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At least 1,135 records · Page 63

Plant litter traits control microbial decomposition and drive soil carbon stabilization

Efforts to manage soils for carbon (C) sequestration remain limited by our understanding of how differences in plant traits and microbial traits mechanistically drive soil organic C (SOC) storage. Addressing this uncertainty is particularly critical in bioenergy agriculture, due to its potential to enhance soil C and provide a C neutral fuel. As such, we examined differences between two contrasting feedstocks, Zea mays (corn) and Miscanthus x giganteus (miscanthus), in the ability of their litter to form new chemically resistant particulate SOC vs. physically protected mineral associated SOC and used this data to improve the parameterization of a microbial SOC model. We tested a hypothesized conceptual model whereby easy to decompose corn litters drive greater microbial carbon use efficiency (CUE) and the formation of more mineral associated SOC over particulate SOC than more complex miscanthus litters. To do this, we performed a soil microcosm experiment where we added 13 C enriched aboveground and belowground litters to soils and traced the fate of the 13 C into microbial respiration and SOC pools. We found that corn litters promoted higher microbial CUE (0.37) than miscanthus litters (0.24). In turn, corn litter formed approximately 50% more mineral associated SOC than miscanthus litters. Similarly, structurally complex root litters promoted a lower CUE and formed less mineral associated SOC than leaf and shoot litters for both crops. When we used our data to parameterize the SOC model, we found that modelling microbial trait differences uniquely allowed the model to capture the fate of litter C in SOC. Collectively, we found a robust link between litter quality, microbial efficiency, and the formation of SOC. This link bridges the empirical uncertainty in how different crops can form new soil C and provides an empirical basis for modelling SOC transformations.

59 BASIC BIOLOGICAL SCIENCES↗

Active populations and growth of soil microorganisms are framed by mean annual precipitation in three California annual grasslands

Climate influences soil microbial composition and function, but the relative importance of a site's historic climate versus its more immediate environmental conditions is unclear. Using quantitative stable isotope probing (qSIP), we characterized actively growing soil microbial communities and soil properties in three California annual grasslands that span a rainfall gradient and have developed on similar parent material. The soils were assayed in the wet winter season, when environmental conditions are most similar across sites. Since growing populations might be expected to be most responsive to contemporary environmental conditions, we hypothesized that the structure of growing microbial communities would be more similar across the gradient than that of total communities (i.e., including non-growing populations). In addition, we hypothesized that population growth rates would be slowest in the driest site, reflecting a legacy effect of low soil moisture on microbial growth. Soils along the rainfall gradient differed in pH, texture, and cation exchange capacity, but not in total C, C:N or dominant minerals. The radiocarbon (14C) age of soil C (reflecting turnover time) increased with mean annual precipitation but soil respiration was uniformly modern, reflecting microbial reliance on recent C inputs across the sites. The structure of both total and growing microbial communities differed across sites. Across major microbial phyla, including the Actinobacteria, Acidobacteria, Bacteroidetes, Gemmatimonadetes and Proteobacteria, bacterial growth rates were consistently lower in the site with the lowest mean annual precipitation. Taxa that were growing at the dry site alone grew more slowly than taxa that grew at multiple sites. These results reflect the influence of climate history and point to the role of environmental filtering at the driest site in shaping its slower growing microbial community, possibly reflecting adaptation to repeated exposure to water stress. Lastly, across taxa, the growth rate of a taxon at one site was correlated with its growth rate in the other sites. Furthermore, this growth rate coherence is likely a consequence of genetically determined physiological traits and is consistent with the idea that evolutionary history constrains growth rate.

Environmental filtering↗

Reactive iron, not fungal community, drives organic carbon oxidation potential in floodplain soils

Wetlands host ∼20% of terrestrial organic carbon and serve as a major sink for atmospheric carbon. Anoxic soils and sediments accrue soil organic carbon (SOC) partly by hampering the activity of extracellular oxidative enzymes that break down phenolic polymers. Upon aeration, fungal-driven oxidative enzymatic depolymerization and microbial respiration of released monomers ensue. Redox-active metals can simultaneously catalyze abiotic nonspecific oxidation of SOC, notable examples including Mn(III) or Fe(II) through Fenton-like, hydrogen peroxide-catalyzed oxidative radical production. However, the extent of reactive metal contributions to biotic and abiotic SOC degradation is not understood in the context of natural environments with diverse redox chemistry. We tested the relative contributions of fungi, Mn(III) and Fe(II) to phenolic substrate (L-DOPA) oxidation in floodplain soils representing a range of transient redox conditions driven by permanent vs. periodic flooding. Phenol oxidative potential was highest in permanently flooded soils with fewer fungal taxa known for observed (per)oxidase activity and instead correlated with HCl-extractable Fe(II), Fe(total) and Fe(II)/Fe(total), suggesting a specific role of Fe(II). Fe(II) additions enhanced phenol oxidative potential in sterilized and non-sterilized soils in the presence of hydrogen peroxide, indicating abiotic Fe-mediated radical chemistry could significantly enhance wetland SOC oxidative depolymerization throughout redox-active floodplain soils. Fungal community composition did not correlate to phenol oxidative potential overall and only more oxic soils adjacent to the river with diverse fungal communities showed declining oxidative potential after sterilization. Mn(III) addition did not significantly enhance phenol oxidative potential across all soils, although it appeared to drive fungal-mediated oxidative potential in the most aerated floodplain soils. Understanding how metals mediate SOC depolymerization as abiotic oxidants or microbially-harnessed enzyme cofactors and substrates in soils under variable hydrologic controls will improve our ability to represent depolymerization in terrestrial carbon models in wetland and other frequently saturated soils.

59 BASIC BIOLOGICAL SCIENCES↗

Thermodynamic control on the decomposition of organic matter across different electron acceptors

The increasing availability of high-resolution characterization of natural organic matter (OM) data has shifted the paradigm of lumped descriptions of OM components and potential microbial activities. Our recent development of a substrate-explicit thermodynamic model uniquely enables incorporating complex OM pools to formulate biogeochemical reaction models based on their elemental compositions. While this previous work facilitates prediction of aerobic respiration of complex OM, it is equally imperative to consider the role of non-oxygenic electron acceptors in regulating OM turnover and the fate of carbon. In this study, we significantly expand our previous model by flexibly incorporating both detailed OM chemistry and electron acceptors other than oxygen. Here, our modeling analysis has revealed substantial variations in the energy status of OM molecules across different soils, which drive the co-occurrence of different electron-accepting processes. We demonstrated the effectiveness of the proposed model using a consistency check with experimental data. Through systematic evaluation of the impact of diverse chemical inputs (both electron donors and acceptors) on OM decomposition, the new model also revealed how key microbial growth parameters such as carbon use efficiency (CUE) and reaction rates vary across different electron-accepting processes. Our model provides a unified framework integrating thermodynamic and kinetic constraints on microbial metabolic activities. It complements traditional kinetic models, which are often designed solely to capture mass fluxes. We conclude that thermodynamic modeling emerges as a powerful tool for describing the mechanisms underlying the interplay between microbial growth and OM chemistry and cycling across different electron acceptors, enhancing our ability to project complex ecosystem behaviors in dynamic environments.

59 BASIC BIOLOGICAL SCIENCES↗

Moisture-mineral interactions drive bacterial and organic matter turnover in glacier-sourced riparian sediments undergoing pedogenesis

Glacial recession is occurring at unprecedented rates resulting in increased sediment accumula-tions in some riverine ecosystems. Increased sediment deposition has implications for ecosystem stability (e.g., floods and river paths) and environmental services (e.g., carbon sequestration). Soils and sediments have an enormous potential to retain carbon (C), predominantly due to sorp-tion to mineral surfaces. However, C persistence may be sensitive to climate-change induced temperature and moisture variations. We coupled ultrahigh resolution organic matter composition classification with bacterial characterization and respiration measurements to test the combined effects of temperature (4 vs 20°C) and moisture (50 vs 100% water-filled pore space) on C turn-over in sediments maintained under different mineralogical conditions (illite-amended vs non-amended). Here we show that the inhibition of CO 2 emissions from the combined effect of in-creased moisture content and illite was reflected in the turnover of key molecular signatures, such as the nominal oxidation state of C, often irrespective of temperature. However, shifts in bacteri-al communities from a coupled moisture-mineral interaction, were temperature-dependent. Our results highlight the importance of moisture in driving mineral-organic interactions and suggest that C in clay-rich, water-saturated sediments is both thermodynamically unfavorable and miner-al-protected from microbial consumption.

58 GEOSCIENCES↗

Shrub and sedge rhizosphere communities display distinct affinities toward exudates and soil organic matter degradation: a quantitative stable isotope probing analysis

Warming temperatures are accelerating permafrost thaw and changing tundra vegetation, where woody shrubs are displacing sedges. Shrubs, such as Betula nana, and sedges, such as Eriophorum vaginatum, exhibit distinct life strategies including unique root-associated, or rhizosphere microbial communities. As permafrost thaws it unlocks previously unavailable carbon and nutrient sources resulting in deeper roots and a translocation of rhizosphere communities. Because permafrost microbial communities contain lower diversity and biomass than rhizosphere communities, the coalescence of rhizosphere and permafrost microbial communities could alter soil organic matter (SOM) degradation rates and increase greenhouse gas emissions. To identify metabolic strategies across distinct rhizosphere and permafrost microbial communities we conducted an isotope tracing incubation experiment. We inoculated thawed permafrost with shrub and sedge rhizosphere communities while adding exudates or water daily and compared this to an uninoculated control. After 46 days, we spiked samples with 18O enriched water or 13C enriched exudates and measured isotope incorporation into microbial DNA with quantitative stable isotope probing (qSIP). Our results indicate that exudate additions had little effect on uninoculated permafrost communities but the addition of exudates and rhizosphere inoculants had a compounding effect on respiration rates. We found that soils inoculated with shrub rhizosphere communities contained a mixture of exudate and SOM degraders while soils inoculated with sedge rhizosphere communities contained mainly SOM degraders. Finally, we found that individual microbial taxa exhibited maximum growth rates under specific combinations of microbial inoculant communities and exudate addition treatments. Our results reveal that microbial niches are strongly influenced by substrate preferences and community context, and suggest that a reduction in sedges and an expansion of shrubs may provide a mechanism by which permafrost carbon losses are mitigated through corresponding shifts in microbial communities and their substrate preferences.

Schaefer, Sean R [Natural Resources and Earth Syst↗

Nitrogen fixation in Pampinifervens , a new species-rich genus of Aquificaceae that inhabits a wide pH range in terrestrial hot springs

Members of the Aquificota play important roles in hydrogen, sulfur, and carbon cycles in geothermal systems as ubiquitous and abundant chemolithoautotrophs; however, their roles in the nitrogen cycle are poorly defined. Here, we show that Aquificaceae isolate T-2 T from Tengchong, China, fixes nitrogen based on growth with dinitrogen as the sole nitrogen source and incorporation of 15 N atoms when grown with 15 N 2 . We further show evidence that suggests its nitrogen fixation (nif) genes are transcribed in situ in a nearby spring. We propose the name Pampinifervens diazotrophicum gen. et sp. nov., with strain T-2 T (= JCM 35475 T = DSM 116324 T ) as the nomenclatural type. Its close relative designated Pampinifervens florentissimum sp. nov. T-8 T (= CGMC 1.5214 T = JCM 33569 T ) does not fix nitrogen but respires nitrate. Analysis of 104 metagenome-assembled genomes from 84 metagenomes allowed us to circumscribe the genus Pampinifervens and identify at least 16 sympatric Pampinifervens species that dominate the Aquificaceae populations in diverse hot springs in southwest China, with distinct species globally. Analysis of these Pampinifervens genomes revealed variable presence of nif and denitrification genes and frequent gene loss and horizontal transfer. Genes for pH homeostasis were also present in Pampinifervens genomes, with a proliferation in species from Tengchong, consistent with the wide pH growth range of both Pampinifervens isolates and the prevalence of Pampinifervens in both alkaline and acidic springs. The dynamic evolution of nif and denitrification genes, along with pH homeostasis genes, may facilitate the diversification of Pampinifervens into diverse springs with different nitrogen availability.

Aquificae↗

Mechanistic review of drug-induced steatohepatitis

Drug-induced steatohepatitis is a rare form of liver injury known to be caused by only a handful of compounds. These compounds stimulate the development of steatohepatitis through their toxicity to hepatocyte mitochondria; inhibition of beta-oxidation, mitochondrial respiration, and/or oxidative phosphorylation. Other mechanisms discussed include the disruption of phospholipid metabolism in lysosomes, prevention of lipid egress from hepatocytes, targeting mitochondrial DNA and topoisomerase, decreasing intestinal barrier function, activation of the adenosine pathway, increasing fatty acid synthesis, and sequestration of coenzyme A. It has been found that the majority of compounds that induce steatohepatitis have cationic amphiphilic structures; a lipophilic ring structure with a side chain containing a cationic secondary or tertiary amine. Within the last decade, the ability of many chemotherapeutics to cause steatohepatitis has become more evident coining the term chemotherapy-associated steatohepatitis (CASH). The mechanisms behind drug-induced steatohepatitis are discussed with a focus on cationic amphiphilic drugs and chemotherapeutic agents. - Highlights: • Reviewed the mechanisms underlying drug-induced steatohepatitis for many compounds • Mitochondrial dysfunction is critical in the development of drug-induced steatohepatitis. • Majority of drugs that induce steatohepatitis are cationic amphiphilic drugs. • Chemotherapeutics that induce CASH are cationic amphiphilic drugs. • Majority of drugs that induce steatohepatitis are carnitine palmitoyltransferase-I inhibitors.

60 APPLIED LIFE SCIENCES↗

HSP90 and pCREB alterations are linked to mancozeb-dependent behavioral and neurodegenerative effects in a marine teleost

The pesticide mancozeb (mz) is recognized as a potent inducer of oxidative stress due to its ability to catalyze the production of reactive oxygen species plus inhibiting mitochondrial respiration thus becoming an environmental risk for neurodegenerative diseases. Despite numerous toxicological studies on mz have been directed to mammals, attention on marine fish is still lacking. Thus, it was our intention to evaluate neurobehavioral activities of ornate wrasses (Thalassoma pavo) exposed to 0.2 mg/l of mz after a preliminary screening test (0.07–0.3 mg/l). Treated fish exhibited an evident (p < 0.001) latency to reach T-maze arms (> 1000%) while exploratory attitudes (total arm entries) diminished (− 50%; p < 0.05) versus controls during spontaneous exploration tests. Moreover, they showed evident enhancements (+ 111%) of immobility in the cylinder test. Contextually, strong (− 88%; p < 0.01) reductions of permanence in light zone of the Light/Dark apparatus along with diminished crossings (− 65%) were also detected. Conversely, wrasses displayed evident enhancements (160%) of risk assessment consisting of fast entries in the dark side of this apparatus. From a molecular point of view, a notable activation (p < 0.005) of the brain transcription factor pCREB occurred during mz-exposure. Similarly, in situ hybridization supplied increased HSP90 mRNAs in most brain areas such as the lateral part of the dorsal telencephalon (Dl; + 68%) and valvula of the cerebellum (VCe; + 35%) that also revealed evident argyrophilic signals. Overall, these first indications suggest a possible protective role of the early biomarkers pCREB and HSP90 against fish toxicity. - Highlights: • Fish exposed to mancozeb exhibited an evident latency to reach T-maze arms. • Mancozeb caused immobility and reduction of explorative attitudes. • Fish exposed to mancozeb showed anxiogenic performances in the Light/Dark apparatus. • The brain of fish exposed to mancozeb supplied pCREB plus HSP90 mRNA up-regulations. • Some brain areas of fish exposed to mancozeb revealed an evident neurodegeneration.

60 APPLIED LIFE SCIENCES↗

Composting of the solid fraction of digestate derived from pig slurry: Biological processes and compost properties

Highlights: • Anaerobic digestion leads to the production of a biologically stable digestate. • Solid–liquid separation produces a solid fraction having high fertilizer value. • Composting process shows low biological activity due to high biological stability of digestate. • Solid digestate fraction can be composted in a short time or used directly as organic fertilizer. - Abstract: The aim of this paper was to assess the characteristics of the solid fractions (SF) obtained by mechanical separation of digestate, their compostability and compost quality. To do so, the SF of digestates obtained from anaerobic digestion of pig slurry, energy crops and agro-industrial residues were sampled in five plants located in Northern Italy. Results obtained indicated that anaerobic digestion by itself promoted the high biological stability of biomasses with a Potential Dynamic Respiration Index (PDRI) close to 1000 mgO{sub 2} kg V S{sup −1} h{sup −1}. Subsequent composting of digestates, with an added bulking agent, did not give remarkably different results, and led only to a slight modification of the characteristics of the initial non-composted mixtures; the composts obtained fully respected the legal limits for high quality compost. Chemical studies of organic matter composition of the biomasses by using CP MAS {sup 13}C NMR, indicated that the compost was composed of a high relative content of O-alkyl-C (71.47% of total C) (cellulose and hemicelluloses) and a low alkyl-C (12.42%) (i.e. volatile fatty acids, steroid-like molecules, aliphatic biopolymers and proteins)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Organic colloid composition in variable-redox porewaters within a mountainous floodplain

Redox gradients, often driven by changes in sediment moisture levels in porous, heterogeneous groundwater systems, create dynamic conditions that may promote the production and transport of colloids within natural waters. While much research has focused on the inorganic composition of colloids, the organic composition remains less well understood. Organic matter (OM) in colloids may associate with minerals, complex metal ions, and serve as an electron donor for microbial respiration; therefore, its composition is of high interest. We examined the composition of porewater OM along a redox gradient in a riparian soil located along the Slate River in Crested Butte, Colorado, USA as a function of depth (90, 130, 200, and 350 cm below ground surface). All depths were oxic to suboxic, except 200 cm, where the products of iron and sulfate reduction were observed concomitant with an increase in dissolved and/or colloidal OM, pH, alkalinity, and conductivity. We investigated the composition of porewater using correlated scanning transmission X-ray microscopy and transmission electron microscopy. We observed a change in the OM chemistry from carboxylate-rich at the 200 cm depth (where it was also enmeshed with non-crystalline iron) to phenol- and substituted-aromatic-rich at other depths. Radiocarbon dating revealed carbon in porewater at 200 cm was younger than depths above and below. Soil porewater can flow down into the underlaying gravel bed during baseflow conditions, thus we speculate whether riparian porewater could transport iron- and carboxylate-rich organic colloids into surrounding surface waters through the gravel bed conduit.

Alpine floodplain↗

Mitochondria control acute and chronic responses to hypoxia

There are numerous mechanisms by which mammals respond to hypoxia. These include acute changes in pulmonary arterial tone due to smooth muscle cell contraction, acute increases in respiration triggered by the carotid body chemosensory cells, and chronic changes such as induction of red blood cell proliferation and angiogenesis by hypoxia inducible factor targets erythropoietin and vascular endothelial growth factor, respectively. Mitochondria account for the majority of oxygen consumption in the cell and have recently been appreciated to serve as signaling organelles required for the initiation or propagation of numerous homeostatic mechanisms. Mitochondria can influence cell signaling by production of reactive oxygen species and metabolites. Here we review recent evidence that mitochondrial signals can imitate acute and chronic hypoxia responses. - Highlights: • Mitochondrial electron transport chain function plays a key role in organismal hypoxia sensing. • ETC Complex III ROS are necessary for acute hypoxic contraction of pulmonary smooth muscle cells. • ETC Complex I function is essential for acute glomus cell sensing of hypoxemia in the carotid body. • mROS are required for HIF stabilization and organismal adaptation to hypoxia.

60 APPLIED LIFE SCIENCES↗

Bioactivity and gene expression profiles of hiPSC-generated retinal ganglion cells in MT-ND4 mutated Leber's hereditary optic neuropathy

Highlights: • hiPSCs were obtained from LHON-mutation affected and carrier individuals. • LHON-specific hiPSCs were differentiated to RGCs to create in vitro disease model. • LHON-affected RGCs have defective neuritogenesis. • LHON-specific RGCs have increased compensatory mitochondrial biogenesis. • LHON-affected mitochondria have decreased spare respiratory capacity. Leber’s hereditary optic neuropathy (LHON) is the maternally inherited mitochondrial disease caused by homoplasmic mutations in mitochondrial electron transport chain Complex I subunit genes. The mechanism of its incomplete penetrance is still largely unclear. In this study, we created the patient-specific human induced pluripotent stem cells (hiPSCs) from MT-ND4 mutated LHON-affected patient, asymptomatic mutation carrier and healthy control, and differentiated them into retinal ganglion cells (RGCs). We found the defective neurite outgrowth in affected RGCs, but not in the carrier RGCs which had significant expression of SNCG gene. We observed enhanced mitochondrial biogenesis in affected and carrier derived RGCs. Surprisingly, we observed increased NADH dehydrogenase enzymatic activity of Complex I in hiPSC-derived RGCs of asymptomatic carrier, but not of the affected patient. LHON mutation substantially decreased basal respiration in both affected and unaffected carrier hiPSCs, and had the same effect on spare respiratory capacity, which ensures normal function of mitochondria in conditions of increased energy demand or environmental stress. The expression of antioxidant enzyme catalase was decreased in affected and carrier patient hiPSC-derived RGCs as compared to the healthy control, which might indicate to higher oxidative stress-enriched environment in the LHON-specific RGCs. Microarray profiling demonstrated enhanced expression of cell cycle machinery and downregulation of neuronal specific genes.

60 APPLIED LIFE SCIENCES↗

Leucyl-tRNA synthetase is required for the myogenic differentiation of C2C12 myoblasts, but not for hypertrophy or metabolic alteration of myotubes

Highlights: • siRNA-mediated Lars knockdown blocked C2C12 myoblast differentiation into myotubes. • Lars knockdown decreased Igf2 mRNA expression from an early differentiation stage. • Lars knockdown decreased phosphorylated p70 S6 kinase but did not activate Akt. • Lars knockdown did not decrease phospho-mTOR nor affect hypertrophy or metabolism of myotube. Mammalian target of rapamycin (mTOR) signaling controls skeletal muscle cell differentiation, growth, and metabolism by sensing the intracellular energy status and nutrients. Recently, leucyl-tRNA synthetase (Lars) was identified as an intracellular sensor of leucine involved in the activation of mTOR signaling. However, there is still no evidence for the activation of mTOR signaling by Lars and its physiological roles in skeletal muscle cells. In this study, we determined the potential roles of Lars for the activation of mTOR signaling, skeletal muscle cell differentiation, hypertrophy, and metabolism using small interfering (si)-RNA knockdown. siRNA-mediated knockdown of Lars decreased phosphorylated p70 S6 kinase and inhibited the differentiation of C2C12 mouse myoblasts into myotubes, as evidenced by a decreased fusion index and decreased mRNA and protein expression levels of myogenic markers. Importantly, si-Lars decreased the level of Insulin-like growth factor 2 (Igf2) mRNA expression from the early stages of differentiation, indicating the possibility of an association between the mTOR–IGF2 axis and Lars. However, Lars knockdown did not decrease phosphorylated mTOR in differentiated myotubes, nor did it affect the hypertrophy of myotubes as evidenced by measuring their diameters and detecting the mRNA and protein expression of hypertrophy markers. Similarly, an extracellular flux analyzer showed that Lars knockdown did not affect the metabolism (glycolysis and mitochondrial respiration) of myotubes. These results demonstrate that Lars is required for skeletal muscle differentiation through the activation of mTOR signaling, but not for hypertrophy or metabolic alteration of myotubes.

60 APPLIED LIFE SCIENCES↗

Radiocarbon analysis of soil microbial biomass via direct chloroform extraction

Microbial processing of soil organic matter is a significant driver of C cycling, yet we lack an understanding of what shapes the turnover of this large terrestrial pool. In part, this is due to limited options for accurately identifying the source of C assimilated by microbial communities. Laboratory incubations are the most common method for this; however, they can introduce artifacts due to sample disruption and processing and can take months to produce sufficient CO 2 for analysis. We present a biomass extraction method which allows for the direct 14 C analysis of microbial biomolecules and compare the results to laboratory incubations. In the upper 50 cm soil depths, the Δ 14 C from incubations was indistinguishable from that of extracted microbial biomass. Below 50 cm, the Δ 14 C of the biomass was more depleted than that of the incubations, either due to the stimulation of labile C decomposition in the incubations, the inclusion of biomolecules from non-living cells in the biomass extractions, or differences in C used for assimilation versus respiration. Our results suggest that measurement of Δ 14 C of microbial biomass extracts can be a useful alternative to soil incubations.

54 ENVIRONMENTAL SCIENCES↗

Scanning Electrochemical Microscopy: An Evolving Toolbox for Revealing the Chemistry within Electrochemical Processes

The parallel development of ultramicroelectrodes (UMEs) and groundbreaking scanning probe microscopy techniques in the late 1980s led to the development of the scanning electrochemical microscope. Scanning electrochemical microscopy (SECM) was born from the idea of using a tiny electrode to measure the local electrochemical behavior at operating electrodes. From its foundations, the technique displayed an inherent versatility in measuring sample properties beyond topography. It allowed experimenters to measure and map chemical reactions occurring at diverse interfaces, from inspecting the reversibility of redox mediators at metal electrodes, to detecting the hallmarks of cellular respiration on living plant leaves. Related but distinct electrochemical scanning probe techniques, such as electrochemical atomic force microscopy (EC-AFM), scanning ion conductance microscopy (SICM), and scanning electrochemical cell microscopy (SECCM) have developed in parallel. These techniques have demonstrated exquisite spatial resolution down to the nanoscale regime. However, it is the proposition of this review that SECM remains unmatched at revealing the chemical aspects of electrochemistry. Furthermore, it is our intention to review and demonstrate that the versatile architecture of SECM continues to evolve and address fundamental and emerging challenges in the fields of energy storage and conversion, chemical biology, materials science, and environmental chemistry, among others.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Redox potential tuning through differential quinone binding in the photosynthetic reaction center of Rhodobacter sphaeroides

Ubiquinone forms an integral part of the electron transport chain in cellular respiration and photosynthesis across a vast number of organisms. Prior experimental results have shown that the photosynthetic reaction center (RC) from Rhodobacter sphaeroides is only fully functional with a limited set of methoxy-bearing quinones, suggesting that specific interactions with this substituent are required to drive electron transport and the formation of quinol. The nature of these interactions has yet to be determined. Through parameterization of a CHARMM-compatible quinone force field and subsequent molecular dynamics simulations of the quinone-bound RC, in this paper we have investigated and characterized the interactions of the protein with the quinones in the Q A and Q B sites using both equilibrium simulation and thermodynamic integration. In particular, we identify a specific interaction between the 2-methoxy group of ubiquinone in the Q B site and the amide nitrogen of GlyL225 that we implicate in locking the orientation of the 2-methoxy group, thereby tuning the redox potential difference between the quinones occupying the Q A and Q B sites. Finally, disruption of this interaction leads to weaker binding in a ubiquinone analogue that lacks a 2-methoxy group, a finding supported by reverse electron transfer electron paramagnetic resonance experiments of the Q A –Q B – biradical and competitive binding assays.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Global Life Cycle and Techno-Economic Assessment of Algal-Based Biofuels

Techno-economic analyses (TEAs) and life cycle assessments (LCAs) of algal biofuels often focus on locations in suboptimal latitudes for algal cultivation, which can under-represent the sustainability potential of the technology. This study identifies the optimal global productivity potential, environmental impacts, and economic viability of algal biofuels by using validated biophysical and sustainability modeling. The biophysical model simulates growth rates of Scenedesmus obliquusbased on temperature, photoinhibition, and respiration effects at 6685 global locations. Region-specific labor costs, construction factors, and tax rates allow for spatially resolved TEA, while the LCA includes regional impacts of electricity, hydrogen, and nutrient markets across ten environmental categories. The analysis identifies optimal locations for algal biofuel production in terms of environmental impacts and economic viability which are shown to follow biomass yields. Modeling results highlight the global variability of productivity with maximum yields ranging between 24.8 and 27.5 g m -2 d -1 in equatorial regions. Environmental impact results show favorable locations tracked with low-carbon electricity grids, with the well-to-wheels global warming potential (GWP) ranging from 31 to 45 g CO 2eq MJ -1 in South America and Central Africa. When including direct land use change impacts, the GWP ranged between 44 and 55 g CO 2eq MJ -1 in these high-productivity regions. Low-carbon electricity also favors air quality and eutrophication impacts. The TEA shows that minimum algal fuel prices of $\$1.89$-$\$2.15$ per liter of gasoline-equivalent are possible in southeast Asia and Venezuela. Furthermore, this discussion focuses on the challenges and opportunities to reduce fuel prices and the environmental impacts of algal biofuels in various global regions.

09 BIOMASS FUELS↗