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Variations in radiative heating of humid biomass burning aerosols in the southeast Atlantic from airborne observations and reanalysis

The atmosphere over the southeast Atlantic Ocean (SEA) experiences consistent springtime biomass burning (BB) smoke from widespread agricultural fires on the African continent. This smoke layer is initially lofted high in a continental mixed layer (~5-6km) and is then transported westward into the free troposphere where it overlies and ultimately mixes into a stratocumulus-topped oceanic boundary layer. Coincident with this smoke is an elevated humidity signal which is present from the time a given airmass is over the continental source region. ORACLES (ObseRvations of Aerosols above CLouds and their intEractionS) was a NASA Earth Venture Suborbital mission with the goal of measuring aerosol, cloud, and atmospheric properties over this region over three deployments in September 2016, August 2017, and October 2018. Measurements included in situ profile measurements of aerosol physical and optical properties, trace gas concentrations, and cloud properties, as well as column measurements of aerosol optical depth and trace gas concentrations from an airborne sun photometer. Here we present results from each of the ORACLES deployments over the southeast Atlantic Ocean. Despite the differing locations and season of each deployment, we show that there is good agreement between the airborne ORACLES dataset and large-scale reanalyses, specifically the ECMWF ERA5 reanalyses (and, to a degree, the CAMS product) as compared to other available products. This agreement allows us to examine multi-year seasonal patterns and trends beyond the three months with available aircraft data. In both the data and reanalysis, we find distinct variations between each deployment in terms of vertical smoke distribution and correlation to atmospheric specific humidity, due to changing conditions over the BB season. We trace the origin and the history of these smoky airmasses and finally, we briefly discuss the broader radiative and dynamical implications of these results for conditions of aerosols overlying stratocumulus clouds.

K. Pistone↗
DOE OSTI2026

Handling and Properties of Methanol as a Marine Fuel

Given the increasing concern around greenhouse gas emissions and the decline in the availability of fossil fuels, there is increasing global demand to develop alternate fuels for maritime transportation that are sustainable and which have lower greenhouse gas emissions. Methanol is one such alternative fuel that has garnered considerable attention given its potential to be produced by more sustainable processes and its more favorable greenhouse gas emission profile in comparison with current fossil fuels. Understanding the physical and chemical properties of methanol under a range of conditions is essential for its development as a marine fuel. In this study, we seek to define physical and chemical properties of different methanol samples to simulate real-world storage conditions as these data are lacking in the literature. Several methanol samples were evaluated: nearly pure methanol; International Organization for Standardization (ISO) marine methanol (MM) grades A, B, and C; and methanol plus higher alcohols. We first evaluated all methanol samples for impurities, acetic acid content, density, and distillation range. We then characterized the effects of water absorption and found that methanol can easily absorb unacceptable water content from humid air within hours, necessitating storage conditions that prevent this process. In eight-week aging experiments at 20 °C and 40 °C in ambient air, we did not observe significant oxidation for any of the methanol samples; however, we did observe increases in acid number. We assessed the impact of contamination of methanol with water, marine gas oil (MGO), and an MGO–biodiesel mixture on density, viscosity, distillation range, and lubricity. Finally, we show that MGO contamination of methanol results in a slight increase in sooting tendency. In aggregate, our results provide an in-depth analysis of physical and chemical properties of methanol as well as the impacts of storage conditions and impurities on the properties of fuel methanol.

09 BIOMASS FUELS↗
DOE OSTI2021

Production of Gaseous Olefins from Syngas over a Cobalt-HZSM-5 Catalyst

Light olefins (C2–C5) are high-value platform chemicals used to produce plastics, lubricants, coating material, and surfactants, and can be intermediates to produce transportation fuels. In this study we report on the development of a Co-based catalyst for direct conversion of fossil as well as biomass derived syngas into light olefins that enables high conversion and olefin/paraffin (O/P) product ratio, minimal selectivity to CO2 (<?1%) and wax formation (C14+ selectivity?<?1%). Over a Co/HZSM-5 bi-functional catalyst 38% CO conversion with C2–C5 olefin selectivity of 48%, and O/P ratio of 4.0 was achieved at 240 °C, 17 bar, and 1.5 L/(g–h). In addition to a gaseous olefin-rich stream a C6–C13 mixed olefin/paraffin liquid byproduct was also produced with 25% selectivity. Both Co loading and the HZSM-5 acidity levels were optimized to maintain the balance between the hydrogenation and the cracking activity to generate high levels of C2–C4 olefins. A suite of catalyst characterization tools were used to correlate the physical and chemical property of the catalyst to the performance of the catalyst towards syngas conversion and C2–C4 olefin selectivity.

Maddi, Balakrishna↗
DOE OSTI2023

Plastic from CO2 and Inedible Biomass (CRADA Final Report)

As part of the Cyclotron Road program, ReSource Chemical Corp. sought to investigate the conversion of inedible biomass and CO₂ to FDCA. FDCA is a performance monomer widely viewed as a green replacement for the petroleum-derived monomer PTA, which is produced at approximately 60 Mt per year with over 100 Mt of annual GHG emissions. The major polyester made from PTA, called PET, is a >$\$$100B industry with applications in bottling, food packaging, and fibers. The FDCA analogue of PET, called PEF, had superior gas barrier, mechanical, and thermal properties that enable increased shelf life of perishable goods while using less plastic.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

One thousand soils for molecular understanding of belowground carbon cycling

While significant progress has been made in understanding global carbon (C) cycling, the mechanisms regulating belowground C fluxes and storage are still uncertain. New molecular technologies have the power to elucidate these processes, yet we have no widespread standardized implementation of molecular techniques. To address this gap, we introduce the Molecular Observation Network (MONet), a decadal vision from the Environmental Molecular Sciences Laboratory (EMSL), to develop a national network for understanding the molecular composition, physical structure, and hydraulic and biological properties of soil and water. These data are essential for advancing the next generation of multiscale Earth systems models. In this paper, we discuss the 1000 Soils Pilot for MONet, including a description of standardized sampling materials and protocols and a use case to highlight the utility of molecular-level and microstructural measurements for assessing the impacts of wildfire on soil. While the 1000 Soils Pilot generated a plethora of data, we focus on assessments of soil organic matter (SOM) chemistry via Fourier-transform ion cyclotron resonance-mass spectrometry and microstructural properties via X-ray computed tomography to highlight the effects of recent fire history in forested ecosystems on belowground C cycling. We observed decreases in soil respiration, microbial biomass, and potential enzyme activity in soils with high frequency burns. Additionally, the nominal oxidation state of carbon in SOM increased with burn frequency in surface soils. This results in a quantifiable shift in the molecular signature of SOM and shows that wildfire may result in oxidation of SOM and structural changes to soil pore networks that persist into deeper soils.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Production of chitosan-based composite film reinforced with lignin-rich lignocellulose nanofibers from rice husk

Lignocellulosic nanofibers (LCNFs), implying lignin-containing cellulose fibers, maintain the properties of both lignin and cellulose, which are hydrophobic and hydrophilic, respectively. The presence of hydrophobic lignin in LCNFs is expected to be an economical and attractive option that can improve the thermal and mechanical properties of polymers. Thus, this study was conducted to produce lignin-rich LCNFs from sugar-rich waste obtained from rice husks after acidic pretreatment. The LCNFs were produced from the lignin-rich solid fractions obtained after pretreatment and enzymatic hydrolysis, which were then incorporated as an additive into a chitosan-based film. The variations in lignin content in the range of approximately 50.6%-66.8% in differently obtained LCNFs gave significantly different optical strengths and mechanical properties. These controllable processes may allow for customized film formation. Additionally, the glucose-rich liquid fractions obtained after pretreatment and enzymatic hydrolysis were used as a substrate for ethanol fermentation to achieve total utilization of rice husk biomass waste. In conclusion, the lignin-rich biomass fraction holds promise as a suitable material for chitosan-LCNF film and has the potential to increase the economic feasibility of the biomaterial industry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

SWIFT: Single-pass, Weather Independent Fractionation Technology for Improved Property Control of Corn Stover Feedstock

Corn stover is an abundant source of biomass that can be utilized for bioenergy production, representing 70% of the available crop residues in the U.S. However, recent projections estimate that over 60% of corn stover will be collected at moisture levels that exceed 20% moisture (wet basis), resulting in instability in conventional baled logistics systems due to unwanted microbial degradation. This biomass challenge can be solved with a paradigm-shifting technology or SWIFT: Single-pass, Weather Independent Fractionation Technology. SWIFT streamlines collection by eliminating multiple time-consuming, costly, non-value-added, field and weather-dependent steps that comprise the current state of the art in corn stover harvest. The unique approach envisions simultaneous harvest and collection of high, dry matter, whole-plant corn (i.e., stover plus grain) combined with anaerobic storage and fractionation as a means to positively influence the physical and chemical characteristics of corn stover biomass and the resulting feedstock.

09 BIOMASS FUELS↗
NASA NTRS2023

Health and Safety Effects of Airborne Soil Dust in the Americas and Beyond

Risks associated with dust hazards are often underappreciated, a gap between the knowledge pool and public awareness that can be costly for impacted communities. This study reviews the emission sources and chemical, physical, and biological characteristics of airborne soil particles (dust) and their effects on human and environmental health and safety in the Pan-American region. American dust originates from both local sources (western United States, northern Mexico, Peru, Bolivia, Chile, and Argentina) and long-range transport from Africa and Asia. Dust properties, as well as the trends and interactions with criteria air pollutants, are summarized. Human exposure to dust is associated with adverse health effects, including asthma, allergies, fungal infections, and premature death. In the Americas, a well-documented and striking effect of soil dust is its association with Coccidioidomycosis, commonly known as Valley fever, an infection caused by inhalation of soil-dwelling fungi unique to this region. Besides human health, dust affects environmental health through nutrients that increase phytoplankton biomass, contaminants that diminish water supply and affect food (crops/fruits/vegetables and ready-to-eat meat), spread crop and marine pathogens, cause Valley fever among domestic and wild animals, transport heavy metals, radionuclides and microplastics, and reduce solar and wind power generation. Dust is also a safety hazard to road transportation and aviation, in the southwestern US where blowing dust is one of the deadliest weather hazards. To mitigate the harmful effects, coordinated regional and international efforts are needed to enhance dust observations and prediction capabilities, soil conservation measures, and Valley fever and other disease surveillance.

health↗
NASA NTRS2021

An overview of the ORACLES (ObseRvations of Aerosols above CLouds and their intEractionS) project: aerosol–cloud–radiation interactions in the southeast Atlantic basin

Southern Africa produces almost a third of the Earth’s biomass burning (BB) aerosol particles, yet the fate of these particles and their influence on regional and global climate is poorly understood. ORACLES (ObseRvations of Aerosols above CLouds and their intEractionS) is a 5-year NASA EVS-2 (Earth Venture Suborbital-2) investigation with three intensive observation periods designed to study key atmospheric processes that determine the climate impacts of these aerosols. During the Southern Hemisphere winter and spring (June–October), aerosol particles reaching 3–5 km in altitude are transported westward over the southeast Atlantic, where they interact with one of the largest subtropical stratocumulus (Sc) cloud decks in the world. The representation of these interactions in climate models remains highly uncertain in part due to a scarcity of observational constraints on aerosol and cloud properties, as well as due to the parameterized treatment of physical processes. Three ORACLES deployments by the NASA P-3 aircraft in September 2016, August 2017, and October 2018 (totaling ~ 350 science flight hours), augmented by the deployment of the NASA ER-2 aircraft for remote sensing in September 2016 (totaling ~ 100 science flight hours), were intended to help fill this observational gap. ORACLES focuses on three fundamental science themes centered on the climate effects of African BB aerosols: (a) direct aerosol radiative effects, (b) effects of aerosol absorption on atmospheric circulation and clouds, and (c) aerosol–cloud microphysical interactions. This paper summarizes the ORACLES science objectives, describes the project implementation, provides an overview of the flights and measurements in each deployment, and highlights the integrative modeling efforts from cloud to global scales to address science objectives. Significant new findings on the vertical structure of BB aerosol physical and chemical properties, chemical aging, cloud condensation nuclei, rain and precipitation statistics, and aerosol indirect effects are emphasized, but their detailed descriptions are the subject of separate publications. The main purpose of this paper is to familiarize the broader scientific community with the ORACLES project and the dataset it produced.

Jens Redemann↗
DOE OSTI2021

An overview of the ORACLES (ObseRvations of Aerosols above CLouds and their intEractionS) project: aerosol–cloud–radiation interactions in the southeast Atlantic basin

Southern Africa produces almost a third of the Earth's biomass burning (BB) aerosol particles, yet the fate of these particles and their influence on regional and global climate is poorly understood. ORACLES (ObseRvations of Aerosols above CLouds and their intEractionS) is a 5-year NASA EVS-2 (Earth Venture Suborbital-2) investigation with three intensive observation periods designed to study key atmospheric processes that determine the climate impacts of these aerosols. During the Southern Hemisphere winter and spring (June-October), aerosol particles reaching 3-5 km in altitude are transported westward over the southeast Atlantic, where they interact with one of the largest subtropical stratocumulus (Sc) cloud decks in the world. The representation of these interactions in climate models remains highly uncertain in part due to a scarcity of observational constraints on aerosol and cloud properties, as well as due to the parameterized treatment of physical processes. Three ORACLES deployments by the NASA P-3 aircraft in September 2016, August 2017, and October 2018 (totaling ~350 science flight hours), augmented by the deployment of the NASA ER-2 aircraft for remote sensing in September 2016 (totaling ~100 science flight hours), were intended to help fill this observational gap. ORACLES focuses on three fundamental science themes centered on the climate effects of African BB aerosols: (a) direct aerosol radiative effects, (b) effects of aerosol absorption on atmospheric circulation and clouds, and (c) aerosol–cloud microphysical interactions. This paper summarizes the ORACLES science objectives, describes the project implementation, provides an overview of the flights and measurements in each deployment, and highlights the integrative modeling efforts from cloud to global scales to address science objectives. Significant new findings on the vertical structure of BB aerosol physical and chemical properties, chemical aging, cloud condensation nuclei, rain and precipitation statistics, and aerosol indirect effects are emphasized, but their detailed descriptions are the subject of separate publications. The main purpose of this paper is to familiarize the broader scientific community with the ORACLES project and the dataset it produced.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2018

Exoplanet Biosignatures: A Review of Remotely Detectable Signs of Life

In the coming years and decades, advanced space- and ground-based observatories will allow an unprecedented opportunity to probe the atmospheres and surfaces of potentially habitable exoplanets for signatures of life. Life on Earth, through its gaseous products and reflectance and scattering properties, has left its fingerprint on the spectrum of our planet. Aided by the universality of the laws of physics and chemistry, we turn to Earth's biosphere, both in the present and through geologic time, for analog signatures that will aid in the search for life elsewhere. Considering the insights gained from modern and ancient Earth, and the broader array of hypothetical exoplanet possibilities, we have compiled a comprehensive overview of our current understanding of potential exoplanet biosignatures, including gaseous, surface, and temporal biosignatures. We additionally survey biogenic spectral features that are well known in the specialist literature but have not yet been robustly vetted in the context of exoplanet biosignatures. We briefly review advances in assessing biosignature plausibility, including novel methods for determining chemical disequilibrium from remotely obtainable data and assessment tools for determining the minimum biomass required to maintain short-lived biogenic gases as atmospheric signatures. We focus particularly on advances made since the seminal review by Des Marais et al. The purpose of this work is not to propose new biosignature strategies, a goal left to companion articles in this series, but to review the current literature, draw meaningful connections between seemingly disparate areas, and clear the way for a path forward.

biosignatures↗
NASA NTRS2010

Tidal Marsh Outwelling of Dissolved Organic Matter and Resulting Temporal Variability in Coastal Water Optical and Biogeochemical Properties

Coastal wetlands are highly dynamic environments at the land-ocean interface where human activities, short-term physical forcings and intense episodic events result in high biological and chemical variability. Long being recognized as among the most productive ecosystems in the world, tidally-influenced coastal marshes are hot spots of biogeochemical transformation and exchange. High temporal resolution observations that we performed in several marsh-estuarine systems of the Chesapeake Bay revealed significant variability in water optical and biogeochemical characteristics at hourly time scales, associated with tidally-driven hydrology. Water in the tidal creek draining each marsh was sampled every hour during several semi-diurnal tidal cycles using ISCO automated samplers. Measurements showed that water leaving the marsh during ebbing tide was consistently enriched in dissolved organic carbon (DOC), frequently by more than a factor of two, compared to water entering the marsh during flooding tide. Estimates of DOC fluxes showed a net DOC export from the marsh to the estuary during seasons of both low and high biomass of marsh vegetation. Chlorophyll amounts were typically lower in the water draining the marsh, compared to that entering the marsh during flooding tide, suggesting that marshes act as transformers of particulate to dissolved organic matter. Moreover, detailed optical and compositional analyses demonstrated that marshes are important sources of optically and chemically distinctive, relatively complex, high molecular weight, aromatic-rich and highly colored dissolved organic compounds. Compared to adjacent estuarine waters, marsh-exported colored dissolved organic matter (CDOM) was characterized by considerably stronger absorption (more than a factor of three in some cases), larger DOC-specific absorption, lower exponential spectral slope, larger fluorescence signal, lower fluorescence per unit absorbance, and higher fluorescence at visible wavelengths. Observed patterns in water optical and biogeochemical variables were very consistent among different marsh systems and throughout the year, despite continued tidal exchange, implying rapid transformation of marsh DOM in the estuary through both photochemical and microbial processes. These findings illustrate the importance of tidal marsh ecosystems as sources, sinks and/or transformers of biologically important nutrients, carbon and colored dissolved organic compounds, and their influence on short-term biological, optical and biogeochemical variability in coastal waters.

Tzortziou, Maria↗
DOE OSTI2025

Surface Texture of Macroplastic Pollution in Streams Alters the Physical Structure and Diversity of Biofilm Communities

ABSTRACT Biofilms can develop on nearly any surface, and in aquatic ecosystems they are essential components of biogeochemical cycles and food webs. Plastic waste in waterways is a new type of surface for biofilm colonisation. To analyse the influence of plastic pollution on the development and diversity of microbial freshwater biofilms that colonised them, we incubated 388 cm 2 veneers of high‐density polyethylene (HDPE) with two veneer textures, smooth and rough, and tulip tree wood ( Liriodendron tulipifera ), in three rural headwater streams at the Savannah River Site (Aiken, SC, USA). We collected biofilms from veneers after 14, 28 and 56 days of incubation and analysed 16S rRNA genes and biofilm properties. We found that plastic negatively affected species richness of biofilms compared with wood, but that evenness was greatest on rough textured HDPE. Beta diversity was primarily influenced by stream site. Beta diversity differed more between wood and plastic veneers than with plastic surface texture and became more different over time. Wood had nine times more biomass than rough HDPE and 40 times more biomass than smooth HDPE. Given the projected increase of macroplastic pollution in aquatic ecosystems, our findings emphasise the need to further understand its effects on biofilm characteristics.

Lopez Avila, Fabiola [Odum School of Ecology Unive↗
NASA NTRS2016

Aerosol-Radiation-Cloud Interactions in the South-East Atlantic: Future Suborbital Activities to Address Knowledge Gaps in Satellite and Model Assessments

Southern Africa produces almost a third of the Earth's biomass burning (BB) aerosol particles. Particles lofted into the mid-troposphere are transported westward over the South-East (SE) Atlantic, home to one of the three permanent subtropical stratocumulus (Sc) cloud decks in the world. The SE Atlantic stratocumulus deck interacts with the dense layers of BB aerosols that initially overlay the cloud deck, but later subside and may mix into the clouds. These interactions include adjustments to aerosol-induced solar heating and microphysical effects, and their global representation in climate models remains one of the largest uncertainties in estimates of future climate. Hence, new observations over the SE Atlantic have significant implications for global climate change scenarios. Our understanding of aerosol-cloud interactions in the SE Atlantic is hindered both by the lack of knowledge on aerosol and cloud properties, as well as the lack of knowledge about detailed physical processes involved. Most notably, we are missing knowledge on the absorptive and cloud nucleating properties of aerosols, including their vertical distribution relative to clouds, on the locations and degree of aerosol mixing into clouds, on the processes that govern cloud property adjustments, and on the importance of aerosol effects on clouds relative to co-varying synoptic scale meteorology. We discuss the current knowledge of aerosol and cloud property distributions based on satellite observations and sparse suborbital sampling. Recent efforts to make full use of A-Train aerosol sensor synergies will be highlighted. We describe planned field campaigns in the region to address the existing knowledge gaps. Specifically, we describe the scientific objectives and implementation of the five synergistic, international research activities aimed at providing some of the key aerosol and cloud properties and a process-level understanding of aerosol-cloud interactions over the SE Atlantic: NASA's ORACLES, the UK Met Office's CLARIFY-2016, the DoE's LASIC, NSF's ONFIRE, and CNRS' AEROCLO-SA.

aerosols↗
NASA NTRS2019

Extending XBAER Algorithm to Aerosol and Cloud Condition

The retrieval of cloud optical properties for aerosol contaminated water cloud is challenging because of the complexity of physical processes in such situations. Conventionally, cloud optical data products are typically derived, ignoring the aerosol impacts on radiative transfer in the retrieval process. This is potentially a significant source of error. In this paper, the eXtensible Bremen Aerosol Retrieval (XBAER) algorithm has been optimized for the retrieval of aerosol/cloud properties for the aerosol contaminated cloud (ACC) scenarios. This version of XBAER delivers cloud optical thickness (COT) and cloud effective radius (CER) for ACCs and simultaneously retrieves aerosol optical thickness (AOT). The surface parameterization and aerosol types used in the standard XBAER algorithm have been adapted in this retrieval to account for the ACC conditions. Aerosol types in XBAER for the retrieval of ACC scenarios have been parameterized to comprise weak and strong absorptions. The comparisons of COT, CER, and AOT retrieved using this adapted XBAER algorithm and two new NASA algorithms show good agreements, especially for biomass burning aerosol. The correlation coefficients are >0.9 for AOT, ~0.8 for CER, and ~0.7 for COT. There is also a good agreement for dust plume contaminated cloud scene. The XBAER derived AOT values for dust aerosols are systematically smaller than the NASA retrieval, but both products have the same spatial distribution patterns. The comparison of COT retrieved using the adapted XBAER algorithm and that retrieved from ground-based microwave radiometer (MWR) measurements shows much better agreement for ACC conditions with high AOT.

satellite↗
NASA NTRS2023

The Coupling Between Tropical Meteorology, Aerosol Lifecycle, Convection, and Radiation, During the Clouds, Aerosol and Monsoon Processes Philippines Experiment (CAMP2Ex)

The NASA Cloud, Aerosol, and Monsoon Processes Philippines Experiment (CAMP2Ex) employed the NASA P-3, Stratton Park Engineering Company (SPEC) Learjet 35, and a host of satellites and surface sensors to characterize the coupling of aerosol processes, cloud physics, and atmospheric radiation within the Maritime Continent’s complex southwest monsoonal environment. Conducted in the late summer of 2019 from Luzon Philippines in conjunction with the Office of Naval Research Propagation of Intraseasonal Tropical OscillatioNs (PISTON) experiment with its R/VSally Ride stationed in the North Western Tropical Pacific, CAMP2Ex documented diverse biomass burning, industrial and natural aerosol populations and their interactions with small to congestus convection. The 2019 season exhibited El Nino and associated drought, high biomass burning emissions, and an early monsoon transition allowing for observation of pristine to massively polluted environments as they advected through intricate diurnal mesoscale and radiative environments into the monsoonal trough. CAMP2Ex’s preliminary results indicate 1) increasing aerosol loadings tend to invigorate congestus convection in height and increase liquid water paths; 2) lidar, polarimetry, and geostationary Advanced Himawari Imager remote sensing sensors have skill in quantifying diverse aerosol and cloud properties and their interaction; and 3) high resolution remote sensing technologies are able to greatly improve our ability to evaluate the radiation budget in complex cloud systems. Through the development of innovative informatics technologies, CAMP2Ex provides a benchmark dataset of an environment of extremes for the study of aerosol, cloud and radiation processes as well as a crucible for the design of future observing systems.

CAMP2Ex↗
DOE OSTI2026

Zwitterion Moieties in Polypeptides Synergistically Enhance the Release of Cellulose and Amorphous Polysaccharides from Plant Cell Walls

This study demonstrated that covalently localized zwitterionic moieties in zwitterionic polypeptides (ZIPs) effectively disrupt hydrogen bonds in cellulosic substrates, including filter paper and plant cell wall materials, without significant cytotoxicity. ZIPs with varying densities of zwitterionic side chains were synthesized via the postpolymerization modification of histidinecontaining oligopeptides. The newly developed ZIPs predominantly comprised repeating units with zwitterionically converted side chains. Such ZIPs can cleave multiple hydrogen bonds by anchoring the zwitterionic structure at specific sites, thereby partially dissociating the polysaccharide chains in the cell wall. They are especially effective in dissolving amorphous cellulose, even at low concentrations in aqueous solutions. Importantly, this effect was achieved with minimal cellular toxicity, harnessing the advantages of ionic liquid-like properties while mitigating their high-toxicity limitations. This biofriendly approach to cell wall denaturation highlights a novel method for controlling hydrogen bond networks in polysaccharides and cell walls. These findings indicate a new approach for reducing biomass recalcitrance and developing next-generation biobased materials and fuels derived from plant cell walls.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Bioenabled Platform to Access Polyamides with Built-In Target Properties

The diversification of platform chemicals is key to today’s petroleum industry. Likewise, the flourishing of tomorrow’s biorefineries will rely on molecules with next-generation properties from biomass. Herein, we explore this opportunity with a novel approach to monomers with custom property enhancements. Cyclic diacids with alkyl and aromatic decorations were synthesized from muconic acid by Diels-Alder cycloaddition and copolymerized with hexamethylenediamine and adipic acid to yield polyamides with built-in hydrophobicity and flame retardancy. Testing shows a 70% reduction in water uptake and doubling of char production while largely retaining other key properties of the parent Nylon-6,6. In conclusion, the present approach can be generalized to access a wide range of performance-advantaged polyamides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗