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At least 199 records · Page 11

Mapping microhabitats of lignocellulose decomposition by a microbial consortium

The leaf-cutter ant fungal garden ecosystem is a naturally evolved model system for efficient plant biomass degradation. Degradation processes mediated by the symbiotic fungus Leucoagaricus gongylophorus are difficult to characterize due to dynamic metabolisms and spatial complexity of the system. Herein, we performed microscale imaging across 12-µm-thick adjacent sections of Atta cephalotes fungal gardens and applied a metabolome-informed proteome imaging approach to map lignin degradation. This approach combines two spatial multiomics mass spectrometry modalities that enabled us to visualize colocalized metabolites and proteins across and through the fungal garden. Spatially profiled metabolites revealed an accumulation of lignin-related products, outlining morphologically unique lignin microhabitats. Metaproteomic analyses of these microhabitats revealed carbohydrate-degrading enzymes, indicating a prominent fungal role in lignocellulose decomposition. Integration of metabolome-informed proteome imaging data provides a comprehensive view of underlying biological pathways to inform our understanding of metabolic fungal pathways in plant matter degradation within the micrometer-scale environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Product specific thermal degradation kinetics of bisphenol F epoxy in inert and oxidative atmospheres using evolved gas analysis–mass spectrometry

Knowledge of the degradation kinetics for polymer materials is important for understanding thermal stability. In this study, evolved gas analysis–mass spectrometry and pyrolysis gas-chromatography-mass spectrometry were evaluated for the potential to deliver additional insight into thermal degradation kinetics of diglycidal ether of bisphenol F (DGEBF) epoxy thermoset under inert and oxidative atmospheres. Degradation products of selected precursor ions were evaluated for their uniqueness to the specific precursor using extracted ion thermographs. Unique mass peaks, solely attributed to a single reaction pathway of a specific product, were determined from extracted ion thermographs and used to determine both activation energy (E a ) and pre-exponential factors for the specific primary reaction pathways. These primary reaction pathways for DGEBF epoxy degradation were then evaluated in the context of transition state theory (TST) and related transition state enthalpies (ΔH ‡ ) and entropies (ΔS ‡ ) of activation to further elucidate the degradation process. It was determined under pyrolysis conditions, as suggested by the E a , the formation of bisphenol F monomer was the rate-limiting step toward the formation of xanthene and phenol. In contrast, under thermo-oxidative conditions, reactions involving oxygen containing species were identified as the rate-limiting step for all observed products based on the large negative ΔS ‡ calculated from TST. This work demonstrates a powerful combination of technique and theory that can provide new insight into the degradation of polymer materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In planta production of the nylon precursor beta-ketoadipate

Beta-ketoadipate (βKA) is an intermediate of the βKA pathway involved in the degradation of aromatic compounds in several bacteria and fungi. Beta-ketoadipate also represents a promising chemical for the manufacturing of performance-advantaged nylons. We established a strategy for the in planta synthesis of βKA via manipulation of the shikimate pathway and the expression of bacterial enzymes from the βKA pathway. Using Nicotiana benthamiana as a transient expression system, we demonstrated the efficient conversion of protocatechuate (PCA) to βKA when plastid-targeted bacterial-derived PCA 3,4-dioxygenase (PcaHG) and 3-carboxy-cis,cis-muconate cycloisomerase (PcaB) were co-expressed with 3-deoxy-D-arabinoheptulosonate 7-phosphate synthase (AroG) and 3-dehydroshikimate dehydratase (QsuB). This metabolic pathway was reconstituted in Arabidopsis by introducing a construct (pAtβKA) with stacked pcaG, pcaH, and pcaB genes into a PCA-overproducing genetic background that expresses AroG and QsuB (referred as QsuB-2). The resulting QsuB-2 x pAtβKA stable lines displayed βKA titers as high as 0.25 % on a dry weight basis in stems, along with a drastic reduction in lignin content and improvement of biomass saccharification efficiency compared to wild-type controls, and without any significant reduction in biomass yields. Using biomass sorghum as a potential crop for large-scale βKA production, techno-economic analysis indicated that βKA accumulated at titers of 0.25 % and 4 % on a dry weight basis could be competitively priced in the range of $2.04-34.49/kg and $0.47-2.12/kg, respectively, depending on the selling price of the residual biomass recovered after βKA extraction. This study lays the foundation for a more environmentally-friendly synthesis of βKA using plants as production hosts.

Kazaz, Sami↗

Phosphorolytic degradation of leaf starch via plastidic α-glucan phosphorylase leads to optimized plant growth and water use efficiency over the diel phases of Crassulacean acid metabolism

In plants with Crassulacean acid metabolism (CAM), it has been proposed that the requirement for nocturnal provision of phosphoenolpyruvate as a substrate for CO 2 uptake has resulted in a re-routing of chloroplastic starch degradation from the amylolytic route to the phosphorolytic route. To test this hypothesis, we generated and characterized four independent RNAi lines of the obligate CAM species Kalanchoë fedtschenkoi with a >10-fold reduction in transcript abundance of plastidic α-glucan phosphorylase (PHS1). The rPHS1 lines showed diminished nocturnal starch degradation, reduced dark CO 2 uptake, a reduction in diel water use efficiency (WUE), and an overall reduction in growth. A re-routing of starch degradation via the hydrolytic/amylolytic pathway was indicated by hyperaccumulation of maltose in all rPHS1 lines. Further examination indicated that whilst operation of the core circadian clock was not compromised, plasticity in modulating net dark CO 2 uptake in response to changing photoperiods was curtailed. The data show that phosphorolytic starch degradation is critical for efficient operation of the CAM cycle and for optimizing WUE. This finding has clear relevance for ongoing efforts to engineer CAM into non-CAM species as a means of boosting crop WUE for a warmer, drier future.

59 BASIC BIOLOGICAL SCIENCES↗

Evaluating Possible Formation Mechanisms of Criegee Intermediates during the Heterogeneous Autoxidation of Squalene

Organic molecules in the environment oxidatively degrade by a variety of free radical, microbial, and biogeochemical pathways. A significant pathway is heterogeneous autoxidation, in which degradation occurs via a network of carbon and oxygen centered free radicals. Recently, we found evidence for a new heterogeneous autoxidation mechanism of squalene that is initiated by hydroxyl (OH) radical addition to a carbon–carbon double bond and apparently propagated through pathways involving Criegee Intermediates (CI) produced from β-hydroxy peroxy radicals (β-OH-RO 2 •). It remains unclear, however, exactly how CI are formed from β-OH-RO 2 •, which could occur by a unimolecular or bimolecular pathway. Combining kinetic models and multiphase OH oxidation measurements of squalene, we evaluate the kinetic viability of three mechanistic scenarios. Scenario 1 assumes that CI are formed by the unimolecular bond scission of β-OH-RO 2 •, whereas Scenarios 2 and 3 test bimolecular pathways of β-OH-RO 2 • to yield CI. Scenario 1 best replicates the entire experimental data set, which includes effective uptake coefficients vs [OH] as well as the formation kinetics of the major products (i.e., aldehydes and secondary ozonides). Finally, although the unimolecular pathway appears to be kinetically viable, future high-level theory is needed to fully explain the mechanistic relationship between CI and β-OH-RO 2 • in the condensed phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

GhBZR3 suppresses cotton fiber elongation by inhibiting very‐long‐chain fatty acid biosynthesis

SUMMARY The BRASSINAZOLE‐RESISTANT (BZR) transcription factor is a core component of brassinosteroid (BR) signaling and is involved in the development of many plant species. BR is essential for the initiation and elongation of cotton fibers. However, the mechanism of BR‐regulating fiber development and the function of BZR is poorly understood in Gossypium hirsutum L. (cotton). Here, we identified a BZR family transcription factor protein referred to as GhBZR3 in cotton. Overexpression of GhBZR3 in Arabidopsis caused shorter root hair length, hypocotyl length, and hypocotyl cell length, indicating that GhBZR3 negatively regulates cell elongation. Pathway enrichment analysis from VIGS ‐GhBZR3 cotton plants found that fatty acid metabolism and degradation might be the regulatory pathway that is primarily controlled by GhBZR3. Silencing GhBZR3 expression in cotton resulted in taller plant height as well as longer fibers. The very‐long‐chain fatty acid (VLCFA) content was also significantly increased in silenced GhBZR3 plants compared with the wild type. The GhKCS13 promoter, a key gene for VLCFA biosynthesis, contains two GhBZR3 binding sites. The results of yeast one‐hybrid, electrophoretic mobility shift, and luciferase assays revealed that GhBZR3 directly interacted with the GhKCS13 promoter to suppress gene expression. Taken together, these results indicate that GhBZR3 negatively regulates cotton fiber development by reducing VLCFA biosynthesis. This study not only deepens our understanding of GhBZR3 function in cotton fiber development, but also highlights the potential of improving cotton fiber length and plant growth using GhBZR3 and its related genes in future cotton breeding programs.

Shi, Zemin↗

Investigating the mechanism of chloroplast singlet oxygen signaling in the Arabidopsis thaliana accelerated cell death 2 mutant

As sessile organisms, plants have evolved complex signaling mechanisms to sense stress and acclimate. This includes the use of reactive oxygen species (ROS) generated during dysfunctional photosynthesis to initiate signaling. One such ROS, singlet oxygen ( 1 O 2 ), can trigger retrograde signaling, chloroplast degradation, and programmed cell death. However, the signaling mechanisms are largely unknown. Several proteins (e.g. PUB4, OXI1, EX1) are proposed to play signaling roles across three Arabidopsis thaliana mutants that conditionally accumulate chloroplast 1 O 2 (fluorescent in blue light (flu), chlorina 1 (ch1), and plastid ferrochelatase 2 (fc2)). We previously demonstrated that these mutants reveal at least two chloroplast 1 O 2 signaling pathways (represented by flu and fc2/ch1). Here, we test if the 1 O 2 -accumulating lesion mimic mutant, accelerated cell death 2 (acd2), also utilizes these pathways. The pub4–6 allele delayed lesion formation in acd2 and restored photosynthetic efficiency and biomass. Conversely, an oxi1 mutation had no measurable effect on these phenotypes. acd2 mutants were not sensitive to excess light (EL) stress, yet pub4–6 and oxi1 both conferred EL tolerance within the acd2 background, suggesting that EL-induced 1 O 2 signaling pathways are independent from spontaneous lesion formation. Thus, 1 O 2 signaling in acd2 may represent a third (partially overlapping) pathway to control cellular degradation.

59 BASIC BIOLOGICAL SCIENCES↗

Carbon Tetrachloride Degradation Results for 200-ZP-1 Operable Unit

Carbon tetrachloride (CT) contamination in the 200-ZP-1 Operable Unit (OU) at the Hanford Site originated from large-volume discharges to the subsurface during plutonium production operations between 1955 and 1973. Contamination migrated through more than 70 meters of unsaturated sediment to reach the underlying unconfined aquifer, where it persists as a large and complex groundwater plume. The 200-ZP-1 OU Record of Decision (ROD) requires that groundwater CT concentrations be reduced to 3.4 µg/L within 125 years. Current groundwater modeling projections estimate that the existing pump-and-treat, even when combined with monitored natural attenuation (specifically hydrolysis), will not achieve this target within the designated timeframe. A fundamental contributor to this shortfall is the extremely slow rate of CT hydrolysis under Hanford aquifer conditions, which has been estimated to have a half-life of 630 years. If faster-acting biotic and abiotic degradation processes are operating within the aquifer, their contribution to CT mass reduction could have a meaningful impact. However, site-specific measurements of these processes and their rates have not previously been performed. This report documents the results of a two-phase laboratory investigation designed to characterize and quantify the capacity of site-specific 200-ZP-1 OU sediments and groundwater to support natural attenuation of CT through biotic and abiotic pathways. In this context, degradation capacity is defined as the intrinsic potential of the subsurface matrix to transform CT under optimized, controlled conditions. System capacity is evaluated in two ways: (1) as rate-limited capacity, which establishes the maximum kinetic velocity of CT transformation and is measured using half-lives and first order rate constants; and (2) as mass limited capacity, which defines the total contaminant mass the batch experimental system can degrade before reactants are exhausted, representing the maximum amount of contaminant the microbial community and reactive mineral phases can transform under the experimental conditions.

abiotic degradation↗

Mechanistic Studies of Oxidative Degradation in Diamine-Appended Metal–Organic Frameworks Exhibiting Cooperative CO 2 Capture

Understanding the impact of O 2 during a carbon capture process is vital for designing robust, cost-effective materials for carrying it out. However, mechanistic studies of the O 2 -induced degradation of materials are not easily undertaken owing to the complex sequential reaction pathways that arise. Here, we report comprehensive mechanistic investigations of the O 2 -induced degradation of diamine-appended metal−organic frameworks (MOFs) exhibiting cooperative CO 2 adsorption. Oxygen exposure experiments were performed on seven different diamine-appended MOFs, including e-2−Mg 2 (dobpdc) (e-2 = N-ethylethylenediamine, dobpdc 4− = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate), under various temperatures and O 2 pressures. These experiments show that diamine degradation inhibits CO 2 chemisorption and that the degradation rate is significantly influenced by the diamine structure. In contrast, the parent frameworks remain essentially intact upon O 2 exposure. Detailed characterization of O 2 -exposed e-2−Mg 2 (dobpdc) revealed the formation of various degradation products, including acetaldehyde, carbon dioxide, water, ethylamine, and other aldehyde- and imine-containing species. Together, these observations suggest that diamine degradation occurs via C−N bond cleavage through pathways involving C-centered radicals. Furthermore, computational evaluation of the initiation and propagation pathways for amine degradation in diamine-appended MOFs indicates that (i) degradation is likely initiated by OH • , (ii) carbon-centered radicals generated via radical transfer reactions react with O 2 , leading to amine degradation, and (iii) the ratelimiting step of the degradation reactions likely involves O−O bond cleavage. Overall, these mechanistic insights could inform strategies for mitigating O 2 -induced amine degradation in next-generation carbon capture technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

MarK, a Novosphingobium aromaticivorans kinase required for catabolism of multiple aromatic monomers

The aromatic compounds used in a variety of industrial products are currently obtained from nonrenewable petroleum sources. Alternatively, the plant polymer lignin is an abundant renewable source of aromatics, and its depolymerization generates a variety of products that can include acetovanillone, a vanillin derivative containing an acetyl side chain. The Alphaproteobacterium Novosphingobium aromaticivorans DSM12444 can metabolize several chemically modified aromatics in deconstructed lignin, but not acetovanillone. In this work, adaptive laboratory evolution identified a single amino acid change in the previously uncharacterized gene product Saro_1862 that is necessary and sufficient for N. aromaticivorans growth with acetovanillone as a sole growth substrate, as well as other aromatic monomers not metabolized by wild-type cells. We show that a glutamate (E) to lysine (K) substitution at amino acid residue 16 of Saro_1862 results in a ~1600-fold increase in the rate of ATP-dependent acetovanillone phosphorylation. We also find that recombinant Saro_1862 E16K phosphorylates several other aromatic compounds in vitro , defining the first reported catalytic activity for the widespread UPF0261 protein domain contained in Saro_1862. Thus, we propose naming Saro_1862 MarK, for multiple aromatic kinase. A 1.57 Å crystal structure of MarK E16K predicts that the E16K substitution lies in a potential ATP binding site, suggesting how this amino acid change increased catalytic activity. A search for homologs of MarK and other proteins required for acetovanillone degradation predicts that this pathway for aromatic metabolism exists throughout the bacterial phylogeny.

Novosphingobium↗

Corrosion of novel reactive silver ink and commercial silver-based metallizations in diluted acetic acid

Silver-based metallizations in photovoltaic modules are susceptible to corrosion by acetic acid generated in ethylene vinyl acetate encapsulated modules, resulting in power losses over time. Here, three silver-based metallizations are exposed to diluted acetic acid, in concentrations representative of that found in field-exposed modules. Compositional, morphological, and structural changes of the metallizations are studied over 3000 h of exposure to diluted acetic acid using Raman spectroscopy mapping, X-ray diffraction, and scanning electron microscopy. The three metallizations studied are: 1) a commercial high-temperature fire-through Ag paste, commonly used for Si diffused junction solar cells; 2) a commercial low-temperature paste normally used for silicon heterojunction cells; and 3) a novel low-temperature reactive silver ink shown to be suitable for photovoltaic applications. We find distinct corrosion rates for the high-temperature silver paste and reactive silver ink in the presence of diluted acetic acid. However, the low-temperature silver paste appears to be more corrosion resistant, likely due to a polymer layer that protects the silver particles.

36 MATERIALS SCIENCE↗

Topotaxially grown composite cathodes for cobalt-free high-energy long-life Li-ion batteries

The vehicle industry’s increasing demand for electrification necessitates the removal of expensive and rare cobalt from current high-energy batteries. However, eliminating cobalt poses challenges due to its vital role in maintaining the layered structural ordering and cycling stability of commonly used Li(NiMnCo)O 2 cathodes. As an alternative to conventional layered oxide designs, we report a lithium nickelate cathode with a composite structure comprising major stoichiometric layered and minor rocksalt phases within the same oxygen lattice. This material outperforms conventional designs by maintaining stable battery operation at voltages up to 4.8 V vs. Li|Li + , with 88% capacity retention after 1000 cycles at 2C. The topotaxial-growth-enabled interlock between the two components mitigates chemo-mechanical degradation, offering a promising pathway to cobalt-free cathodes. Additionally, we reveal a miscibility gap in the Li-Ni-O system that enables kinetic adjustment of composition and structure during sintering, thereby tuning the functionality of high-energy cathodes.

25 ENERGY STORAGE↗

The future of subsurface monitoring: AEC’s breakthroughs in CCS technology

Carbon capture and storage (CCS) has emerged as a key solution in the fight against climate change. However, for CCS to succeed, it is crucial to ensure that the sequestered CO2 stays safely trapped underground. The U.S. Department of Energy (DOE) has emphasized the need for advancements in subsurface monitoring, measurement, reporting, and verification. Aside from caprock integrity failure, the other primary failure points usually involve defective cement in the casing annulus of wellbores or plugged and abandoned wells. In addition, many energy producers (e.g., oil and gas, geothermal) and storage and disposal operators (e.g., H2 and water) must deal with the same issue. Poorly placed or degraded cement can create pathways for gas or fluid to escape from casing annuli and in plugged and abandoned or orphan wells, posing environmental risks. Yet, a reliable and cost-effective way to monitor cement and well integrity over multiple decades is still unavailable. Traditional geophysical methods like 4D seismic imaging and surface-based electromagnetic monitoring lack the resolution and accuracy for detecting these types of failures (Vasco et al., 2022; Fawad and Mondol, 2021). Wireline logging is expensive to run continuously and is obtrusive to the operation. While fiber optics can potentially be a solution, its bulkiness can significantly compromise the cement's integrity. To address these challenges, the Advanced Energy Consortium (AEC) at The University of Texas at Austin’s Bureau of Economic Geology (the Bureau) has been pioneering research in subsurface monitoring using its portfolio of distributed autonomous microfabricated sensors for harsh subsurface environments since 2008. A class of these microsensors [System on a Chip (SoC)] can be mixed in cement and permanently placed without compromising the cement column; the sensors would then communicate with each other or a data acquisition (DAQ) master node. Another class of the AEC microsensors can be fully autonomous, with rechargeable micro-batteries capable of exceeding 100°C, flash memory, and, currently, a pressure and temperature sensor. They are designed to circulate in mud, geothermal fluids, U-loops, or pipelines. They can log data into memory and are unobtrusive to operations. Our team has been working on a multi-year DOE-funded project (DE-FE0031856)—supported by $2.95M in federal funding and $0.75M in cost-matching from the AEC—to demonstrate SoC sensor utility for CO2 leakage monitoring in CCS applications. This multi-institutional collaboration developed a novel sensing architecture utilizing radiofrequency (RF) microsensors embedded within the cement sheath. These sensors detect CO2 migration and are interrogated via a Smart Casing Collar (SCC).

58 GEOSCIENCES↗

Multi-strain analysis of Pseudomonas putida reveals the metabolic and genetic diversity of the species

Pseudomonas putida is a gram-negative bacterial species increasingly utilized in biotechnology due to its robust growth, ability to degrade aromatic compounds, solvent tolerance, and genetic tractability. In this study, we report a comprehensive multi-strain analysis of 164 P. putida strains based on the reconstruction of a pan-putida metabolic network and the formulation of strain-specific genome-scale metabolic models (GEMs). We performed whole-genome sequencing and hybrid assembly for 40 strains, contributing a ~8% increase to the available genomic data for P. putida . Furthermore, high-throughput phenotypic profiling using the Biolog phenotype microarray system for 24 strains on 190 unique carbon sources, along with 15 aromatic compounds not present on Biolog plates, yielded 4,920 unique strain-phenotype measurements. These data were leveraged to curate GEMs for 24 representative strains, including a refined model for strain KT2440, which comprised 1,480 genes and 2,191 metabolites, achieving a prediction accuracy of 91.2% in carbon utilization. Systematic comparison of genomes and GEMs revealed both conserved core pathways and significant allelic and functional divergence across strains, highlighting strain-specific variation in aromatic degradation. While pathways for protocatechuate and phenylacetate degradation were widely conserved, metabolic capabilities for compounds such as ferulate, phenol, and cresols varied markedly, suggesting adaptation to distinct ecological niches. Alleleome analysis of enzymes, such as PcaI and PcaJ, revealed distinct, functionally similar clades, indicating possible convergent evolution or horizontal gene transfer. These results provide computable resources and informative models for selecting P. putida strains with desired traits for biomanufacturing and bioremediation and offer insights into the evolution and phylogeny of the P. putida species.

aromatics utilization↗

Adsorption-Engineered Hydrocarbon Ionomers for Durable Proton-Exchange Membrane Fuel Cells

Reducing reliance on perfluoroalkyl substances (PFAS) in proton-exchange membrane fuel cells requires hydrocarbon ionomers that combine high performance with long-term durability, a persistent challenge in catalyst-layer design. Here, we identify oxidation-driven ionomer-catalyst interfacial degradation as a dominant failure pathway in hydrocarbon ionomer-bonded cathodes and introduce an adsorption-engineering strategy to overcome this limitation. The comparison of a commercial sulfonated poly(phenylene) (Pemion) with structurally engineered sulfonated poly(fluorene)s demonstrated that electrode durability is governed by the interplay between ionomer adsorption strength and resistance to oxidative degradation on carbon-supported Pt catalysts. A poly(fluorene) ionomer with mobile alkyl sulfonic acid groups forms resilient interfaces, delivering 1.28 A cm−2 at 0.65 V under fully humidified H2/air conditions (80°C and 150 kPaabs), comparable to Pemion. After 90,000 accelerated potential cycles, the poly(fluorene)-bonded cathode exhibits significantly improved durability, with only 29% performance loss compared to 58% for Pemion; further molecular refinement reduces the loss to 17%, approaching that of Nafion-bonded cathodes (14%). These findings establish adsorption-engineered ionomer design that decouples interfacial anchoring from oxidative degradation as a general strategy for achieving durable, high-performance PFAS-free PEM fuel cell electrodes.

08 HYDROGEN↗

ShadeLab/PAPER_Howe_2023_switchgrass_MetaT

The raw data (metagenomes and metatranscriptomes) for this study are available in the Joint Genomes Institute Genome Portal (https://genome.jgi.doe.gov/portal/ Project ID 503249) with projects designated by year and product type. The MAG genomes analyzed in this paper are available on NCBI, as bioproject PRJNA800073. Plants and microorganisms form beneficial associations. Understanding plant-microbe interactions will inform microbiome management to enhance crop productivity and resilience to stress. Here, we apply a genome-centric approach to identify ecologically important leaf microbiome members on field-grown switchgrass and miscanthus and to quantify their activities for switchgrass over two growing seasons. We integrate metagenome and metatranscriptome sequencing from 192 leaf samples collected over representative time points in crop phenology. We curated 40 medium- and high-quality metagenome-assembled-genomes (MAGs) and focused analysis on seasonal transcript recruitment to them. Classes represented by these focal MAGs (Actinomycetia, Alpha- and Gamma- Proteobacteria, and Bacteroidota) were active and had increases in transcripts for short-chain dehydrogenase, molybdopterin oxidoreductase, and polyketide cyclase in the late season. The majority of MAGs had activated stress-associated pathways, including trehalose metabolism, indole acetic acid degradation, betaine biosynthesis, and reactive oxygen species degradation, suggesting direct engagement with the host environment. We also detected seasonally activated biosynthetic pathways for terpenes (carotenoids and isoprenoids) and for various non-ribosomal peptide pathways that were poorly annotated. Overall, this study overcame laboratory and bioinformatic challenges associated with field-based leaf metatranscriptome analysis to inform both general and likely specialized activities of these phyllosphere populations. These activities collectively support that leaf-associated bacterial populations are seasonally dynamic, responsive to host cues, and interactively engage in feedback with the plant. This analysis represented quality filtering of metagenomes and metatranscriptomes (data-preparation folder), metagenome assemblies (metagenome-assembly folder) and metagenome-assembled genome binning, curation, refinement, annotation (mag-evaluation folder). Abundances of sequencing libraries were calculated based on reads mapped (mapping folder). Additionallly, analysis of our annotated results are also included (analysis folder).

Howe, Adina↗

Nanoscopic strain evolution in single-crystal battery positive electrodes

Single-crystal Ni-rich layered oxides (SC-NMC) with a grain-boundary-free configuration have effectively addressed the long-standing cracking issue of conventional polycrystalline Ni-rich materials (PC-NMC) in lithium-ion batteries, prompting a shift in optimization strategies. However, continued reliance on anisotropic lattice volume change—a well-established failure indicator in PC-NMC—as a metric for understanding strain and guiding compositional design for SC-NMC becomes controversial. Here, in this study, by leveraging multiscale diagnostic techniques, we unravelled the distinct nanoscopic strain evolution in SC-NMC during battery operation, challenging the conventional composition-driven strategies and mechanical degradation indicators used for PC-NMC. Through particle-level chemomechanical analysis, we reveal a decoupling between mechanical stability and lattice volume change in SC-NMC, identifying that structural instability in SC materials is primarily driven by multidimensional lattice distortions induced by kinetics-driven reaction heterogeneity and progressively deactivating chemical phases. Using this mechanical failure mode, we redefine the roles of cobalt and manganese in maintaining mechanical stability. Unlike cobalt’s detrimental role in PC-NMC, we find cobalt to be critical in enhancing the longevity of SC-NMC by mitigating localized strain along the extended diffusion pathway, whereas manganese exacerbates mechanical degradation.

36 MATERIALS SCIENCE↗

Evolving a New Electron Transfer Pathway for Nitrogen Fixation Uncovers an Electron Bifurcating-Like Enzyme Involved in Anaerobic Aromatic Compound Degradation

There is increasing evidence that protein electron carriers like Fd evolved to form specific partnerships with select electron donors and acceptors to keep native electron transfer pathways insulated from one another. This makes it challenging to integrate a Fd-dependent pathway such as biological nitrogen fixation into non-nitrogen-fixing organisms and provide the high-energy reducing power needed to fix nitrogen.

59 BASIC BIOLOGICAL SCIENCES↗