A Water-Soluble Multifunctional Probe for Colorimetric Copper Sensing, Lysosome Labelling and Live-Cell Imaging.

We report a water-soluble fluorescence and colorimetric copper probe (LysoBC1); this system can also serve for lysosome labeling and for the dynamic tracking of Cu2+ in living cells. The sensing mechanism takes advantage of the synergic action by the following three components: i) a lysosome targeting unit, ii) the spirolactam ring-opening for the selective copper chelation and iii) the metal-mediated hydrolysis of the rhodamine moiety for fluorescence enhancement. In aqueous environment the molecule acts as a fluorescent reversible pH sensor and as colorimetric probe for Cu2+ at physiological pH; the hydrolysis of the copper targeting unit resulted in a 50-fold increase of the fluorescence intensity. Most importantly, in vitro cell analyses in undifferentiated (SH SY5Y) and differentiated (d-SH SY5Y) neuroblastoma cells, LysoBC1 is able to selectively accumulate into lysosome while the copper binding ability allowed us to monitor intracellular copper accumulation into lysosome.

Simple Air-Stable [3]Radialene Anion Radicals as Environmentally Switchable Catholytes in Water.

The hexacyano[3]radialene radical anion (1) is an attractive catholyte material for use in redox flow battery (RFB) applications. The substitution of cyano groups with ester moieties enhances solubility while maintaining redox reversibility and favorable redox potentials. Here we show that these ester-functionalized, hexasubstituted [3]radialene radical anions dimerize reversibly in water. The dimerization mode is dependent on the substitution pattern and can be switched in solution. Stimuli-responsive behavior is achieved by exploiting an unprecedented tristate switching mechanism, wherein the radical can be toggled between the free radical, a π-dimer, and a σ-dimer-each with dramatically different optical, magnetic, and redox properties-by changing the solvent environment, temperature, or salinity. The symmetric, triester-tricyano[3]radialene (3) forms a solvent-responsive, σ-dimer in water that converts to the radical anion with the addition of organic solvents or to a π-dimer in brine solutions. Diester-tetracyano[3]radialene (2) exists primarily as a π-dimer in aqueous solutions and a radical anion in organic solvents. The dimerization behavior of both 2 and 3 is temperature dependent in methanol solutions. Dimerization equilibrium has a direct impact on catholyte stability during galvanostatic charge-discharge cycling in static H-cells. Specifically, conditions that favor the free radical anion or π-dimer exhibit significantly enhanced cycling profiles.

Emergent Properties in Chemistry - Relating Molecular Properties to Bulk Behavior.

Certain properties of an object only emerge when a sufficient number of those objects are present in a definite arrangement. For example, one or two water molecules cannot said to be in a liquid state, but a drop of water can be. This concept of emergence has been studied extensively, but only occasionally discussed explicitly in the context of chemistry. In this paper, we aim to show the fruitfulness of the concept of emergence for chemical inquiry by considering four case studies of emergent chemical properties, i. e., the liquidity and freezing of water, structural properties of crystals, thermodynamical phase transitions and quantum mechanical phenomena. We show that some of these properties emerge gradually, some at discrete points, and some should be taken to emerge only when the number of constituents tends to infinity. We argue that studying the way in which chemical properties emerge presents a useful avenue for research that promises greater insight into the nature of those properties.

Size-dependent effects of dams on river ecosystems and implications for dam removal outcomes.

Understanding the relationship between a dam's size and its ecological effects is important for prioritization of river restoration efforts based on dam removal. Although much is known about the effects of large storage dams, this information may not be applicable to small dams, which represent the vast majority of dams being considered for removal. To better understand how dam effects vary with size, we conducted a multidisciplinary study of the downstream effect of dams on a range of ecological characteristics including geomorphology, water chemistry, periphyton, riparian vegetation, benthic macroinvertebrates, and fish. We related dam size variables to the downstream-upstream fractional difference in measured ecological characteristics for 16 dams in the mid-Atlantic region ranging from 0.9 to 57 m high, with hydraulic residence times (HRTs) ranging from 30 min to 1.5 years. For a range of physical attributes, larger dams had larger effects. For example, the water surface width below dams was greater below large dams. By contrast, there was no effect of dam size on sediment grain size, though the fraction of fine-grained bed material was lower below dams independently of dam size. Larger dams tended to reduce water quality more, with decreased downstream dissolved oxygen and increased temperature. Larger dams decreased inorganic nutrients (N, P, Si), but increased particulate nutrients (N, P) in downstream reaches. Aquatic organisms tended to have greater dissimilarity in species composition below larger dams (for fish and periphyton), lower taxonomic diversity (for macroinvertebrates), and greater pollution tolerance (for periphyton and macroinvertebrates). Plants responded differently below large and small dams, with fewer invasive species below large dams, but more below small dams. Overall, these results demonstrate that larger dams have much greater impact on the ecosystem components we measured, and hence their removal has the greatest potential for restoring river ecosystems.

Photooxidation-Initiated Aqueous-Phase Formation of Organic Peroxides: Delving into Formation Mechanisms.

Formation of highly oxygenated molecules (HOMs) such as organic peroxides (ROOR, ROOH, and H2O2) is known to degrade food and organic matter. Gas-phase unimolecular autoxidation and bimolecular RO2 + HO2/RO2 reactions are prominently renowned mechanisms associated with the formation of peroxides. However, the reaction pathways and conditions favoring the generation of peroxides in the aqueous phase need to be evaluated. Here, we identified bulk aqueous-phase ROOHs in varying organic precursors, including a laboratory model compound and monoterpene oxidation products. Our results show that formation of ROOHs is suppressed at enhanced oxidant concentrations but exhibits complex trends at elevated precursor concentrations. Furthermore, we observed an exponential increase in the yield of ROOHs when UV light with longer wavelengths was used in the experiment, comparing UVA, UVB, and UVC. Water-soluble organic compounds represent a significant fraction of ambient cloud-water components (up to 500 µM). Thus, the reaction pathways facilitating the formation of HOMs (i.e., ROOHs) during the aqueous-phase oxidation of water-soluble species add to the climate and health burden of atmospheric particulate matter.

Traceability of gushing water in the MiddleRoute of the South-to-North Water Diversion (Beijing section) through the river area.

To trace the origin of the gushing water in the riverine area of the Beijing section of The Middle Route of South-to-North Water Diversion Project, a dataset was established comprising water chemistry, three-dimensional fluorescence spectra, and stable isotopes for different water bodies. Results indicated significant differences in Electrical Conductivity (EC), Total Dissolved Solids (TDS), and Ca2+ concentration among the gushing water, river water, and the water from the Middle Route of South-to-North Water Diversion Project (MRSD). Analysis using parallel factor analysis (PARAFAC) and fluorescence index revealed that dissolved organic matter (DOM) in the MRSD mainly originated from endogenous sources, while the river water and gushing water showed influences from both endogenous and exogenous sources. Nitrate sources varied among the water bodies, with distinct contributions from domestic sewage and fertilizer sources. The evaporation lines of river water and gushing water exhibited similar intercepts and slopes, but their intercepts and slopes are much smaller than those of the MRSD, suggesting stronger kinetic evaporative fractionation. In conclusion, the gushing water in the riverine area of the MRSD was determined to originate from the river, providing a fast and efficient method for gushing water source identification.

Hydrogen Peroxide Production of Individual Nanosecond Pulsed Discharges Submerged in Water of Elevated Conductivity.

The production of hydrogen peroxide (H2 O2 ) is a key parameter for the performance of pulsed discharges submerged in water utilized as advanced oxidation process. So far, any related assessment of the underlying mechanism was conducted for the application of several hundred discharges, which did not allow for a correlation with physical processes. Moreover, the production was rarely investigated depending on water conductivity as one of the most important parameters for the development of submerged discharges. Accordingly, hydrogen peroxide generation was investigated here for individual single discharge events instigated with 100 ns high-voltage pulses in water with three different conductivities and was associated with the discharge development, i. e. spatial expansion and dissipated electrical energy. The approach necessitated the improvement of an electrochemical flow injection analysis based on the reaction of Prussian blue with H2 O2 . Hydrogen peroxide concentrations were quadratically increasing with propagation time and stable for different water conductivities. H2 O2 production per unit volume of a discharge was constant over time with an estimated rate constant of 3.2 mol ⋅ m-1 s-1 , averaged over the crosssectional area of all discharge filaments. However, the individually dissipated energy increased with conductivity, hence, the production efficiency decreased from 6.1 g ⋅ kWh-1 to 1.4 g ⋅ kWh-1 , which was explained by increased resistive losses within the bulk liquid.

Environment and Host Genetics Influence the Biogeography of Plant Microbiome Structure.

To understand how microbiota influence plant populations in nature, it is important to examine the biogeographic distribution of plant-associated microbiomes and the underlying mechanisms. However, we currently lack a fundamental understanding of the biogeography of plant microbiomes across populations and the environmental and host genetic factors that shape their distribution. Leveraging the broad distribution and extensive genetic variation in duckweeds (the Lemna species complex), we identified key factors that governed plant microbiome diversity and compositional variation geographically. In line with the microbial biogeography of free-living microbiomes, we observed higher bacterial richness in temperate regions relative to lower latitudes in duckweed microbiomes (with 10% higher in temperate populations). Our analyses revealed that higher temperature and sodium concentration in aquatic environments showed a negative impact on duckweed bacterial richness, whereas temperature, precipitation, pH, and concentrations of phosphorus and calcium, along with duckweed genetic variation, influenced the biogeographic variation of duckweed bacterial community composition. Analyses of plant microbiome assembly processes further revealed that niche-based selection played an important role (26%) in driving the biogeographic variation of duckweed bacterial communities, alongside the contributions of dispersal limitation (33%) and drift (39%). These findings add significantly to our understanding of host-associated microbial biogeography and provide important insights for predicting plant microbiome vulnerability and resilience under changing climates and intensifying anthropogenic activities.

Application of nanofibrous protein for the purification of contaminated water as a next generational sorption technology: a review.

Globally, wastes from agricultural and industrial activities cause water pollution. Pollutants such as microbes, pesticides, and heavy metals in contaminated water bodies beyond their threshold limits result in several diseases like mutagenicity, cancer, gastrointestinal problems, and skin or dermal issues when bioaccumulated via ingestion and dermal contacts. Several technologies have been used in modern times to treat wastes or pollutants such as membrane purification technologies and ionic exchange methods. However, these methods have been recounted to be capital intensive, non-eco-friendly, and need deep technical know-how to operate thus, contributing to their inefficiencies and non-efficacies. This review work evaluated the application of Nanofibrils-protein for the purification of contaminated water. Findings from the study indicated that Nanofibrils protein is economically viable, green, and sustainable when used for water pollutant management or removal because they have outstanding recyclability of wastes without resulting in a secondary phase-pollutant. It is recommended to use residues from dairy industries, agriculture, cattle guano, and wastes from a kitchen in conjunction with nanomaterials to develop nanofibrils protein which has been recounted for the effective removal of micro and micropollutants from wastewater and water. The commercialization of nanofibrils protein for the purification of wastewater and water against pollutants has been tied to novel methods in nanoengineering technology, which depends strongly on the environmental impact in the aqueous ecosystem. So, there is a need to establish a legal framework for the establishment of a nano-based material for the effective purification of water against pollutants.

Freshwater fishes maintain multi-trait phenotypic stability across an environmental gradient in aqueous calcium.

Reductions in a limiting nutrient might be expected to necessitate compromises in the functional traits that depend on that nutrient; yet populations existing in locations with low levels of such nutrients often do not show the expected degradation of functional traits. Indeed, logperch (Percina caprodes), pumpkinseed sunfish (Lepomis gibbosus) and yellow perch (Perca flavescens) residing in low-calcium water in the Upper St. Lawrence River were all previously found to maintain levels of scale calcium comparable to those of conspecific populations in high-calcium water. Yet it remains possible that the maintenance of one functional trait (i.e., scale calcium) under nutrient-limited (i.e., low calcium) conditions could come at the expense of maintaining other functional traits that depend on the same nutrient. The present study therefore examines other calcium-dependent traits, specifically skeletal element sizes and bone densities in the same fish species in the same area. Using radiographs of 101 fish from the three species across four locations (two in high-calcium water and two in low-calcium water), this new work documents multi-trait "homeostasis" along the gradient of water calcium. That is, no effect of calcium regime (low-calcium vs. high-calcium) was detected on any of the measured variables. Further, effect sizes for the skeletal traits were very low - lower even than effect sizes previously documented for scale calcium. These results thus show that native fishes maintain phenotypic stability across a suite of functional traits linked to calcium regulation, perhaps pointing to an "organismal-level homeostasis" scenario rather than a "trait-level homeostasis" scenario.

Interaction among biofilter microbiome, fecal metabolome and water quality and regulation of sewage discharge in the recirculating aquaculture system of Apostichopus japonicus.

With the aggravation of environmental pollution caused by traditional culture of Apostichopus japonicus, the concept of A. japonicus recirculating aquaculture system (RAS) came into being. To plan the sewage discharge time reasonably, we explored the temporal variation of water quality, biofilter microbe and fecal metabolome in RAS and relevant mechanism. The results showed that monitored water quality in RAS were within the safe living range of A. japonicus. Proteobacteria and Desulfobacterota were dominant bacteria in biofilter. The RDA results and correlation heatmap showed that NH4-N and NO2-N significantly affected the microbial community composition. The expression pattern of fecal metabolites changed with the passage of time after feeding. And ROC curve analysis and VIP bar chart showed that there were inter group biomarkers with predictive performance, which could help to remind timely sewage discharge. Topological analysis of KEGG pathway enrichment showed that metabolic pathways such as alanine, aspartate and glutamate metabolism changed significantly after feeding (P < 0.01). Additionally, the correlation analysis results showed that biofilter microbe and fecal metabolites were related to water quality (P < 0.05). Combined with the above research results, this study concluded that the RAS could discharge sewage 25-30 h after feeding. These findings were of direct significance to the management of RAS environment and the protection of A. japonicus healthy growth.

Evaluation of groundwater quality with microbiological and physicochemical parameters in Bartin, Turkey.

In this study, the physicochemical and microbiological quality of groundwater samples was investigated in rainy and dry periods. Forty samples were collected from 10 sampling points. TDS, EC, color, turbidity, NO3, SO4, PO4, Cl, total hardness, E. coli, and F. streptococci analyses were performed. Cl, TH, and NO3 were higher in the rainy period unlike TDS, EC, SO4, and PO4. Physicochemical parameters did not exceed the acceptable values reported for drinking waters in TS/WHO. However, groundwater samples were not suitable for drinking water in terms of microbiological parameters. Both bacteria were found in higher numbers in the dry period. However, E. coli was more abundant in the dry period in contrast to F. streptococci. According to the nitrate/Cl ratio and other analyses (correlation matrix and principal component analysis) groundwater quality was affected by many sources. The results of analytic and statistical analyzes showed that F. streptococci is mostly related to animal waste unlike E. coli. According to the EC/FS ratio, microbiological pollution in rural areas was affected by animal wastes in both periods. On the other hand, animal waste in the urban areas may be effective during the rainy period. PCA and correlation matrix also confirmed these results. According to PCA results, groundwater quality may be affected by geogenic sources, fecal sources, and use of fertilizer in the study area. According to WQI, 5% and 16% of the groundwater samples were not found suitable as drinking water in dry and rainy periods, respectively.

Water Self-Dissociation is Insensitive to Nanoscale Environments.

Nanoconfinement effects on water dissociation and reactivity remain controversial, despite their importance to understand the aqueous chemistry at interfaces, pores, or aerosols. The pKw in confined environments has been assessed from experiments and simulations in a few specific cases, leading to dissimilar conclusions. Here, with the use of carefully designed ab initio simulations, we demonstrate that the energetics of bulk water dissociation is conserved intact to unexpectedly small length-scales, down to aggregates of only a dozen molecules or pores of widths below 2 nm. The reason is that most of the free-energy involved in water autoionization comes from breaking the O-H covalent bond, which has a comparable barrier in the bulk liquid, in a small droplet of nanometer size, or in a nanopore in the absence of strong interfacial interactions. Thus, dissociation free-energy profiles in nanoscopic aggregates or in 2D slabs of 1 nm width reproduce the behavior corresponding to the bulk liquid, regardless of whether the corresponding nanophase is delimited by a solid or a gas interface. The present work provides a definite and fundamental description of the mechanism and thermodynamics of water dissociation at different scales with broader implications on reactivity and self-ionization at the air-liquid interface.

Quantitative Determination of Water in Organic Liquids by Ambient Mass Spectrometry.

This study uses a rapid tandem mass-spectrometry method to determine water content in complex organic solutions. Emphasis is placed on trace-water analysis by a fast and accurate alternative to the Karl-Fischer method. In this new method, water is captured by a charge-labeled molecular probe. Water binds strongly with high specificity to the strongly electrophilic aldehyde site in a charge-labelled molecule (N-methylpyridinium); competitive binding by other analytes is effectively discriminated against in the mass-measurement step. Quantitative determinations are made over a wide concentration range, 0.001 % (10 ppm) to 99 %, with better than 10 % relative standard deviation, along with short (1 min) analysis times using small sample volumes (several µL). Applications include water measurement in simple organic solvents, for example, deuterated solvents, as well as in complex mixtures, for example, organic reaction mixtures. Additionally, this method allows for water monitoring in levitated droplets. Mechanistic investigations into the impact of water on important chemical processes in organic synthesis and environmental science are reported.

Introducing Water and Deep Eutectic Solvents in Organosodium Chemistry: Chemoselective Nucleophilic Functionalizations in Air.

Advancing the development of perfecting the use of polar organometallics in bio-inspired solvents, we report on the effective generation in batch of organosodium compounds, by the oxidative addition of a C-Cl bond to sodium, a halogen/sodium exchange, or by direct sodiation, when using sodium bricks or neopentylsodium in hexane as sodium sources. C(sp3 )-, C(sp2 )-, and C(sp)-hybridized alkyl and (hetero)aryl sodiated species have been chemoselectively trapped (in competition with protonolysis), with a variety of electrophiles when working "on water", or in biodegradable choline chloride/urea or L-proline/glycerol eutectic mixtures, under hydrous conditions and at room temperature. Additional benefits include a very short reaction time (20 s), a wide substrate scope, and good to excellent yields (up to 98 %) of the desired adducts. The practicality of the proposed protocol was demonstrated by setting up a sodium-mediated multigram-scale synthesis of the anticholinergic drug orphenadrine.

Photocatalytic Terminal C-C Coupling Reaction Inside Water Soluble Nanocages.

Developing methods that activate C-H bonds directly with high selectivity for C-C bond formation in complex organic synthesis has been a major chemistry challenge. Recently it has been shown that photoactivation of weakly polarized C-H bonds can be carried out inside a cationic water-soluble nanocage with visible light-mediated host-guest charge transfer (CT) chemistry. Using this novel photoredox activation paradigm, here we demonstrate C-C bond formation to photo-generate 1,3-diynes at room temperature in water from terminal aromatic alkynes for the first time. The formation of cavity-confined alkyne radical cation and the proton-removed neutral radical species highlight the unique C-C coupling step driven by supramolecular preorganization.

Synthesis of Hydrophilic Phosphorus Ligands and Their Application in Aqueous-Phase Metal-Catalyzed Reactions.

Transition metal-catalyzed reactions in aqueous media are experiencing a constant increase in interest. In homogenous catalysis the use of water as a solvent offers advantages in cost, safety, the possibility of two-phase catalysis and simplified separation strategies. In the life sciences, transition metal catalysis in aqueous systems enables the ligation or modification of biopolymers in buffer systems or even in their cellular environment. In biocatalysis, aqueous systems allow the simultaneous use of enzymes and transition metal catalysts in cascade reactions. The use of water-soluble phosphine ligands still represents the most reliable and popular strategy for transferring metal catalysts into the aqueous phase. This review summarizes the recent advancements in this field since 2009 and describes current synthetic strategies for the preparation of hydrophilic phosphines and phosphites. In addition, recent applications of transition metal catalysis in aqueous solvents using these hydrophilic ligands are presented.

Influences on tidal channel and aquaculture shrimp pond water chemical composition in Southwest Bangladesh.

Detailed geochemical studies of both major and minor elements in Bangladesh surface waters are sparse, particularly in shrimp aquaculture pond environments. Therefore, water samples from shrimp aquaculture ponds and tidal channels were collected in high precipitation (July) and low precipitation (May) months from 2018-2019 in Southwest Bangladesh and analyzed for complete water chemistry. Selenium (Se) and arsenic (As) were elevated above WHO guidelines in 50% and ~ 87% of samples, respectively, but do not show any recognizable spatial patterns. Shrimp pond and tidal channel water compositions in the dry season (May) are similar, illustrating their connectivity and minimal endogenous effects within shrimp ponds. Tidal channels are less saline in July than shrimp ponds still irrigated by tidal channels, suggesting that either farmers limit irrigation to continue farming saltwater shrimp, or the irrigation flux is low and leads to a lag in aquaculture-tidal channel compositional homogenization. δ18O and δ2H isotopic compositions from samples in May of 2019 reveal tidal channel samples are closer to the local meteoric water line (LMWL) than shrimp pond samples, because of less evaporation. However, evaporation in May shrimp ponds has a minimal effect on water composition, likely because of regular drainage/exchange of pond waters. Dissolved organic carbon (DOC) is positively correlated with both δ18O and δ2H in shrimp ponds, suggesting that as evaporation increases, DOC becomes enriched. Multiple linear regression reveals that As and Se can be moderately predicted (adjusted R2 values between 0.4 and 0.7, p < 0.01) in surface waters of our study with only 3-4 independent predictor variables (e.g., Ni, V and DOC for Se prediction; Cu, V, Ni and P for As prediction). Thus, this general approach should be followed in other regions throughout the world when measurements for certain hazardous trace elements such as Se and As may be lacking in several samples from a dataset.

Ligand-Functionalization-Controlled Activity of Metal-Organic Framework-Encapsulated Pt Nanocatalyst toward Activation of Water.

We first report the systematic control of the reactivity of H2O vapor in metal-organic frameworks (MOFs) with Pt nanocrystals (NCs) through ligand functionalization. We successfully synthesized Pt NCs covered with a water-stable MOF, UiO-66 (Pt@UiO-66), having different metal ions or functionalized ligands. The ligand functionalization of UiO-66 significantly affected the catalytic performance of the water-gas shift reaction, and the replacement of Zr4+ ions with Hf4+ ions in UiO-66 had no impact on the catalytic activity. The introduction of a -Br group lowered the reactivity of Pt@UiO-66 by nearly half, whereas the substitution of -Br with a -Me2 group triply enhanced the activity. The origin of the enhanced catalytic activity was found to be the change in H2O activity in the UiO-66 pores by the ligand functionalization, which was investigated using H2O sorption, solid-state NMR, X-ray photoelectron spectroscopy, and in situ IR measurements. This work opens a new prospect to develop MOFs as a platform to activate H2O.

Diels-Alder Reactions in Water Are Determined by Microsolvation.

Nanoconfined aqueous environments and the recent advent of accelerated chemistry in microdroplets are increasingly being investigated for catalysis. The mechanisms underlying the enhanced reactivity in alternate solvent environments and whether the enhanced reactivity due to nanoconfinement is a universal phenomenon are not fully understood. Here, we use ab initio molecular dynamics simulations to characterize the free energy of a retro-Diels-Alder reaction in bulk water at very different densities and in water nanoconfined by parallel graphene sheets. We find that the broadly different global solvation environments accelerate the reactions to a similar degree with respect to the gas-phase reaction, with activation free energies that do not differ by more than kbT from each other. The reason for the same acceleration factor in the extremely different solvation environments is that it is the microsolvation of the dienophile's carbonyl group that governs the transition-state stabilization and mechanism, which is not significantly disrupted by either the lower density in bulk water or the strong nanoconfinement conditions used here. Our results also suggest that significant acceleration of Diels-Alder reactions in microdroplets or on-water conditions cannot arise from local microsolvation when water is present but instead must come from highly altered reaction environments that drastically change the reaction mechanisms.