Physicochemical Environment Research Articles

In Vitro Cell Model Investigation of Alpha-Synuclein Aggregate Morphology Using Spectroscopic Imaging.

Recently, it has been hypothesized that alpha-synuclein protein strain morphology may be associated with clinical subtypes of alpha-synucleinopathies, like Parkinson's disease and multiple system atrophy. However, direct evidence is lacking due to the caveat of conformation-specific characterization of protein strain morphology. Here we present a new cell model based in vitro method to explore various alpha-synuclein (αsyn) aggregate morphotypes. We performed a spectroscopic investigation of the HEK293 cell model, transfected with human wildtype-αsyn and A53T-αsyn variants, using the amyloid fibril-specific heptameric luminescent oligomeric thiophene h-FTAA. The spectral profile of h-FTAA binding to aggregates displayed a blue-shifted spectrum with a fluorescence decay time longer than in PBS, suggesting a hydrophobic binding site. In vitro spectroscopic binding characterization of h-FTAA with αsyn pre-formed fibrils suggested a binding dissociation constant Kd < 100 nM. The cells expressing the A53T-αsyn and human wildtype-αsyn were exposed to recombinant pre-formed fibrils of human αsyn. The ensuing intracellular aggregates were stained with h-FTAA followed by an evaluation of the spectral features and fluorescence lifetime of intracellular αsyn/h-FTAA, in order to characterize aggregate morphotypes. This study exemplifies the use of cell culture together with conformation-specific ligands to characterize strain morphology by investigating the spectral profiles and fluorescence lifetime of h-FTAA, based upon its binding to a certain αsyn aggregate. This study paves the way for toxicity studies of different αsyn strains in vitro and in vivo. Accurate differentiation of specific alpha-synucleinopathies is still limited to advanced disease stages. However, early subtype-specific diagnosis is of the utmost importance for prognosis and treatment response. The potential association of αsyn aggregates morphotypes detected in biopsies or fluids to disease phenotypes would allow for subtype-specific diagnosis in subclinical disease stage and potentially reveal new subtype-specific treatment targets. Notably, the method may be applied to the entire spectrum of neurodegenerative diseases by using a combination of conformation-specific ligands in a physicochemical environment together with other types of polymorphic amyloid variants and assess the conformation-specific features of various protein pathologies.

Migrating is not enough for modern planktonic foraminifera in a changing ocean.

Rising carbon dioxide emissions are provoking ocean warming and acidification1,2, altering plankton habitats and threatening calcifying organisms3, such as the planktonic foraminifera (PF). Whether the PF can cope with these unprecedented rates of environmental change, through lateral migrations and vertical displacements, is unresolved. Here we show, using data collected over the course of a century as FORCIS4 global census counts, that the PF are displaying evident poleward migratory behaviours, increasing their diversity at mid- to high latitudes and, for some species, descending in the water column. Overall foraminiferal abundances have decreased by 24.2 ± 0.1% over the past eight decades. Beyond lateral migrations5, our study has uncovered intricate vertical migration patterns among foraminiferal species, presenting a nuanced understanding of their adaptive strategies. In the temperature and calcite saturation states projected for 2050 and 2100, low-latitude foraminiferal species will face physicochemical environments that surpass their current ecological tolerances. These species may replace higher-latitude species through poleward shifts, which would reduce low-latitude foraminiferal diversity. Our insights into the adaptation of foraminifera during the Anthropocene suggest that migration will not be enough to ensure survival. This underscores the urgent need for us to understand how the interplay of climate change, ocean acidification and other stressors will impact the survivability of large parts of the marine realm.

Engineering of Single-Atomic Sites for Electro- and Photo-Catalytic H2O2 Production.

Direct electro- and photo-synthesis of H2O2 through the 2e- O2 reduction reaction (ORR) and H2O oxidation reaction (WOR) offer promising alternatives for on-demand and on-site production of this chemical. Exploring robust and selective active sites is crucial for enhancing H2O2 production through these pathways. Single-atom catalysts (SACs), featuring isolated active sites on supports, possess attractive properties for promoting catalysis and unraveling catalytic mechanisms. This review first systematically summarizes significant advancements in atomic engineering of both metal and nonmetal single-atom sites for electro- and photo-catalytic 2e- ORR to H2O2, as well as the dynamic behaviors of active sites during catalytic processes. Next, the progress of single-atom sites in H2O2 production through 2e- WOR is overviewed. The effects of the local physicochemical environments on the electronic structures and catalytic behaviors of isolated sites, along with the atomic catalytic mechanism involved in these H2O2 production pathways, are discussed in detail. This work also discusses the recent applications of H2O2 in advanced chemical transformations. Finally, a perspective on the development of single-atom catalysis is highlighted, aiming to provide insights into future research on SACs for electro- and photo-synthesis of H2O2 and other advanced catalytic applications.

Evidence for phospholipid self-organisation in concentrated ammonia-water environments

Titan, the largest moon of Saturn is thought to have the potential to support primordial life. The surface of Titan contains bodies of liquid hydrocarbons, and modelling suggests that an ammonia-water ocean resides deep beneath the surface, both of which have been speculated to support primordial chemistry. Here we present the first evidence that both preformed and self-organised phospholipid vesicles remain stable and can maintain concentration gradients in ammonia-water environments; a fundamental requirement for primordial chemistry and biology to originate. We further reveal the remarkable stability of a diether phospholipid, such as those found in extremophilic bacteria, under these conditions and demonstrate that electron microscopy and tomography are useful tools to investigate macromolecular structure under diverse physico-chemical environments.

Effects of long-term biodegradable film mulching on yield and water productivity of maize in North China Plain

Biodegradable films are considered ideal alternatives to polyethylene films because of their advantages in increasing crop yield and controlling soil pollution. However, the influences of biodegradable film mulching on soil physicochemical environments and water productivity after long-term mulching remain poorly understood. Therefore, a field experiment after long-term mulching (since 2016) was conducted to explore the effects of black biodegradable film (BB), transparent biodegradable film (TB), and traditional polyethylene film (PE) on soil physicochemical environments, aboveground biomass accumulation, grain yield, evapotranspiration, and water productivity (WP) of maize in the 2021 and 2022 in the North China Plain. The results showed that polyethylene films and biodegradable films had a similar ability to preserve soil moisture, promote maize growth, reduce evapotranspiration, and increase WP. Moreover, the performances of BB were more equivalent to PE, and there was no significant difference on WP and yield under BB and PE. Compared with traditional flat planting without mulching (CK), BB and PE significantly increased yield (9.5 % and 12.7 % in 2021; 5.25 % and 6.37 % in 2022) and WP (11.54 % and 21.47 % in 2021; 24.28 % and 23.42 % in 2022). Film mulching treatments increased the soil organic carbon sequestration rate, and the content of soil organic carbon, microbial activity, and urease activity in the 0–20 cm soil layer compared with CK. According to structural equation modeling, the increasing soil water storage because of films mulching positively influenced yield by enhancing enzyme activities which were related to soil nutrients. Over all, these results showed that black biodegradable film is an ideal replacement for polyethylene films under long-term mulching conditions because of its comparable agronomic performance and influence on soil physicochemical environments in the North China Plain.

Entangling roles of cholesterol-dependent interaction and cholesterol-mediated lipid phase heterogeneity in regulating listeriolysin O pore-formation.

Cholesterol-dependent cytolysins (CDCs) are the distinct class of β-barrel pore-forming toxins (β-PFTs) that attack eukaryotic cell membranes, and form large, oligomeric, transmembrane β-barrel pores. Listeriolysin O (LLO) is a prominent member in the CDC family. As documented for the other CDCs, membrane cholesterol is essential for the pore-forming functionality of LLO. However, it remains obscure how exactly cholesterol facilitates its pore formation. Here, we show that cholesterol promotes both membrane-binding and oligomerization of LLO. We demonstrate cholesterol not only facilitates membrane-binding, it also enhances the saturation threshold of LLO-membrane association, and alteration of the cholesterol-recognition motif in the LLO mutant (LLOT515G-L516G) compromises its pore-forming efficacy. Interestingly, such defect of LLOT515G-L516G could be rescued in the presence of higher membrane cholesterol levels, suggesting cholesterol can augment the pore-forming efficacy of LLO even in the absence of a direct toxin-cholesterol interaction. Furthermore, we find the membrane-binding and pore-forming abilities of LLOT515G-L516G, but not those of LLO, correlate with the cholesterol-dependent rigidity/ordering of the membrane lipid bilayer. Our data further suggest that the line tension derived from the lipid phase heterogeneity of the cholesterol-containing membranes could play a pivotal role in LLO function, particularly in the absence of cholesterol binding. Therefore, in addition to its receptor-like role, we conclude cholesterol can further facilitate the pore-forming, membrane-damaging functionality of LLO by asserting the optimal physicochemical environment in membranes. To the best of our knowledge, this aspect of the cholesterol-mediated regulation of the CDC mode of action has not been appreciated thus far.

Mimicking and analyzing the tumor microenvironment.

The tumor microenvironment (TME) is increasingly appreciated to play a decisive role in cancer development and response to therapy in all solid tumors. Hypoxia, acidosis, high interstitial pressure, nutrient-poor conditions, and high cellular heterogeneity of the TME arise from interactions between cancer cells and their environment. These properties, in turn, play key roles in the aggressiveness and therapy resistance of the disease, through complex reciprocal interactions between the cancer cell genotype and phenotype, and the physicochemical and cellular environment. Understanding this complexity requires the combination of sophisticated cancer models and high-resolution analysis tools. Models must allow both control and analysis of cellular and acellular TME properties, and analyses must be able to capture the complexity at high depth and spatial resolution. Here, we review the advantages and limitations of key models and methods in order to guide further TME research and outline future challenges.

Sub-habitat classification of temperate salt marshes in Japan based on aquatic fauna

Salt marshes are being lost worldwide even though they provide essential ecosystem services. Habitat classification of salt marshes based on fauna, which is an effective indicator of their ecosystems, is expected to be useful to effectively assess the baseline for conservation and restoration; however, it has not been well studied. This study aimed to identify the diversity of salt marsh sub-habitats for fauna, where biota was collected and the physicochemical environments were measured in 101 small patches of salt marsh (i.e., survey sites) across 32 temperate tidal rivers and inlets in Fukuoka Prefecture, Kyushu, Japan. A total of 78 aquatic animal species (decapod crustaceans, gastropod mollusks, bivalves, nereidid polychaetes, and fish) were observed, 63 of which were used as indicators for sub-habitat identification. Although reed plants covered 90 of the 101 survey sites, the survey sites were classified into six clusters based on fauna. Representative aquatic animals were identified in each cluster, and these six clusters had different physicochemical environments, such as salinity and sediment conditions. The results indicated that the six sub-habitats had different biotic and abiotic characteristics. On the other hand, the results of the ordination analysis indicated that the fauna of the six sub-habitats do not occur independently of each other but are composed of continuous and gradually changing fauna along environmental gradients. Although no significant differences in the areas of salt marsh patches among the clusters, species richness differed significantly, suggesting that physicochemical environments, such as salinity and sediment conditions, rather than spatial factors, may affect species diversity. The findings emphasize that each sub-habitat supports species diversity in temperate salt marshes and are expected to contribute to planning targets for future salt marsh conservation/restoration and further improvements in artificial marshes.

Ion-mediated condensation controls the mechanics of mitotic chromosomes

During mitosis in eukaryotic cells, mechanical forces generated by the mitotic spindle pull the sister chromatids into the nascent daughter cells. How do mitotic chromosomes achieve the necessary mechanical stiffness and stability to maintain their integrity under these forces? Here we use optical tweezers to show that ions involved in physiological chromosome condensation are crucial for chromosomal stability, stiffness and viscous dissipation. We combine these experiments with high-salt histone depletion and theory to show that chromosomal elasticity originates from the chromatin fibre behaving as a flexible polymer, whereas energy dissipation can be explained by modelling chromatin loops as an entangled polymer solution. Taken together, we show how collective properties of mitotic chromosomes, a biomaterial of incredible complexity, emerge from molecular properties, and how they are controlled by the physico-chemical environment.

A Machine Learning Method for RNA-Small Molecule Binding Preference Prediction.

The interaction between RNA and small molecules is crucial in various biological functions. Identifying molecules targeting RNA is essential for the inhibitor design and RNA-related studies. However, traditional methods focus on learning RNA sequence and secondary structure features and neglect small molecule characteristics, and resulting in poor performance on unknown small molecule testing. To overcome this limitation, we developed a double-layer stacking-based machine learning model called ZHMol-RLinter. This approach more effectively predicts RNA-small molecule binding preferences by learning RNA and small molecule features to capture their interaction information. ZHMol-RLinter also combines sequence and secondary structural features with structural geometric and physicochemical environment information to capture the specificity of RNA spatial conformations in recognizing small molecules. Our results demonstrate that ZHMol-RLinter has a success rate of 90.8% on the published RL98 testing set, representing a significant improvement over existing methods. Additionally, ZHMol-RLinter achieved a success rate of 77.1% on the unknown small molecule UNK96 testing set, showing substantial improvement over the existing methods. The evaluation of predicted structures confirms that ZHMol-RLinter is reliable and accurate for predicting RNA-small molecule binding preferences, even for challenging unknown small molecule testing. Predicting RNA-small molecule binding preferences can help in the understanding of RNA-small molecule interactions and promote the design of RNA-related drugs for biological and medical applications.

Cellular and Microbial In Vitro Modelling of Gastrointestinal Cancer.

Human diseases are multifaceted, starting with alterations at the cellular level, damaging organs and their functions, and disturbing interactions and immune responses. In vitro systems offer clarity and standardisation, which are crucial for effectively modelling disease. These models aim not to replicate every disease aspect but to dissect specific ones with precision. Controlled environments allow researchers to isolate key variables, eliminate confounding factors and elucidate disease mechanisms more clearly. Technological progress has rapidly advanced model systems. Initially, 2D cell culture models explored fundamental cell interactions. The transition to 3D cell cultures and organoids enabled more life-like tissue architecture and enhanced intercellular interactions. Advanced bioreactor-based devices now recreate the physicochemical environments of specific organs, simulating features like perfusion and the gastrointestinal tract's mucus layer, enhancing physiological relevance. These systems have been simplified and adapted for high-throughput research, marking significant progress. This review focuses on in vitro systems for modelling gastrointestinal tract cancer and the side effects of cancer treatment. While cell cultures and in vivo models are invaluable, our main emphasis is on bioreactor-based in vitro modelling systems that include the gut microbiome.

The influence of relative humidity on the physicochemical environment of moisture in wood cell wall

The influence of relative humidity on the physicochemical environment of moisture in wood cell wall

Fish size structures in lakes of the Lower Mississippi River floodplain

Abstract The Lower Mississippi River has a floodplain that includes &gt;1350 perennial lakes carved by shifts in river courses and other hydro‐fluvial processes over eons. Notwithstanding their similar provenances, these waterbodies exhibit an immense variety of morphologies and successional stages that illustrate their natural trajectory from aquatic to forested wetlands. A result of this geographical, morphological and temporal diversity is dynamic and varied fish communities. We examined how size structures of fish communities in these floodplain lakes were associated with key in‐lake and off‐lake environmental drivers. Fish lengths were collected with standardised procedures in a sample of 30 of these lakes to construct a lake‐by‐length group matrix. Likewise, in‐lake and off‐lake environmental descriptors were collected to construct a lake‐by‐covariate matrix. Distance‐based linear models were used to assess associations between fish size structure and environmental descriptors. Smaller fish were typically associated with increasing levels of turbidity, chlorophyll‐a, phycocyanin and surrounding agriculture. Shallow, hypereutrophic floodplain lakes associated with agricultural landscapes and reduced connectivity experience harsh physicochemical environments. These conditions appeared to hinder the formation of sustained fish communities but may confer a survival advantage to juveniles or small short‐lived species. Conversely, larger fish were associated with increasing lake depth, water clarity, connectivity, and extent of surrounding forests‐wetlands. Enhanced stability and size structure were observed in communities residing in deeper and clearer lakes, suggesting that these conditions facilitated the development of longer‐lived species spanning multiple age groups. The enhanced connectivity that facilitated this increased stability also permitted the presence of larger itinerant species. Size‐structure assessments can serve as a valuable ecological and biodiversity indicator in floodplain lakes. Size‐structure assessments could supplement and, depending on objectives, even supplant conventional taxonomic analyses, and enhance surveillance of this vast and important natural resource.

Diagnostic and prophylactic potential of a stabilized foot-and-mouth disease serotype Asia1 virus like particles designed through a structure guided approach

Intact capsids of foot-and-mouth disease virus (FMDV) play a vital role in eliciting a protective immune response. Any change in the physico-chemical environment of the capsids results in dissociation and poor immunogenicity. Structural bioinfomatics studies have been carried out to predict the amino acids at the interpentameric region that resulted in the identification of mutant virus-like particles(VLPs) of FMDV serotype Asia1/IND/63/1972. The insect cell expressed VLPs were evaluated for their stability by sandwich ELISA. Among 10 mutants, S93H showed maximum retention of antigenicity at different temperatures, indicating its higher thermal stability as revealed by the in-silico analysis and retained the antigenic sites of the virus demonstrated by Sandwich ELISA. The concordant results of the liquid phase blocking ELISA for estimation of antibody titre of known sera with stable mutant VLP as antigen in place of virus antigen demonstrate its diagnostic potential. The stable mutant VLP elicited a robust immune response with 85.6 % protection in guinea pigs against virus challenge. The stabilized VLP based antigen requires minimum biosafety and cold storage for production and transit besides, complying with differentiation of infected from vaccinated animals. It can effectively replace the conventional virus handling during antigen production for prophylactic and diagnostic use.

Soil-sediment connectivity through Bayesian source tracking in an urban naturalised waterway via microbial and isotopic markers

Riverine sediments are important habitats for microbial activity in naturalised waterways to provide potential ecosystem services that improve stormwater quality. Yet, little is known about the sources of these sediment microbes, and the factors shaping them. This study investigated the dominant source of sediments in a tropical naturalised urban waterway, using two Bayesian methods for microbial and isotopic 13C/15N markers concurrently. Additionally, key factors shaping microbial communities from the surrounding landscape were evaluated. A comprehensive two-year field survey identified source land covers of interest based on topology and soil context. Among these land covers, riverbanks were the dominant source of sediments contribution for both edaphic and microbial components. The physico-chemical environment explains most of the variation in sediment communities compared to inter-location distances and microbial source contribution. As microbes provide ecosystem services important for rewilding waterways, management strategies that establish diverse sediment microbial communities are encouraged. Since riverbanks play a disproportionately important role in material contribution to sediment beds, management practices aimed at controlling soil erosion from riverbanks can improve overall functioning of waterway systems.

Castor Bean Meal Fertilizer Improves Peanut Yield and Quality by Regulating the Soil Physicochemical Environment and Soil Enzyme Activities

PurposeFertilization is important for improving crop yield and soil quality. Elucidation of the effects of castor bean meal (CBM) fertilizer on peanut yield and quality and soil fertility can lead to additional fertilization options for peanut and provide a theoretical reference for achieving a high-quality, high-yielding peanut.MethodsDuring 2022–2023, a two-year long-term field experiment was conducted in Tongliao city, Inner Mongolia, China. No fertilizer (CK) was used as the control, and the effects of different treatments, i.e., CBM fertilizer (B1: 2520 kg ha-1, B2: 5040 kg ha-1, and B3: 10,080 kg ha-1), chemical fertilizer alone (F1: 175 kg ha-1, F2: 350 kg ha-1, and F3: 700 kg ha-1), and cow manure alone (N1: 3724 kg ha-1, N2: 7448 kg ha-1, and N3: 14,896 kg ha-1) on peanut yield and quality and soil fertility were investigated.ResultsThe results showed that CBM fertilizer application improved soil ecology. Compared with other fertilization treatments, the soil pH of B3 treatment decreased by 8.5%, but significantly increased the contents of organic carbon (SOC), total nitrogen (TN), total phosphorus (TP), total potassium (TK), alkali-hydrolyzed nitrogen (AN), basic phosphorus (AP) and rapidly available potassium (AK) in the soil, which increased by 86.4%, 64.6%, 70.5%, 11.3%, 75.8%, 150.1%, and 116.2%, respectively, compared with CK. Meanwhile, B1, B2, N1 and N2 treatments also led to the elevation of the above indexes. In addition, the activities of urease (URE), sucrase (SUC), phosphatase (PPL), catalase (CAT), amylase (AMY) and protease (PRO) in the B3 treatment were significantly greater than those in the other fertilization treatments, with increases of 256.4%, 248.4%, 68.2%, 96.8%, 267.3%, and 155.7%, respectively, compared with CK. The B3 treatment also significantly increased the rootlet length(PRL), number of branches(BN), plant height(PLH) and lateral branch length(LBL) of the peanut plants. Compared with the other treatments, the B3 treatment had a greater peanut yields, reaching 8059.5 kg ha-1 and 9935.7 kg ha-1 in 2022 and 2023, respectively. Compared with the other treatments, the B1 treatment significantly increased the contents of protein (Pro), fat (FAT), unsaturated fatty acid (UFA) and vitamin E (VE), which increased by 23.3%, 6.1%, 1.0%, 29.1%, respectively, compared with CK, but the total sugar (TS) content was reduced by 9.1%. Correlation analysis further confirmed that peanut yield and quality were significantly correlated with soil nutrients and enzyme activities.ConclusionsThis study showed that the application of CBM fertilizer has certain positive effects. For example, the B3 treatment has certain potential for increasing peanut yield, and the B1 treatment can be used for peanut quality improvement. Therefore, CBM fertilizer is recommended as a new type of organic fertilizer for improving the peanut quality and yield.

Impact of ultrasound process on cassava starch nanoparticles and Pickering emulsions stability

Using green techniques to convert native starches into nanoparticles is an interesting approach to producing stabilizers for Pickering emulsions, aiming at highly stable emulsions in clean label products. Nanoprecipitation was used to prepare the Pickering starch nanoparticles, while ultrasound technique has been used to modulate the size of these nanoparticles at the same time as the emulsion was developed. Thus, the main objective of this study was to evaluate the stabilizing effect of cassava starch nanoparticles (SNP) produced by the nanoprecipitation technique combined with ultrasound treatment carried out in the presence of water and oil (more hydrophobic physicochemical environment), different from previous studies that carry out the mechanical treatment only in the presence of water. The results showed that the increased ultrasound energy input could reduce particle size (117.58 to 55.75 nm) and polydispersity (0.958 to 0.547) in aqueous dispersions. Subsequently, Pickering emulsions stabilized by SNPs showed that increasing emulsification (ultrasonication) time led to smaller droplet sizes and monomodal size distribution. Despite flocculation, long-term ultrasonication (6 and 9 min) caused little variation in the droplet size after 7 days of storage. The cavitation effects favored the interaction between oil droplets through weak attraction forces and particle sharing, favoring the Pickering stabilization against droplet coalescence. Our results show the potential to use only physical modifications to obtain nanoparticles that can produce coalescence-stable emulsions that are environmentally friendly.

Hot and Fresh: Evidence of Climate-Related Suboptimal Water Conditions for Seagrass in a Large Gulf Coast Estuary

Seagrasses have long been a focal point for management efforts aimed at restoring ecosystem health in estuaries worldwide. In Tampa Bay, Florida (USA), seagrass coverage has declined since 2016 by nearly a third (11,518 acres), despite sustained reductions of nitrogen loads supportive of light environments for growth. Changing physical water quality conditions related to climate change may be stressing seagrasses beyond their optimal growth ranges, requiring an assessment to determine if this decline can be linked to climate stress. Three ambient water quality datasets of varying sampling designs and coverage were evaluated to characterize physicochemical environments in Tampa Bay and the potential relationships with seagrass change. Tampa Bay has become hotter and fresher with water temperature increasing by 0.03–0.04 °C per year and salinity decreasing by 0.04–0.06 ppt per year, translating to an increase of 1.3 to 1.7 °C and a decrease of 1.6 to 2.6 ppt over the last 50 years. Additionally, the number of days when temperature was above 30 °C or salinity was below 25 ppt has increased on average across all bay segments by 48 and 37 days, respectively, since 1975. These changes varied spatially and seasonally, with the most dramatic changes observed in the upper bay. Generalized Additive Models provided a weight-of-evidence that recent seagrass declines are somewhat associated with hotter and fresher conditions. Trends in warming and increased precipitation in the region are likely to continue, further creating suboptimal conditions for seagrasses in Tampa Bay. These results should compel resource managers to consider the likelihood that reduced resilience of estuarine resources due to shifting ecological baselines driven by additional climate change drivers will complicate long-standing management paradigms. While conventional management approaches that focus on limiting nutrient loads should be continued, their future effectiveness may be confounded by climate change drivers and warrant additional, complementary interventions and continuous monitoring data to support ecosystem health into the future.

How Droplets Can Accelerate Reactions─Coacervate Protocells as Catalytic Microcompartments.

ConspectusCoacervates are droplets formed by liquid-liquid phase separation (LLPS) and are often used as model protocells-primitive cell-like compartments that could have aided the emergence of life. Their continued presence as membraneless organelles in modern cells gives further credit to their relevance. The local physicochemical environment inside coacervates is distinctly different from the surrounding dilute solution and offers an interesting microenvironment for prebiotic reactions. Coacervates can selectively take up reactants and enhance their effective concentration, stabilize products, destabilize reactants and lower transition states, and can therefore play a similar role as micellar catalysts in providing rate enhancement and selectivity in reaction outcome. Rate enhancement and selectivity must have been essential for the origins of life by enabling chemical reactions to occur at appreciable rates and overcoming competition from hydrolysis.In this Accounts, we dissect the mechanisms by which coacervate protocells can accelerate reactions and provide selectivity. These mechanisms can similarly be exploited by membraneless organelles to control cellular processes. First, coacervates can affect the local concentration of reactants and accelerate reactions by copartitioning of reactants or exclusion of a product or inhibitor. Second, the local environment inside the coacervate can change the energy landscape for reactions taking place inside the droplets. The coacervate is more apolar than the surrounding solution and often rich in charged moieties, which can affect the stability of reactants, transition states and products. The crowded nature of the droplets can favor complexation of large molecules such as ribozymes. Their locally different proton and water activity can facilitate reactions involving a (de)protonation step, condensation reactions and reactions that are sensitive to hydrolysis. Not only the coacervate core, but also the surface can accelerate reactions and provides an interesting site for chemical reactions with gradients in pH, water activity and charge. The coacervate is often rich in catalytic amino acids and can localize catalysts like divalent metal ions, leading to further rate enhancement inside the droplets. Lastly, these coacervate properties can favor certain reaction pathways, and thereby give selectivity over the reaction outcome.These mechanisms are further illustrated with a case study on ribozyme reactions inside coacervates, for which there is a fine balance between concentration and reactivity that can be tuned by the coacervate composition. Furthermore, coacervates can both catalyze ribozyme reactions and provide product selectivity, demonstrating that coacervates could have functioned as enzyme-like catalytic microcompartments at the origins of life.

Quartz grain microtextures of Holocene sebkhas sediments in southeast Tunisia: Implications for sedimentary processes and depositional environments

Detrital quartz grains extracted from sebkha sediments in southeastern Tunisia underwent scanning electron microscopy analysis to identify sediment sources and assess the influence of the saline environment on the grains. Core sediments collected from Sebkha el Melah and Sebkha Mhabeul cover the last 5000 and 2000 BP, respectively. The uppermost Unit III, present in both cores, exhibits two distinct facies based on the mechanical microtextures of its quartz grains. The aeolian facies sediments are characterized by quartz grains with rounded outlines, upturned plates, and crescentic percussion marks. In contrast, the fluvial facies sediments are associated with quartz grains featuring subangular outlines, v-shaped percussion cracks, conchoidal fractures. Observations on the quartz grains of the sebkhas suggest multiple transportation and processing events, indicating long-distance transport and rapid deposition rates. The majority of quartz grains appear to originate from the surrounding terrain, reflecting the dynamic geological history of the region. This study delves into the connection between microtexture variations on quartz grain surfaces and specific historical climatic conditions in the sebkhas. By examining geochemical variations along the cores, facies with elevated salt concentrations corresponding to warmer periods reveal extensively weathered quartz grains. This substantial chemical alteration is evident through microtextures such as oriented etch pits, anastomosed dissolution networks and solution crevasses. The profound dissolution has significantly impacted the quartz lattice, resulting in the decomposition of the grains and the formation of "cauliflower" or "spongy" shapes, erasing prior microtextures. Conversely, during less warm periods, quartz dissolution was less severe, thereby preserving microtextures.Sand grain surfaces are notably sensitive to both transport processes and variations in the physicochemical environment. In the hypersaline and confined environments of sebkhas in southeastern Tunisia, potent post-sedimentary processes can obliterate and obscure the original microtextures recorded on grains from previous environments due to highly fluctuating physicochemical conditions.