, correlating strongly with wellbore instability observations. This revealed significant wellbore breakout, widening the diameter from 12 ¼ inches to over 16 inches. Advanced technologies like Cerebro Force™ In-Bit Sensing were used to monitor drilling performance with high accuracy. This technology tracks critical metrics such as bit acceleration, vibration in the x, y, and z directions, Gyro RPM, stick-slip indicators, and bending on the bit. Cerebro Force™ readings identified hole drag caused by poor hole conditions, including friction between the drill string and wellbore walls and the presence of cuttings or debris. This led to higher torque and weight on bit (WOB) readings at the surface compared to downhole measurements, affecting drilling efficiency and wellbore stability. Optimal drilling parameters for future deep geothermal wells were determined based on these findings.

Environmental Sciences & Ecology↗

Supramolecular dynamic binary complexes with pH and salt-responsive properties for use in unconventional reservoirs

Hydraulic fracturing of unconventional reservoirs has seen a boom in the last century, as a means to fulfill the growing energy demand in the world. The fracturing fluid used in the process plays a substantial role in determining the results. Hence, several research and development efforts have been geared towards developing more sustainable, efficient, and improved fracturing fluids. Herein, we present a dynamic binary complex (DBC) solution, with potential to be useful in the hydraulic fracturing domain. It has a supramolecular structure formed by the self-assembly of low molecular weight viscosifiers (LMWVs) oleic acid and diethylenetriamine into an elongated entangled network under alkaline conditions. With less than 2 wt% constituents dispersed in aqueous solution, a viscous gel that exhibits high viscosities even under shear was formed. Key features include responsiveness to pH and salinity, and a zero-shear viscosity that could be tuned by a factor of ~280 by changing the pH. Furthermore, its viscous properties were more pronounced in the presence of salt. Sand settling tests revealed its potential to hold up sand particles for extended periods of time. In conclusion, this DBC solution system has potential to be utilized as a smart salt-responsive, pH-switchable hydraulic fracturing fluid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Convergent Manufacturing of Large-Scale Components for Nuclear Applications, via Additive Manufacturing and Powder Metallurgy Hot Isostatic Pressing

Powder metallurgy (PM)–hot isostatic pressing (PM-HIP) has long been recognized as a powerful route for producing fully dense, near net shape metallic components. By consolidating powders under high temperature and pressure, HIP provides isotropic properties, uniform microstructures, and scalability to complex geometries that are vital for sectors such as aerospace, energy, and nuclear power. Yet despite these advantages, the technology has remained constrained by costly trial and error canister fabrication, limitations of conventional forging, and incomplete knowledge about how the canister design influences final part properties. Additive manufacturing (AM), by contrast, thrives on design freedom and geometric flexibility but struggles with speed, scalability, and cost when applied to very large structures. The research presented in this report investigated how a convergent manufacturing approach, combining AM with PM-HIP, can merge the strengths of both technologies, leveraging AM’s flexibility for canister design and HIP’s consolidation capability to deliver reliable, large, and complex parts. The work progressed through three case studies that built on one another in scale and complexity. Small cylindrical canisters fabricated by conventional methods, laser powder bed fusion, and directed energy deposition were filled with stainless steel powders and subjected to HIP. The resulting parts demonstrated near-full density and mechanical properties on par with wrought stainless steel, showing for the first time that AM canisters can be a direct substitute for conventional ones without sacrificing quality. The next step involved a medium-scale, noncentrosymmetric T-valve, which is an enclosed, multibranch geometry that tested the limits of AM + PM-HIP integration. The T-valve achieved predictable shrinkage and uniform densification, confirming feasibility for enclosed designs. However, this study also revealed oxide inclusions and interfacial challenges at the AM + HIP boundary, underscoring the critical importance of controlling interface chemistry and employing robust, in situ strategies, such as melt pool monitoring and thermal monitoring, coupled with nondestructive evaluation techniques such as x-ray computed tomography. Finally, the effort culminated in fabricating a large-scale impeller weighing nearly 2000 lb and spanning 5 ft in diameter. Produced via multirobot wire arc AM and hot isostatic pressed to near-full density, the impeller validated industrial-scale feasibility. Predictive models closely matched experimental shrinkage, tensile properties were spatially uniform across the component, and the AM + PM-HIP interface proved mechanically sound despite the presence of oxide-decorated prior particle boundaries. This large-scale demonstration is a major milestone, showing that hybrid AM + PM‑HIP can reliably deliver components at reactor-relevant scales. Collectively, these studies charted a logical pathway: small-scale work built scientific confidence, medium-scale work highlighted opportunities and challenges, and large-scale work proved industrial impact. The overarching conclusion of this report is that AM + PM-HIP should not be seen as a replacement for forging but as a complementary pathway that provides the US with flexibility, resilience, and new options for manufacturing nuclear-grade components. Looking ahead, several directions emerge as critical to sustaining progress. Predictive modeling must become faster, more accessible, and more accurate, with digital twins and machine learning reducing reliance on trial and error. Powders and alloys must be optimized for HIP, with improved cleanliness, reduced oxides, and tailored chemistries that enhance creep, fatigue, and irradiation resistance. Interfaces between AM and HIP regions must be better engineered through coatings, machining strategies, and surface treatments to mitigate oxide formation and ensure reliable bonding to explore opportunities for HIP of targeted compositional parts, as well as multimaterial HIP cladding applications. Monitoring and nondestructive evaluation need to expand, incorporating multimodal sensors, x-ray computed tomography, and real-time data integration through platforms such as Pelican. At the same time, the pathway to industrial adoption requires techno-economic analysis, machinability studies, and qualification frameworks aligned with industry and regulatory standards. Finally, workforce and academic engagement must be strengthened. Programs that train technicians and engineers for US Navy and US Department of Energy manufacturing challenges should be paired with academic partnerships to support fundamental research, with open sharing of non-export-controlled data to accelerate innovation and build the next generation of experts. In conclusion, this report demonstrates that hybrid AM + PM-HIP is scientifically viable and strategically important. By combining the design agility of AM with the consolidation strength of HIP and embedding modeling, monitoring, and workforce development, this approach provided a transformative new capability for US manufacturing. The path forward is clear: hybrid AM + PM-HIP is not just a promising research direction but is also potentially an industrially relevant pathway that can reshape how nuclear-grade components are designed, qualified, and deployed.

36 MATERIALS SCIENCE↗

Safer Foundation Solar Demands Skill Collaborative

The milestones and accomplishments achieved in Safer’s Solar Demands Skill Training program required a collective effort of stakeholders. The ability to achieve the desired results and impact lives of the population we serve works best when collaborating with community stakeholders such as community-based organizations, faith-based organizations, community activists, local law enforcement, community residents, employers, and elected and appointed officials. We are working harder than ever to place clients in-demand careers and high-growth industry sectors. Our employer engagement with high growth sectors continues to increase, we have been able to deepen our relationships in this space by providing in demand stackable credential training. Launched our initiative in the green job space by partnering with organizations like ComEd, the Department of Energy, community-based organizations, faith-based organizations, and manufacturers that helped to train clients in the green jobs and renewable energy space. By the end of the year, we will have completed our tenth cohort of photovoltaic solar installation training. The training has been used as a foundation for solar panel installers to acquire new skills in in the green jobs career pathways, such as sales and customer service. It has also served as a pipeline to union-level trade positions through the skills participants obtained through partnership engagement. Safer Foundation's policy and advocacy team plays a major role in expanding opportunities for people with records to over one hundred occupations, including the trades. This reform has allowed many to secure living wage employment, reducing the high recidivism rate within Illinois. Safer continues to build our social enterprise with Reconstructive Technology Partners (RTP). RTP is introducing people with records to the construction trades such as solar, carpentry and electrical through residential remodeling of homes on smaller construction projects. Understanding the need to have a greater community presence, outreach was extended to a boots on the ground model, including, but not limited to door-to-door engagement, DE-EE0008571 Safer Foundation Page 4 of 29 local radio broadcasting and print ads in local newspapers. We continue to seek innovative ways to increase Safer Foundations' presence in the renewable energy space. Outreach efforts gave us an opportunity to share critical reentry information and opportunities about our PV installer program. Giving us reach with local and national audiences alike. We launched a systematic approach to improving client data and client tracking through an evidence-based practices initiative. That implemented an agency wide cross-functional data management system. The system supported our goal of reviewing, evaluating, and making recommendations to improve operational processes, program delivery, information sharing, and more. Played a significant part in the success of the solar program. Finally, economists around the nation agree that there is a significant labor shortage. The shortage directly threatens our ability to sustain our economic growth; if employers do not have access to the workers they need, it can lead to a shutdown in the economic recovery. The demand for Safer Foundation services is more important and impactful than ever. We will continue to build upon our 50 years of experience to address the challenges ahead and serve more people in a better way. We are confident we will accomplish beautiful things that benefit everyone involved because together, we are powerful.

14 SOLAR ENERGY↗

Does NASA's Constellation Architecture Offer Opportunities to Achieve Multiple Additional Goals in Space?

Every major NASA human spaceflight program in the last four decades has been modified to achieve goals in space not incorporated within the original design goals: the Apollo Applications Program, Skylab, Space Shuttle, and International Space Station. Several groups in the US have been identifying major future science goals, the science facilities necessary to investigate them, as well as possible roles for augmented versions of elements of NASA's Constellation program. Specifically, teams in the astronomy community have been developing concepts for very capable missions to follow the James Webb Space Telescope that could take advantage of - or require - free-space operations by astronauts and/or robots. Taking as one example, the Single-Aperture Far-InfraRed (SAFIR) telescope with a approx.10+ m aperture proposed for operation in the 2020 timeframe. According to current NASA plans, the Ares V launch vehicle (or a variant) will be available about the same time, as will the capability to transport astronauts to the vicinity of the Moon via the Orion Crew Exploration Vehicle and associated systems. [As the lunar surface offers no advantages - and major disadvantages - for most major optical systems, the expensive system for landing and operating on the lunar surface is not required.] Although as currently conceived, SAFIR and other astronomical missions will operate at the Sun-Earth L2 location, it appears trivial to travel for servicing to the more accessible Earth-Moon L1,2 locations. Moreover, as the recent Orbital Express and Automated Transfer Vehicle missions have demonstrated, future robotic capabilities should offer capabilities that would (remotely) extend human presence far beyond the vicinity of the Earth. In addition to multiplying the value of NASA's architecture for future human spaceflight to achieve the goals multiple major stakeholders, if humans one day travel beyond the Earth-Moon system - say, to Mars - technologies and capabilities for operating for long periods in free space must be developed. The engineering. management, and operational successes of the Space Station have demonstrated that international collaboration is possible. However, there is a danger that the hard-won lessons of current programs will be lost without continuing development of in-space operations. A program to achieve. for example, major astronomical goals in space using astronauts and robots will sustain international capabilities, produce highly visible achievements, and appeal to an additional broad community of stakeholders not currently involved with missions to the lunar surface.

Thronson, Harley A.↗

Covalent Organic Framework (COF) Derived Ni–N–C Catalysts for Electrochemical CO 2 Reduction: Unraveling Fundamental Kinetic and Structural Parameters of the Active Sites

Electrochemical CO 2 reduction is a potential approach to convert CO 2 into valuable chemicals using electricity as feedstock. Abundant and affordable catalyst materials are needed to upscale this process in a sustainable manner. Nickel-nitrogen-doped carbon (Ni-N-C) is an efficient catalyst for CO 2 reduction to CO, and the single-site Ni-N x motif is believed to be the active site. However, critical metrics for its catalytic activity, such as active site density and intrinsic turnover frequency, so far lack systematic discussion. In this work, we prepared a set of covalent organic framework (COF)-derived Ni-N-C catalysts, for which the Ni-N x content could be adjusted by the pyrolysis temperature. The combination of high-angle annular dark-field scanning transmission electron microscopy and extended X-ray absorption fine structure evidenced the presence of Ni single-sites, and quantitative X-ray photoemission addressed the relation between active site density and turnover frequency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning of lattice oxygen reactivity and scaling relation to construct better oxygen evolution electrocatalyst

Developing efficient and low-cost electrocatalysts for oxygen evolution reaction is crucial in realizing practical energy systems for sustainable fuel production and energy storage from renewable energy sources. However, the inherent linear scaling relation for most catalytic materials imposes a theoretical overpotential ceiling, limiting the development of efficient electrocatalysts. Herein, using modeled Na x Mn 3 O 7 materials, we report an effective strategy to construct better oxygen evolution electrocatalyst through tuning both lattice oxygen reactivity and scaling relation via alkali metal ion mediation. Specifically, the number of Na + is linked with lattice oxygen reactivity, which is determined by the number of oxygen hole in oxygen lone-pair states formed by native Mn vacancies, governing the barrier symmetry between O–H bond cleavage and O–O bond formation. On the other hand, the presence of Na + could have specific noncovalent interaction with pendant oxygen in *OOH to overcome the limitation from linear scaling relation, reducing the overpotential ceiling. Combining in situ spectroscopy-based characterization with first-principles calculations, we demonstrate that an intermediate level of Na + mediation (NaMn 3 O 7 ) exhibits the optimum oxygen evolution activity. This work provides a new rational recipe to develop highly efficient catalyst towards water oxidation or other oxidative reactions through tuning lattice oxygen reactivity and scaling relation.

36 MATERIALS SCIENCE↗

First Principles Study of Aluminum Doped Polycrystalline Silicon as a Potential Anode Candidate in Li‐ion Batteries

Addressing sustainable energy storage remains crucial for transitioning to renewable sources. While Li‐ion batteries have made significant contributions, enhancing their capacity through alternative materials remains a key challenge. Micro‐sized silicon is a promising anode material due to its tenfold higher theoretical capacity compared to conventional graphite. However, its substantial volumetric expansion during cycling impedes practical application due to mechanical failure and rapid capacity fading. A novel approach is proposed to mitigate this issue by incorporating trace amounts of aluminum into the micro‐sized silicon electrode using ball milling. Density functional theory (DFT) is employed to establish a theoretical framework elucidating how grain boundary sliding, a key mechanism involved in preventing mechanical failure is facilitated by the presence of trace aluminum at grain boundaries. This, in turn, reduces stress accumulation within the material, reducing the likelihood of failure. To validate the theoretical predictions, capacity retention experiments are conducted on undoped and Al‐doped micro‐sized silicon samples. In conclusion, the results demonstrate significantly reduced capacity fading in the doped sample, corroborating the theoretical framework and showcasing the potential of aluminum doping for improved Li‐ion battery performance.

25 ENERGY STORAGE↗

Catalytic deconstruction of organic additive-containing plastics

Plastics waste ends up in landfills, oceans, and incinerators, posing major environmental and human health threats. Catalytic deconstruction is emerging as a key technological solution to handle complex plastics and has successfully converted virgin polymers into various products. Here, we investigate the resilience of chemical deconstruction technologies to organic additives, which are ubiquitous in plastics. We study catalyst-additive interactions experimentally and via first-principles calculations for plastics additives representative of entire classes. We reveal two deactivation mechanisms and demonstrate that many recently developed catalysts are inadequate for polyolefin conversion due to poisoning caused by the strong adsorption of most additives or their small fragments. Furthermore, we also identify conditions and catalysts that can circumvent the challenge of deconstruction in the presence of additives challenge.

10 SYNTHETIC FUELS↗

High-Temperature Oxidation-Resistant and Low Coefficient of Thermal Expansion NiAl-Base Bond Coat Developed for a Turbine Blade Application

Many critical gas turbine engine components are currently made from Ni-base superalloys that are coated with a thermal barrier coating (TBC). The TBC consists of a ZrO2-based top coat and a bond coat that is used to enhance the bonding between the superalloy substrate and the top coat. MCrAlY alloys (CoCrAlY and NiCrAlY) are currently used as bond coats and are chosen for their very good oxidation resistance. TBC life is frequently limited by the oxidation resistance of the bond coat, along with a thermal expansion mismatch between the metallic bond coat and the ceramic top coat. The aim of this investigation at the NASA Glenn Research Center was to develop a new longer life, higher temperature bond coat by improving both the oxidation resistance and the thermal expansion characteristics of the bond coat. Nickel aluminide (NiAl) has excellent high-temperature oxidation resistance and can sustain a protective Al2O3 scale to longer times and higher temperatures in comparison to MCrAlY alloys. Cryomilling of NiAl results in aluminum nitride (AlN) formation that reduces the coefficient of thermal expansion (CTE) of the alloy and enhances creep strength. Thus, additions of cryomilled NiAl-AlN to CoCrAlY were examined as a potential bond coat. In this work, the composite alloy was investigated as a stand-alone substrate to demonstrate its feasibility prior to actual use as a coating. About 85 percent of prealloyed NiAl and 15 percent of standard commercial CoCrAlY alloys were mixed and cryomilled in an attritor with stainless steel balls used as grinding media. The milling was carried out in the presence of liquid nitrogen. The milled powder was consolidated by hot extrusion or by hot isostatic pressing. From the consolidated material, oxidation coupons, four-point bend, CTE, and tensile specimens were machined. The CTE measurements were made between room temperature and 1000 C in an argon atmosphere. It is shown that the CTE of the NiAl-AlN-CoCrAlY composite bond coat is lower than that of the commercially used coating alloy 16-6. To examine the potential of NiAl-AlN-CoCrAlY as a bond coat, we subjected two samples to cyclic furnace testing. The furnace cycle consisted of 45 min at 1163 C (2125 F ) followed by 15 min of cooling out of the furnace. The current NASA baseline TBC is a NiCrAlY bond coat below the 7YSZ top coat. The average TBC life for this baseline coating on Ren N5 is 188 plus or minus 19 cycles. NiAl-AlN-CoCrAlY specimens coated with the same 7YSZ top coat were still intact even after 1000 cycles. Therefore, the NiAl-AlN-CoCrAlY as a bulk substrate material, exhibits more than 5 times the life of the current state-of-the-art material. The next step is to evaluate this material as a coating on the same superalloy substrate.

Source record↗

Does NASA's Constellation Architecture Offer Opportunities to Achieve Multiple Additional Goals in Space?

Every major NASA human spaceflight program in the last four decades has been modified to achieve goals in space not incorporated within the original design goals: the Apollo Applications Program, Skylab, Space Shuttle, and International Space Station. Several groups in the US have been identifying major future science goals, the science facilities necessary to investigate them, as well as possible roles for augmented versions of elements of NASA's Constellation program. Specifically, teams in the astronomy community have been developing concepts for very capable missions to follow the James Webb Space Telescope that could take advantage of - or require - free-space operations by astronauts and/or robots. Taking as one example, the Single-Aperture Far-InfraRed (SAFIR) telescope with a approx. 10+ m aperture proposed for operation in the 2020 timeframe. According to current NASA plans, the Ares V launch vehicle (or a variant) will be available about the same time, as will the capability to transport astronauts to the vicinity of the Moon via the Orion Crew Exploration Vehicle and associated systems. [As the lunar surface offers no advantages - and major disadvantages - for most major optical systems, the expensive system for landing and operating on the lunar surface is not required.] Although as currently conceived, SAFIR and other astronomical missions will operate at the Sun-Earth L2 location, it appears trivial to travel for servicing to the more accessible Earth-Moon L1,2 locations. Moreover. as the recent Orbital Express and Automated Transfer Vehicle missions have demonstrated, future robotic capabilities should offer capabilities that would (remotely) extend human presence far beyond the vicinity of the Earth. In addition to multiplying the value of NASA's architecture for future human spaceflight to achieve the goals multiple major stakeholders. if humans one day travel beyond the Earth-Moon system - say, to Mars - technologies and capabilities for operating for long periods in free space must be developed. The engineering, management. and operational successes of the Space Station have demonstrated that international collaboratio~i is possible. However, there is a danger that the hard-won lessons of cLul+sent programs will be lost without continuing development of in-space operations. A program to achieve. for example. major astronomical goals in space using astronauts and robots will sustain international capabilities. produce highly visible achievements. and appeal to a11 additional broad community of stakeholders not currently involved with missions to the lunar surface.

Thronson, Harley↗

Airborne Radar Observations of Hurricane Georges during Landfall over the Dominican Republic

On 22 September 1998 hurricane Georges made landfall on the Dominican Republic (DR). Georges cost the DR at least 500 lives, made more than 155,000 people homeless and caused extensive damage to the country's main industries, tourism and agriculture. There was considerable wind damage, with wind gusts up to 58 m/s in Santa Domingo on the south coast, but most of the damage and deaths resulted from mudslides and the flooding of rivers. While this may have been the worst natural disaster to strike the DR, the sustained rapid storm movement saved the island from worse damage. Georges had previously affected several islands in the Lesser Antilles and Puerto Rico, but it had retained much of its circulation strength. Forty raingauge stations across the DR measured rainfall totals from Georges between 0.7 and 41 cm, the latter at the capital Santo Domingo, located on the south coast. At Herrera the maximum 1 h rainfall rate was 72 mm/h. It is suspected that much higher rain rates occurred in DR's mountainous interior. Before landfall the eye was clearly evident in satellite imagery. When the eye moved over southeastern DR, it filled rapidly, and the cloud top height decreased in all storm sectors except in the southern inflow sector, where a long-lived MCS, with a diameter larger than that of the eyewall, slowly became enwrapped in the hurricane circulation. The eye closure was most rapid between 16-18 UTC, when the eyewall circulation felt the mountainous terrain of the Cordillera Central, which rises up to 3,093 m. The estimated central pressure increased from 962 hPa at 15 UTC to 986 hPa at 03Z on 23 Sept, and the maximum sustained surface wind speed decreased from 54 to 36 in s-1 during the same period. The island of Hispaniola has a cross-track width of about 250 km, much wider than the diameter of the eyewall anvil (about 100 km before landfall). So the event can truly be considered to be a landfalling case, even though Georges recovered after crossing Hispaniola, albeit never to the same strength. This talk will summarize satellite and ground observations of Georges, as it passed the DR, and it will focus on EDOP data. In particular, we will try to estimate the rainfall rate over the mountainous terrain of the DR. And we will use detailed sounding data to explain the presence and characteristics of the massive MCS to the south, as well as the upper-level updrafts apparent over this MCS and over the mountains of the DR.

Geerts, B.↗

Molecular-Level Control over Ionic Conduction and Ionic Current Direction by Designing Macrocycle-Based Ionomers

Poor ionic conductivity of the catalyst-binding, submicrometer- thick ionomer layers in energy conversion and storage devices is a huge challenge. However, ionomers are rarely designed keeping in mind the specific issues associated with nanoconfinement. Here, we designed nature-inspired ionomers (calix-2) having hollow, macrocyclic, calix[4]arene-based repeat units with precise, sub-nanometer diameter. In ≤100 nm-thick films, the in-plane proton conductivity of calix-2 was up to 8 times higher than the current benchmark ionomer Nafion at 85% relative humidity (RH), while it was 1-2 orders of magnitude higher than Nafion at 20-25% RH. Confocal laser scanning microscopy and other synthetic techniques allowed us to demonstrate the role of macrocyclic cavities in boosting the proton conductivity. The systematic self-assembly of calix-2 chains into ellipsoids in thin films was evidenced from atomic force microscopy and grazing incidence small-angle X-ray scattering measurements. Moreover, the likelihood of alignment and stacking of macrocyclic units, the presence of one-dimensional water wires across this macrocycle stacks, and thus the formation of long-range proton conduction pathways were suggested by atomistic simulations. We not only did see an unprecedented improvement in thin-film proton conductivity but also saw an improvement in proton conductivity of bulk membranes when calix-2 was added to the Nafion matrices. Nafion-calix-2 composite membranes also took advantage of the asymmetric charge distribution across calix[4]arene repeat units collectively and exhibited voltage-gating behavior. The inclusion of molecular macrocyclic cavities into the ionomer chemical structure can thus emerge as a promising design concept for highly efficient ion-conducting and ion-permselective materials for sustainable energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Meta-omics reveals role of photosynthesis in microbially induced carbonate precipitation at a CO2-rich geyser

Abstract Microbially induced carbonate precipitation (MICP) is a natural process with potential biotechnological applications to address both carbon sequestration and sustainable construction needs. However, our understanding of the microbial processes involved in MICP is limited to a few well-researched pathways such as ureolytic hydrolysis. To expand our knowledge of MICP, we conducted an omics-based study on sedimentary communities from travertine around the CO2-driven Crystal Geyser near Green River, Utah. Using metagenomics and metaproteomics, we identified the community members and potential metabolic pathways involved in MICP. We found variations in microbial community composition between the two sites we sampled, but Rhodobacterales were consistently the most abundant order, including both chemoheterotrophs and anoxygenic phototrophs. We also identified several highly abundant genera of Cyanobacteriales. The dominance of these community members across both sites and the abundant presence of photosynthesis-related proteins suggest that photosynthesis could play a role in MICP at Crystal Geyser. We also found abundant bacterial proteins involved in phosphorous starvation response at both sites suggesting that P-limitation shapes both composition and function of the microbial community driving MICP.

Violette, Marlene J.↗

Dynamical States of Low Temperature Cirrus

Low ice crystal concentration and sustained in-cloud supersaturation, commonly found in cloud observations at low temperature, challenge our understanding of cirrus formation. Heterogeneous freezing from effloresced ammonium sulfate, glassy aerosol, dust and black carbon are proposed to cause these phenomena; this requires low updrafts for cirrus characteristics to agree with observations and is at odds with the gravity wave spectrum in the upper troposphere. Background temperature fluctuations however can establish a dynamical equilibrium between ice production and sedimentation loss (as opposed to ice crystal formation during the first stages of cloud evolution and subsequent slow cloud decay) that explains low temperature cirrus properties. This newly-discovered state is favored at low temperatures and does not require heterogeneous nucleation to occur (the presence of ice nuclei can however facilitate its onset). Our understanding of cirrus clouds and their role in anthropogenic climate change is reshaped, as the type of dynamical forcing will set these clouds in one of two preferred microphysical regimes with very different susceptibility to aerosol.

Barahona, D.↗

Observational Needs for Improving Ocean and Coupled Reanalysis, S2S Prediction, and Decadal Prediction

Developments in ocean data assimilation (DA) and observing system technologies are intertwined. New observation types lead to new DA methods, and new DA methods such as Coupled Data Assimilation can change the value of existing observations or indicate where new observations can have greater utility for monitoring and prediction. Practitioners are encouraged to make better use of observations that are already available, for example in strongly coupled data assimilation where ocean observations can be used to improve atmospheric analyses and vice versa. Ocean reanalyses are useful for the analysis of climate,as well as initializing operational long-range prediction models. There are remaining challenges for ocean reanalyses due to biases and abrupt changes in the ocean observing system throughout its history, the presence of biases and drifts in models, and simplifying assumptions made in the DA methods. From a governance point of view, more support is needed to interface the observing community and the ocean DA community. For prediction applications, the ocean DA community must work with the ocean observing community to establish protocols for rapid communication of ocean observing data on NWP timescales. There is potential for new observations to enhance the observing system by supporting prediction on multiple timescales, ranging from the typical timescale of numerical weather prediction covering hours to weeks, out to multiple decades. It is highly encouraged that communication be fostered between thesecommunities to allow operational prediction centers the ability to provide guidance to the design of a sustained and adaptive observing network.

Ocean reanalysis↗