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Vitamin B 12 (cobalamin, herein B 12 ) is a key cofactor for most organisms being involved in essential metabolic processes. In microbial communities, B 12 is often scarce, largely because only few prokaryotes can synthesize B 12 de novo and are thus considered B 12 -prototrophs. B 12 -auxotrophy is mostly manifested by the absence of the B 12 -independent methionine synthase, MetE. Here, we focus on bacteria that we classified as facultative B 12 consumers as they encode both B 12 -independent and -dependent (MetH) methionine synthases yet largely cannot synthesize B 12 de novo . The genus Vibrio belongs to this group, and our work shows that upon B 12 availability, is linked to AI-2 synthesis. The precursor for AI-2 synthesis is S-adenosyl-L-homocysteine (SAH), which in turn requires methionine as a precursor. In almost all Vibrio campbellii is accelerated and autoinducer-2 (AI-2) concentrations are enhanced. We speculate that methionine synthesis efficiency, dependent on B 12 availability, is linked to AI-2 synthesis. The precursor for AI-2 synthesis is S-adenosyl-L-homocysteine (SAH), which in turn requires methionine as a precursor. In almost all Vibrio -binding protein), which is required for B btuF (B 12 -binding protein), which is required for B 12 uptake, and cobD (Adenosylcobinamide-phosphate synthase), which enables remodeling of B 12 -like compounds, are encoded on the same operon as pfs (or mtnN , Adenosylhomocysteine nucleosidase), the first enzyme in the two-step AI-2 synthesis reaction. Transcriptomic analyses show that virulence factors, such as toxin synthesis, fimbriae formation, and activation of the type-6 secretion system, which have been shown to be regulated by quorum sensing via AI-2, are significantly upregulated in V. campbellii when B 12 is available. Our results demonstrate that V. campbellii is a facultative B 12 is an essential cofactor for important enzymatic reactions, autoinducer-2 mediates interspecies signaling and can regulate the expression of genes that are crucial for virulence and survival. In our study, we hypothesize and present findings how these two important metabolites are linked in 12 availability affects AI-2 levels and thus potentially virulence factor regulation.IMPORTANCEMetabolites play a key role in microbial metabolism and communication. While vitamin B 12 is an essential cofactor for important enzymatic reactions, autoinducer-2 mediates interspecies signaling and can regulate the expression of genes that are crucial for virulence and survival. In our study, we hypothesize and present findings how these two important metabolites are linked in Vibrio species. Vibrio campbellii grows without B 12 but at an accelerated rate when B 12 is present, and we detect higher AI-2 values in cultures with B 12 amendment. Transcriptome analyses show how vitamin B 12 availability significantly upregulates gene expression of virulence factors such as toxin synthesis, fimbrial formation, and activation of the type-6 secretion system in V. campbellii .

Naturally weathered polypropylene (NWPP) samples are useful for investigating the effects of various degradation factors that cannot be obtained in artificial laboratory experiments. In this study, NWPP samples were extracted from beach sediments (Ashiya, Hyogo, Japan). Raman and attenuated total reflection (ATR)-Fourier-transform infrared (FTIR) spectroscopies were used to analyze variations in the composition, crystallinity, orientation, and degradation of NWPP microplastics. The degree of degradation varies from sample to sample, from position to position in a sample, and the inside surface or outside surface of a sample. Significant intensity variations were observed for Raman bands at 1150 and 842 cm⁻¹, indicating changes in the crystallinity and molecular orientation of NWPP due to degradation. The Raman spectra of the elongated pristine PP showed intensity increases at 1150, 998, and 842 cm -1 , indicating variations in the molecular orientation of the polymer chains induced by elongation. The ATR-FTIR spectra of NWPP yield several major new features in the 3600 -3200 cm -1 (OH stretching), 1750-1500 cm -1 (C=O/C=C/COO - stretching), and 1150-900 cm -1 (C-O/C-C stretching) regions. Of particular note is that in the 1750-1500 cm -1 region, at least four bands due to two kinds of vinyl groups and two kinds of carboxylate groups are clearly observed in the second derivative spectra, while bands arising from carbonyl compounds are weak. This may be the first time that the carboxylate bands have ever appeared more strongly than the carbonyl bands in the IR spectra of NWPP. The appearance of the carboxylate bands indicates two possibilities: one is the effect of seawater on the degradation of NWPP samples, and another is the oxidation of keto groups to the carboxylates. Moreover, since a few kinds of vinyl compounds and carboxylates are produced, it is very likely that the degree of degradation is high in the NWPP samples. In this way, IR spectroscopy is useful for exploring the degradation of NWPP while Raman spectroscopy is effective for examining variations in their crystallinity and orientation., Competing Interests: Declarations. Competing interests: The authors declare no competing interests., (© 2025. The Author(s).)

Hypothesis: The adsorption isotherm of alkanols at the haematite|hydrocarbon interface should reflect both chemisorption (chemically bonded fraction) and physisorption (hydrogen bonded fraction)., Experiments and Model: Quartz crystal microbalance (QCM) and X-ray photoelectron spectroscopy (XPS) have been used for characterization of Fe 2 O 3 |hydrocarbon interfaces with absorbed alcohol. A range of Fe 2 O 3 -terminated surfaces, alkanols, hydrocarbons and temperatures have been investigated. A chemisorption-physisorption Langmuir model (CPL) has been developed to interpret the data., Findings: All data show simultaneous physisorption and chemisorption of the alcohol. The CPL analysis reveals variability of the surface chemistry from one sample to another - different fractions of surface sites have been determined for Fe 2 O 3 -coated crystals, Fe 2 O 3 powder, stainless steel-coated crystals etc. However, for a given surface, the fraction of chemisorption sites is stable - it does not change with the alcohol, and changes only slightly with the solvent. The physisorbed alcohol molecules assume configuration normal to the surface, while the chemisorbed molecules assume configuration that is either parallel (high homologues) or normal (low homologues). A transition from normal to parallel orientation has been observed at hexyl. The effects from branching of the alcohol are captured well by CPL. The temperature has been shown to alter both the strength of the physisorption and the fraction of available chemisorption sites., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2025 The Author(s). Published by Elsevier Inc. All rights reserved.)

The highly efficient red-emissive carbon dots (R-CDs) were synthesized from citric acid, polyethyleneimine, and benzil via a facile solvothermal process. The R-CDs displayed maximum fluorescence properties at excitation and emission wavelengths of 550 and 631 nm, respectively, which fall within the red wavelength range. Moreover, the R-CDs exhibited a high fluorescence quantum yield of 11.3 %, and this fluorescence was effectively quenched by Sunset Yellow (SY). Consequently, a novel fluorescent probe was developed for SY detection. This probe exhibited a linear range of 0.085-11.31 μg/mL and limit of detection of 0.026 μg/mL. The R-CDs were validated for SY quantification in various food samples, including carbonate beverages, powdered beverage, cider vinegar, fruit flavored drinks, chocolate, and hard candy samples, achieving recovery rates of 91.2-122 % and a relative standard deviation of 1.0-3.5 %. The synthesized R-CDs therefore show promise for application as a probe for the detection of SY in foods., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The performance of nanomaterials is significantly determined by the interfacial microenvironment, in which a surfactant plays an essential role as the adsorbent, but its involvement in the interfacial reaction is often overlooked. Here, it was discovered that citrate and ascorbic acid, the two primarily used surfactants for colloidal gold nanoparticles (Au NPs), can spontaneously undergo catalytic reaction with trace-level nitrogenous residue under ambient environment to form oxime, which is subsequently cleaved to generate CN - or a compound containing the -CN group. Such a catalytic reaction shows wide universality in both reactants, including various carbonaceous and nitrogenous sources, and metal catalysts, including Au, Ag, Fe, Cu, Ni, Pt, and Pd NPs. Furthermore, with the removal of this reaction, adsorbed CO with diverse adsorption configurations was observed via surface-enhanced Raman spectroscopy under ambient conditions without an applied potential. Our work highlights the non-negligible significance of surfactants in interfacial microenvironments and provides crucial insights into the fundamental understanding of interfacial chemical reactions.

The increasing availability of microbial genomes is essential to gain insights into microbial ecology and evolution that can propel biotechnological and biomedical advances. Recent advances in genome recovery have significantly expanded the catalogue of microbial genomes from diverse habitats. However, the ability to explain how well a set of genomes account for the diversity in a given environment remains challenging for individual studies or biome-specific databases. Here we present EcoPhylo, a computational workflow to characterize the phylogeography of any gene family through integrated analyses of genomes and metagenomes, and our application of this approach to ribosomal proteins to quantify phylogeny-aware genome recovery rates across three biomes. Our findings show that genome recovery rates vary widely across taxa and biomes, and that single amplified genomes, metagenome-assembled genomes, and isolate genomes have non-uniform yet quantifiable representation of environmental microbes. EcoPhylo reveals highly resolved, reference-free, multi-domain phylogenies in conjunction with distribution patterns of individual clades across environments, providing a means to assess genome recovery in individual studies and benchmark biome-level genome collections., Competing Interests: Competing interests Authors declare that they have no conflicts of interest.

The natural Z-scheme of oxygenic photosynthesis efficiently drives electron transfer from photosystem II (PSII) to photosystem I (PSI) via an electron transport chain, despite the lower energy levels of PSII. Inspired by this sophisticated mechanism, we present a layered cascade bio-solar cell (CBSC) that emulates the Z-scheme. In this design, chlorophyll derivatives (Chl) act as PSI analogs, while bacteriochlorophyll derivatives (BChl) serve as PSII analogs in the active layer. The resulting photocurrent, prominently detected in the near-infrared region, is validated through external quantum efficiency measurements. Sub-nanosecond transient absorption spectroscopy reveals a prolonged charge transfer (CT) state from BChl to Chl (Chl-/BChl+ species) compared to the reverse direction (Chl+/BChl- species). This asymmetry highlights a dominant electron flow from BChl (PSII analog) to Chl (PSI analog) under simultaneous excitation, effectively replicating the natural Z-scheme electron transfer. These findings represent a significant advance in the design of bio-inspired solar cells, paving the way for artificial photosynthesis systems and offering profound insights into improving photovoltaic theory and efficiency., (© 2025 Wiley‐VCH GmbH.)

An interzeolite conversion (IZC) method was developed for the rapid synthesis of Cu-SAPO-34 from SAPO-37, achieving isolated Si distribution and optimized Cu states. The resulting Cu-SAPO-34 exhibited exceptional NH 3 -SCR performance, with over 90% NO conversion from 200-600 °C due to proper acidity and Cu status generated from the isolated Si.

The transformation and risk assessment of flavonoids triggered by free radicals deserve extensive attention. In this work, the degradation mechanisms, kinetics, and ecotoxicity of kaempferol and quercetin mediated by ∙OH, ∙OCH 3 , ∙OOH, and 1 O 2 in gaseous and aqueous environments were investigated using cell experiments and quantum chemical calculations. Three radical scavenging mechanisms, including hydrogen atom transfer (HAT), radical adduct formation (RAF) and single electron transfer (SET) were discussed. The results show that RAF and HAT are the main reaction mechanisms for the neutral kaempferol/quercetin, and SET mechanism is important for the anionic kaempferol/quercetin. The overall rate coefficient of kaempferol and quercetin with ∙OH were calculated at 273-323 K, and the aqueous rate coefficients are calculated by considering the rates of neutral and monoanionic forms multiplied with the molar fractions of each form. The values are 2.81 × 10 10 and 8.63 × 10 10  M -1  s -1 in the aqueous environment, and 2.31 × 10 -10 and 1.18 × 10 -10  cm 3 molecule -1  s -1 in the gaseous environment at 298 K. Fluorescence probe and flow cytometry results show that kaempferol and quercetin can be efficiently degraded by free radicals, and quercetin has a better effect, which is consistent with the theoretical results in the aqueous environment. The transformation mechanism of Q-OH-P7a with ∙OH, O 2 and NO was studied, and the stable product is Q-P1. Toxicology results show that most of the subsequent products of quercetin do not bioaccumulate and can be biodegraded, but most products still have toxic properties or harmful properties and show positive mutagenicity. This study provides new guidance for flavonoid degradation behavior and environmental risks., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Precise control of assembled structures of quantum dots (QDs) is crucial for realizing the desired photophysical properties, but this remains challenging. Especially, the one-dimensional (1D) control is rare due to the nearly isotropic nature of QDs. Herein, we propose a novel strategy for controlling the 1D-arrangement range of cubic perovskite QDs in solution based on the morphological modification of a supramolecular polymer (SP) template. The original template with a short and tangled fibrous structure is prepared in a low-polarity solvent mixture via self-assembly of a naphthalenediimide-functionalized cholesterol derivative with an adhesion group for QDs. Mixing this template with QDs leads to the co-aggregation into short-range 1D-arrays of QDs on the templates. Notably, subsequent heating and cooling of the co-aggregate solution forms longer-range 1D-arrays of QDs with lateral growth, where arranged QDs are sandwiched between reconstructed SP templates. Furthermore, the longer-range 1D-array of QDs is achieved via an alternative route involving the pre-organization of templates into longer and dispersed fibers by heating and cooling of the original template, succeeded by co-assembly with QDs. Finally, we reveal continuous fluorescence resonance energy transfer between 1D-arranged QDs by an in-depth analysis of the photoluminescence decay curves., (© 2025 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Caltech Active Strand Cloudwater collectors are used to collect valley fog samples from Mount and North-Lebanon during 2021 for the speciation of organic matter for the first time ever. Numerous compounds including pesticides, phenols, acids, and persistent organic pollutants such as polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and polycyclic aromatic hydrocarbons (PAHs) have been identified in fogwater samples. They are extracted using the liquid-liquid extraction performed on the XTR chromabond columns. The highest contribution to the total organic fraction refers to phenols and acids (around 77 %) due to their better water solubility than others inducing a good affinity to the aqueous phase of fogwater droplets. The lowest contribution refers to the hydrophobic families accounting together for <5 % of the total fraction. Pearson analysis is employed in this study to check correlations between some variables. PAHs are found to be originated from combustion and vehicle exhaust and PCBs are found to be highly correlated with PAHs. Phenols and acids are highly associated with PAHs and PCBs as well as with sulfate and heavy metals (manganese and nickel). This shows that their sources can be either atmospheric oxidation or vehicle exhaust. Pesticides are found to be highly correlated with each other which suggests their simultaneous applications. Despite all, more research is still needed to have a bigger and more reliable data to adopt the beneficial effect of fogwater as an alternative for fresh water at least for the Lebanese agriculture., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Olefin-linked covalent organic frameworks (OL-COFs) show great promise for visible-light-driven photocatalysis. Manipulating atomic-level donor-acceptor interactions in OL-COFs is key to understanding their exciton effects in this system. Here, three OL-COFs are presented with orthorhombic lattice structures, synthesized via Knoevenagel polycondensation reaction of terephthalaldehyde and tetratopic monomers featuring phenyl, benzo[c][1,2,5]oxadiazole, and benzo[c][1,2,5]thiadiazole moieties. These OL-COFs feature tunable donor-acceptor interactions, making them ideal for studying exciton effects in olefin-linked systems. Comprehensive analyses, including temperature-dependent photoluminescence spectra, ultrafast spectroscopy, and theoretical calculations, reveal that stronger donor-acceptor interactions lead to reduced exciton binding energy (E b ), accelerated exciton dissociation, and longer-lived photogenerated charges, thereby enhancing photocatalytic performance. Notably, The TMO-BDA COF, with the lowest E b , demonstrates superior photocatalytic activity in one-pot sequential organic transformation and excellent catalytic performance in gram-scale reactions, highlighting its potential for practical applications. This work provides valuable insights into regulating the exciton effect at the molecular level in OL-COFs, offering pathways to enhance photocatalytic efficiency., (© 2024 Wiley‐VCH GmbH.)

The highly selective conversion of CO 2 into valuable C 2 H 4 is a highly important but particularly challenging reaction. Herein, the metal-organic frameworks MOF-74(Cu) with infinite Cu(II)-O chains and Cu-BTC (BTC=benzene-1,3,5-tricarboxylate) with paddle-wheel binuclear Cu(II) clusters are used as precursors. These MOFs are reduced by NaBH 4 to obtain Cu 0 /Cu δ+ -based photocatalysts denoted as R-MOF-74(Cu) and R-Cu-BTC, respectively. Significantly, R-MOF-74(Cu) achieves a high selectivity of 90.2 % for C 2 H 4 with a yield rate of 6.5 μmol g -1 within 5 h due to its high Cu + content. To the best of our knowledge, this C 2 H 4 product selectivity is a record high among all the photocatalysts reported so far for photocatalytic CO 2 reduction. In contrast, R-Cu-BTC only forms CO as a product with a cumulative yield of 0.7 μmol g -1 within 5 h. Photoelectrochemical characterization and electron paramagnetic resonance results show that R-MOF-74(Cu) has low interfacial transfer resistance, high photogenerated electron separation efficiency, and excellent CO 2 activation and water oxidation performance. In addition, in situ Fourier transform infrared spectroscopy is used to determine the possible reaction pathway from CO 2 to C 2 H 4 over R-MOF-74(Cu). This work demonstrates the great potential of MOF-derived photocatalysts for the conversion of CO 2 into C 2 H 4 and provides guidance for future photocatalyst development., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

The fluorescence quantum yield of berberine in aqueous solution is significantly smaller than those of organic solution. The time profile of fluorescence intensity of berberine was analyzed by a bi-exponential function, showing that two kinds of states of berberine exist in the solutions. The observed fluorescence lifetime of shorter lifetime species of berberine in water (0.08 ns) was markedly smaller than those of organic solvents and the relative amplitude of the shorter lifetime was dominated in the aqueous solution. Thus, this shorter lifetime can be explained by the deactivation via intramolecular electron transfer. These two states of berberine were independent of pH. The enthalpy and entropy changes between these two states were - 23.2 kJ mol -1 and - 90 J K -1  mol -1 , supporting the aggregation of berberine. In the aggregation state, an electrostatic interaction between cationic berberine and chloride ion decreases the electron accepting ability of the isoquinoline moiety of berberine, resulting in the suppression of intramolecular electron transfer. Furthermore, in the presence of clay, the interaction between berberine and clay increased the fluorescence intensity of berberine and its lifetime, showing that the negative charge of clay suppresses the intramolecular electron transfer. Since the electron transfer quenching of the photo-excited berberine is advantageous for suppressing the phototoxic effect of berberine, the inhibition of berberine aggregation is an important process for the phototoxicity prevention., Competing Interests: Declarations. Conflict of interest: The authors declare that there is no competing financial interest., (© 2024. The Author(s), under exclusive licence to the European Photochemistry Association, European Society for Photobiology.)

The rapid increase in the production and global use of chemicals and their mixtures has raised concerns about their potential impact on human and environmental health. With advances in analytical techniques, in particular, high-resolution mass spectrometry (HRMS), thousands of compounds and transformation products with potential adverse effects can now be detected in environmental samples. However, identifying and prioritizing the toxicity drivers among these compounds remain a significant challenge. Effect-directed analysis (EDA) emerged as an important tool to address this challenge, combining biotesting, sample fractionation, and chemical analysis to unravel toxicity drivers in complex mixtures. Traditional EDA workflows are labor-intensive and time-consuming, hindering large-scale applications. The concept of high-throughput (HT) EDA has recently gained traction as a means of accelerating these workflows. Key features of HT-EDA include the combination of microfractionation and downscaled bioassays, automation of sample preparation and biotesting, and efficient data processing workflows supported by novel computational tools. In addition to microplate-based fractionation, high-performance thin-layer chromatography (HPTLC) offers an interesting alternative to HPLC in HT-EDA. This review provides an updated perspective on the state-of-the-art in HT-EDA, and novel methods/tools that can be incorporated into HT-EDA workflows. It also discusses recent studies on HT-EDA, HT bioassays, and computational prioritization tools, along with considerations regarding HPTLC. By identifying current gaps in HT-EDA and proposing new approaches to overcome them, this review aims to bring HT-EDA a step closer to monitoring applications., Competing Interests: Declarations. Competing interests: The authors declare no competing interests., (© 2024. The Author(s).)

CO 2 fixation (i.e. primary production) is a key function of all ecosystems, providing the carbon and energy that fuel the entire food web. It also plays an important role in mitigating climate change as CO 2 is the most important greenhouse gas. While photosynthesis is regarded as the most important carbon fixation pathway, prokaryotes able to fix carbon in the absence of light (chemolithoautotrophs) can also be a significant source of energy in a light-limited ecosystem. Boreal lakes, notoriously colored and stratified with respect to oxygen and nutrients, present ideal conditions for this so-called dark carbon fixation by the chemolithoautotrophs. However, the prevalence of dark carbon fixation in boreal lakes remains unknown. Here, we measured dark carbon fixation in Swedish lakes from the boreal and boreo-nemoral zones, during summer stratification. We detected dark carbon fixation in 16 out of the 17 lakes studied, and concluded that dark fixation is a widespread phenomenon in boreal lakes. Moreover, the average dark primary production ranged from 18.5 % in the epilimnion to 81.4 % in the hypolimnion of all tested lakes. Our data further suggests that chemolithoautotrophic activity is mostly driven by iron-oxidizing bacteria. The chemolithoautotrophic guild is diverse and seems to be composed of both ubiquitous bacteria, like Gallionellaceae or Chromatiaceae, and endemic taxa, such as Ferrovaceae, which appears to be favored by a low pH. These results are particularly exciting as they suggest that dark carbon fixation could partly compensate for the low photosynthetic capacity in lakes with dark-colored water., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Published by Elsevier B.V.)

Ecology and evolution are considered distinct processes that interact on contemporary time scales in microbiomes. Here, to observe these processes in a natural system, we collected a two-decade, 471-metagenome time series from Lake Mendota (Wisconsin, USA). We assembled 2,855 species-representative genomes and found that genomic change was common and frequent. By tracking strain composition via single nucleotide variants, we identified cyclical seasonal patterns in 80% and decadal shifts in 20% of species. In the dominant freshwater family Nanopelagicaceae, environmental extremes coincided with shifts in strain composition and positive selection of amino acid and nucleic acid metabolism genes. These genes identify organic nitrogen compounds as potential drivers of freshwater responses to global change. Seasonal and long-term strain dynamics could be regarded as ecological processes or, equivalently, as evolutionary change. Rather than as distinct interacting processes, we propose a conceptualization of ecology and evolution as a continuum to better describe change in microbial communities., Competing Interests: Competing interests: The authors declare no competing interests., (© 2025. The Author(s), under exclusive licence to Springer Nature Limited.)

The packing fashion of an organic molecule in the crystal plays a critical role in the global nonlinear optical (NLO) responses under ambient conditions. To better understand how the crystal packing affects the first hyperpolarizability (β) and achieve efficient NLO material, herein, the three positional isomers (regioisomers) through changing the substituted position of 3-carbazole-pyrazine-based isomers were performed. The phenyl groups with different positions ( ortho -, meta -, and para -) of pyrazine, named 23-B3C , 25-B3C , and 26-B3C , are theoretically studied in gas, solvent, and solid states by using the polarizable continuum model and the combined quantum mechanics and molecular mechanics method, respectively. These two regioisomers ( 23-B3C and 25-B3C ) exhibit totally different aggregation behaviors. Through density functional theory (DFT) and time-dependent DFT (TDDFT) calculations, it has been concluded that the geometric changes of 23-B3C and 25-B3C are mainly contributed by the bond length and dihedral angle from gas to the solid phase. Herein, a lower HOMO-LUMO energy gap and a better intramolecular charge-transfer absorption are found for 25-B3C owing to a more sizable π-conjugation effect with smaller bond length alternation. Importantly, the β value of 25-B3C in the crystal with the π-π stacking with the same CT direction between the whole backbones (H-aggregate) and the end-groups (J-aggregate) commonly can substantially increase compared to that of the monomer. However, the obtained reduction of β value for 23-B3C is mainly because of V-aggregate (α > 90°) and reverse J-aggregate in crystal. Thus, our work showcases a profound understanding of the relationship between solid-state packing and macroscopic second-order NLO properties and provides a feasible molecule strategy for the development of high-efficiency NLO materials.

Background: The Antarctic krill Euphausia superba is a keystone species in the Southern Ocean ecosystem. This crustacean has an ancestral clock whose main components have been identified and characterized in the past few years. However, the second feedback loop, modulating clock gene expression through two transcription factors, VRI and PDP1, has yet to be described. The presence of this second regulatory mechanism is suggested by the identification of its negative component, vrille, at the transcriptional level., Results: Here, we describe the second feedback loop of krill by identifying the positive component, pdp1, and functionally characterizing both pdp1 and vrille. Starting from the online transcriptome database KrillDB 2 , we identified and cloned three putative pdp1 sequences which were subsequently analyzed for tissue expression and functional activity using luciferase assays, individually and in combination with two vrille isoforms. Among the pdp1 isoforms, Espdp1&#95;3 displayed higher expression levels in relevant circadian districts than the other two. Furthermore, EsPDP1&#95;3 and EsVRI&#95;2 exhibited the expected positive and negative regulation of the V/P-box in our in vitro system. Finally, Espdp1&#95;3 and Esvrille also showed rhythmic expression in light-dark cycles, supporting their involvement in the regulation of the main circadian clock of the Antarctic krill., Conclusions: This study expands our knowledge about the molecular architecture of the Antarctic krill circadian clock by defining the components that take part in the modulation of clock expression, establishing a second feedback loop., Competing Interests: Declarations. Ethics approval and consent to participate: Not applicable. Consent for publication: Not applicable. Competing interests: The authors declare no competing interests., (© 2024. The Author(s).)

Arylborane complexes ligated by N-heterocyclic carbenes (NHCs) can be synthesized by photoirradiation of a mixture of NHC-boranes and sulfonyl(hetero)arenes. The reaction occurs under mild and convenient conditions without any photocatalyst, which are realized by a radical chain mechanism involving NHC-boryl radicals and sulfonyl radicals. This reaction offered the opportunity to reveal the photophysical property of a 2-borylnaphtho[1,2- d ]thiazole derivative.

Since ether moieties are often found not only in petrochemical products but also in natural organic molecules, the development of methods for manipulating C-O bonds of ethers is important for expanding the range of compound libraries synthesized from biomass resources, which should contribute to the goal of carbon neutrality. We report herein that gold nanoparticles supported on Lewis acidic metal oxides, namely α-Fe 2 O 3 , showed excellent catalytic activity for the reaction of dialkyl ethers and diborons, which enables the conversion of unactivated C(sp 3 )-O bonds to C(sp 3 )-B bonds at around room temperature. Various acyclic and cyclic ethers as well as a series of diborons participated in the heterogeneous gold-catalyzed borylation of unactivated C(sp 3 )-O bonds, to give a series of alkylboronates in high yields. Mechanistic studies corroborated that the present borylation of C(sp 3 )-O bonds of dialkyl ethers proceeded at the interface between gold nanoparticles and Lewis acidic metal oxides. Furthermore, adsorption IR measurements supported the notion that strong Lewis acid sites were generated at the boron atom of diborons adsorbed at the interface between Lewis acidic metal oxides and gold nanoparticles, which enabled us to ensure that the cooperation of gold nanoparticles and Lewis acidic metal oxides was responsible for the efficient transformation of unactivated C(sp 3 )-O bonds in ethers under mild conditions. This novel reaction technology which is specific to heterogeneous catalysts enables the activation of stable C(sp 3 )-O bonds of oxygenated chemical feedstock, which is beneficial for the sustainable synthesis of value-added organoboron compounds.

A sodium trifluoromethanesulfinate-mediated photocatalytic strategy for the aerobic oxidative esterification of aromatic aldehydes and alcohols has been developed, in which the in situ formed pentacoordinate sulfide derived from readily available and inexpensive sodium trifluoromethanesulfinate and oxygen acts as the photocatalyst, and the corresponding aromatic esters were provided in moderate to good yields. The present method is an economical and environmentally friendly protocol.

Gliomas are primary malignant brain tumors with a typically poor prognosis, exhibiting significant heterogeneity across different cancer types. Each glioma type possesses distinct molecular characteristics determining patient prognosis and therapeutic options. This study aims to explore the molecular complexity of gliomas at the transcriptome level, employing a comprehensive approach grounded in network discovery. The graphical lasso method was used to estimate a gene co-expression network for each glioma type from a transcriptomics dataset. Causality was subsequently inferred from correlation networks by estimating the Jacobian matrix. The networks were then analyzed for gene importance using centrality measures and modularity detection, leading to the selection of genes that might play an important role in the disease. To explore the pathways and biological functions these genes are involved in, KEGG and Gene Ontology (GO) enrichment analyses on the disclosed gene sets were performed, highlighting the significance of the genes selected across several relevent pathways and GO terms. Spectral clustering based on patient similarity networks was applied to stratify patients into groups with similar molecular characteristics and to assess whether the resulting clusters align with the diagnosed glioma type. The results presented highlight the ability of the proposed methodology to uncover relevant genes associated with glioma intertumoral heterogeneity. Further investigation might encompass biological validation of the putative biomarkers disclosed., Competing Interests: Declarations. Ethics approval and consent to participate: Not applicable. Consent for publication: Not applicable. Competing interests: The authors declare no competing interests., (© 2024. The Author(s).)

Synthesis of an intrinsically chiral cofacial ABCD-Pt(II)-porphyrin (Por) dimer was achieved by the simple Pt-templated synthesis of Por, followed by Suzuki-Miyaura cross-coupling. The isolated enantiomers exhibited bright red circularly polarized phosphorescence with a B CPP value above 10 1 M -1 cm -1 .

Vehicle electrification is an important means of reducing urban air pollution. However, vehicle electrification does not necessarily reduce particulate matter (PM 2.5 and PM 10 ) and heavy metals (HM) due to the increase in non-exhaust emissions. In this study, we established the emission inventories of PM 2.5 , PM 10 , and their associated heavy metals (PM 2.5 -HM and PM 10 -HM) from the on-road vehicles in the Xiamen-Zhangzhou-Quanzhou metropolitan area in southeastern China between 2015 and 2060. In the base year 2021, brake wear emissions account for 66.6% of PM 2.5 -HM and 76.9% of PM 10 -HM, much higher than the contributions of exhaust emissions to PM 2.5 -HM (12.4%) and PM 10 -HM (6.2%). Light-duty passenger vehicles, heavy-duty trucks, and light-duty trucks are the three main contributors to PM and HM. HM emissions have a high emission density in urban areas. In the business-as-usual (BAU) scenario, HM emissions continue to increase from 2021 to 2060 due to the combined effects of the stricter emission standards and the growth of vehicle population, while the health risk of HM shows an initial decrease and then an increasing trend. Compared with BAU, moderate and aggressive electrification scenarios show a significant reduction in PM 2.5 -HM emissions between 2030 and 2060, but not in PM 10 -HM emissions. Further increases in vehicle electrification will bring forward the peak of PM 2.5 -HM emissions, with the potential to reduce adverse health effects. In the process of vehicle electrification, the reduction of heavy metal emissions from the braking system should be prioritized in order to effectively reduce traffic pollution., Competing Interests: Declarations. Ethical approval: Not applicable. Consent to participate: Not applicable. Consent for publication: The authors give their consent to publish all submitted material. Competing interests: The authors declare no competing interests., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

We report the physical properties of a new class of triarylmethyl-based carbocations containing both an electron-donating diphenyl ether moiety and an electron-accepting carbonyl group with a helical plane framework. Their unique packing patterns were clarified by X-ray crystallographic analysis, which depend on the counter anions to influence their photophysical properties in the solid states. Notably, the interactions between π-cation species and planar anion species lead to a unique panchromatic property, accompanying a near-infrared absorption with a λonset value of 1030 nm, which can be assigned to intermolecular charge transfer transition. We found that the π-cation species with planar anion formed cation dimers, being stacked in opposite directions. The two cation molecules are flanked by two anions on both the top and bottom side. Pair interaction energy decomposition analysis (PIEDA) calculations imply that the origins of the unique packing patterns of the π-cations originate from the electrostatic forces of four neighbouring π-anion species., (© 2024 Wiley‐VCH GmbH.)

Kelps (Laminariales, Phaeophyceae) are foundation species along Arctic rocky shores, providing the basis for complex ecosystems and supporting a high secondary production. Due to ongoing climate change glacial and terrestrial run-off are currently accelerating, drastically changing physical and chemical water column parameters, e.g., water transparency for photosynthetically active radiation or dissolved concentrations of (harmful) elements. We investigated the performance and functioning of Arctic kelp holobionts in response to run-off gradients, with a focus on the effect of altered element concentrations in the water column. We found that the kelp Saccharina latissima accumulates harmful elements (e.g., cadmium, mercury) originating from coastal run-off. As kelps are at the basis of the food web, this might lead to biomagnification, with potential consequences for high-latitude kelp maricultures. In contrast, the high biosorption potential of kelps might be advantageous in monitoring environmental pollution or potentially extracting dissolved rare earth elements. Further, we found that the relative abundances of several kelp-associated microbial taxa significantly responded to increasing run-off influence, changing the kelps functioning in the ecosystem, e.g., the holobionts nutritional value and elemental cycling. The responses of kelp holobionts to environmental changes imply cascading ecological and economic consequences for Arctic kelp ecosystems in future climate change scenarios., Competing Interests: Declarations. Competing interests: The authors declare no competing interests., (© 2024. The Author(s).)

The Mediterranean diet is a well-known dietary pattern that has gained considerable popularity worldwide for its ability to prevent the progression of nonalcoholic fatty liver disease. This is largely attributed to the use of virgin olive oil as the primary source of fat, which contains a substantial amount of squalene, a natural antioxidant. In order to enhance the delivery of squalene and amplify its effects due to its highly hydrophobic nature, herein, squalene has been incorporated into chitosan nanoparticles. The characterization of the resulting nanoparticles was conducted via scanning electron microscopy, dynamic light scattering, ζ potential, Fourier transform infrared spectroscopy, and gas chromatography-mass spectrometry. Reactive oxygen species (ROS) generation and cell viability assays were conducted in oxidative and endoplasmic reticulum (ER) stress in AML12 and a TXNDC5-deficient AML12 cell line, which was generated by CRISPR/Cas9 technology. The results demonstrated that squalene was successfully encapsulated in chitosan nanoparticles and exhibited rapid and efficient cellular uptake at a 150 μM squalene concentration within 48 h. In conclusion, the encapsulation of squalene in chitosan nanoparticles, compared to the poly(d,l-lactide- co -glycolic acid) and ethanol drug carriers, significantly enhanced its cellular uptake. This allows the administration of higher doses, which improve hepatocyte viability and reduce ROS levels, effectively compensating for the adverse effects of TXNDC5 deficiency under the context of hepatocyte stress protection., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Neonicotinoids (NEOs) are ubiquitous in global surface waters. However, the occurrence of NEOs in artificial waterways is unclear. The South-to-North Water Diversion Project (SNWDP) is the largest water diversion project in the world. Water samples from the Luoma Lake to Dongping Lake section of the Eastern Route (ER)-SNWDP were collected and analyzed for eight widely used NEOs to study their spatiotemporal distribution, ecological risks, and health risks. The total NEO concentration was 9-666, 34-138, 8-126, and 7-103 ng L -1 in the water diversion channel, Luoma Lake, Nansi Lake, and Dongping Lake, respectively. The average total NEO concentration in the water diversion channel in the dry season was twice as high as it was in the wet season, due to the precipitation dilution effect. Rather than Luoma Lake, Nansi Lake and Dongping Lake showed a seasonal difference in the average total NEO concentration. NEO concentrations in the three lakes were influenced by the inputs from natural rivers and the water diversion channels under artificial regulation. The seasonal variation in NEO composition between the water diversion channel and the three lakes suggested the channel water was not the only source for NEOs in lakes. For individual NEO ecological risks, thiamethoxam, clothianidin, and imidacloprid in the two seasons would result in high chronic risks in the water diversion channel, and moderate to high risks in Nansi Lake and Luoma Lake. Thiacloprid would result in high chronic risks in Dongping Lake in the two seasons and Luoma Lake in the wet season. For the integral NEO risks, none of the lake water sites exceeded the acute ecological threshold. Health risk assessment suggested drinking water obtained from the ER-SNWDP was safe for public health. The health risks for children exposed to NEOs from the water intake and dermal intake were higher than that for adults., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Mercury pollution is increasing both in the environment and in various organisms, especially top-predators. If variation in individual mercury concentrations is underpinned by genetic among-individual differences in traits related to mercury uptake, storage or excretion, and results in variation in fitness, populations may have the potential to evolve in response to this development. Few studies, however, have been able to collect sufficient information to investigate the genetic basis of pollution levels. We ran Bayesian quantitative genetic analyses, combining pedigree information obtained from a marine top-predator, the common tern (Sterna hirundo), with total mercury concentrations (THg) measured in 1364 blood and 1560 back feather samples obtained from >600 individual birds across seven years. Blood and back feather THg concentrations differed in repeatability (19 vs. 64 %, respectively), but showed similar levels of heritability (c. 9 %) and evolvability (c. 2 %). Blood and back feather THg concentrations were positively correlated at the phenotypic, but not genetic, level. Although further work is needed to elucidate the uptake, storage or excretion pathways underlying these patterns, our study provides pioneering insights into the architecture of THg concentrations, and suggests that adaptation to environmental pollution may to some extent be possible., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Interlaminar shear strength (ILSS) and compressive strength are two of the most critical properties of carbon fiber-reinforced polymer (CFRP). In this report, three types of epoxy resins-4,4'-diaminodiphenylmethane epoxy resin (AG-80), bisphenol A epoxy resin (E-1NT), and novolac epoxy (EPN)-were studied. E-1NT is characterized by low viscosity and low cost but exhibits poor mechanical properties, while AG-80 offers better wetting with carbon fiber. These two epoxy resins were mixed in various mass ratios. The study revealed that as the AG-80 content increased, the ILSS of the composite also increased, reaching a maximum of 94.04 MPa when the AG-80 content reached 60%. Beyond this point, further increases in AG-80 did not enhance the ILSS. Conversely, the compressive strength initially increased but then declined sharply as the AG-80 ratio increased. The maximum compressive strength was recorded at 748.52 MPa when the AG-80 content reached 60%, which was 21% higher than pure AG-80 and 32% higher than pure E-1NT. Additionally, the study examined three different types of ionic sizing agents and four different resin matrices (E-1NT/DDS, AG-80/DDS, AG-80/E-1NT/DDS, EPN/DDS). Among them, the 60% AG-80/40% E-1NT/DDS/CF formulation demonstrated the best balance in both ILSS and compressive strength.

This study focuses on optimizing catalytic activity in photocatalytic hydrogen evolution reaction by precisely designing and modulating the electronic structure of metal single atoms. The catalyst, denoted as PtSA@S-TFPT, integrates low-valence platinum single atoms into sulfur-containing covalent organic frameworks. The robust asymmetric four-coordination between sulfur and platinum within the framework enables a high platinum loading of 12.1 wt%, resulting in efficient photocatalytic hydrogen production activity of 11.4 mmol g -1  h -1 and stable performance under visible light. These outcomes are attributed to a reduced hydrogen desorption barrier and enhanced photogenerated charge separation, as indicated by density functional theory calculations and dynamic carrier analysis. This work challenges traditional notions and opens an avenue for developing low-valence metal single atom-loaded covalent organic framework catalysts to advance photocatalytic hydrogen evolution., Competing Interests: Competing interests: The authors declare no competing interests., (© 2024. The Author(s).)

Contamination by neonicotinoid (NEO) insecticides in surface waters is a global problem. Nevertheless, the occurrence of NEOs in lakes is not well known. Hongze Lake, the largest impounded lake on the Eastern Route of the South-to-North Water Diversion Project, was selected to investigate the distribution, ecological risks, and health risks of NEOs. Water samples from the lake and nearby rivers were collected and analyzed for 8 widely used NEOs in three seasons. The results indicated the average total NEO concentration in summer, winter, and spring was 222, 211, and 244 ng L -1 for the river water, and 265, 213, and 181 ng L -1 for the lake water, respectively, with no statistical seasonal difference. For the river water, the highest total NEO concentration in the three seasons was observed in the Andong River. For the lake water, the total NEO concentrations in summer were relatively high in sites near the inflow river estuaries due to the high riverine inputs during the flood period. The spatial difference in NEO concentration was relatively low in winter, which may be related to the wind-driven lake current. The seasonal variation in NEO compositions in the lake was generally similar to that in the river, indicating riverine input was the important source for the lake. Huai River was the largest contributor to the NEO inputs to the lake, and Sanhe Gate was the major output pathway. Clothianidin and imidacloprid in the river and lake water would produce moderate acute ecological risks in summer. Thus, the usage of the above two NEOs should be decreased or restricted. For integral NEO risks, 53% and 58% of the river and lake water sites exceeded the acute ecological threshold, respectively. Health risk assessment suggested drinking the water obtained from the lake would not produce a negative impact on public health., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

While many plastic additives show endocrine disrupting properties, this has not been studied for micro- and nanoplastics (MNPs) particles despite their ubiquitous presence in humans. The objective of this study was to determine the effects of various sizes and concentrations of polystyrene (PS)-MNPs (50-10,000 nm, 0.01-100 μg/mL) on estrogen- and androgen receptor (ER and AR) activity and steroidogenesis in vitro. Fluorescent (F)PS-MNPs of ≤1000 nm were internalized in VM7 and H295R cells and FPS-MNPs ≤200 nm in AR-ecoscreen cells. H295R cells displayed the highest uptake and particles were closer to the nucleus than other cell types. None of the sizes and concentrations PS-MNPs tested affected ER or AR activity. In H295R cells, PS-MNPs caused some statistically significant changes in hormone levels, though these showed no apparent concentration or size-dependent patterns. Additionally, PS-MNPs caused a decrease in estriol (E3) with a maximum of 37.5 % (100 μg/mL, 50 nm) and an increase in gene expression of oxidative stress markers GPX1 (1.26-fold) and SOD1 (1.23-fold). Taken together, our data show limited endocrine-disrupting properties of PS-MNPs in vitro. Nevertheless the importance of E3 in the placenta warrants further studies in the potential effects of MNPs during pregnancy., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Traditionally, mathematical models in ecology placed an emphasis on asymptotic, long-term dynamics. However, a large number of recent studies highlighted the importance of transient dynamics in ecological and eco-evolutionary systems, in particular 'long transients' that can last for hundreds of generations or even longer. Many models as well as empirical studies indicated that a system can function for a long time in a certain state or regime (a 'metastable regime') but later exhibits an abrupt transition to another regime not preceded by any parameter change (or following the change that occurred long before the transition). This scenario where tipping occurs without any apparent source of a regime shift is also referred to as 'metastability'. Despite considerable evidence of the presence of long transients in real-world systems as well as models, until recently research into long-living transients in ecology has remained in its infancy, largely lacking systematisation. Within the past decade, however, substantial progress has been made in creating a unifying theory of long transients in deterministic as well as stochastic systems. This has considerably accelerated further studies on long transients, in particular on those characterised by more complicated patterns and/or underlying mechanisms. The main goal of this review is to provide an overview of recent research on long transients and related regime shifts in models of ecological dynamics. We pay special attention to the role of environmental stochasticity, the effect of multiple timescales (slow-fast systems), transient spatial patterns, and relation between transients and spatial synchronisation. We also discuss current challenges and open questions in understanding transients with applications to ecosystems dynamics., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier B.V. All rights reserved.)

Non-flow aqueous zinc-bromine batteries (AZBBs) are highly attractive owing to their lightweight construction and largely reduced cost compared with the flow ones. Yet, their development is restricted by the sluggish reaction kinetics of Br 2 /Br - , the shuttle of soluble polybromide species (Br n - , n is odd), and the poor stability of Zn-based anode. Herein, an effective alkaline-neutral electrolyte decoupling system is constructed to mitigate these issues, where nitrogen-doped carbon felt with high catalytic activity to Br 2 reaction is developed for cathode, a cost-effective cation exchange membrane (CEM) of polyethersulfone/sulfonated polyether ether ketone (PES/SPEEK-M) that can stop Br - reaction is developed for cathode, a cost-effective cation exchange membrane (CEM) of polyethersulfone/sulfonated polyether ether ketone (PES/SPEEK-M) that can stop Br n - is used as separator, and glucose that can inhibit dendrites is introduced as anolyte additive. The constructed flowless AZBB mainly consists of two separate redox couples, including Zn/Zn(OH) 4 2- in alkaline anolyte and Br 2 /Br - in neutral media, where non-cations (e.g. OH - , Zn(OH) 4 2- , H 2 O,  and Br n - ) can be restricted to their respective chamber by the PES/SPEEK-M while cations can pass by. In the optimized system, good electrochemical performance is achieved, mainly including a surprising discharge voltage of 2.01 V, a high average Coulombic efficiency of 96.7%, and a good cycling life of ≈1000 cycles without obvious capacity decay at a fixed charge capacity of 2 mAh cm -2 ., (© 2024 Wiley‐VCH GmbH.)

Adrenergic receptors (ARs) are preferentially expressed by innate lymphocytes such as natural killer (NK) cells. Here, we study the effect of epinephrine-mediated stimulation of the β2-adrenergic receptor (β2AR) on the function of human NK cells. Epinephrine stimulation inhibited early NK cell signaling events and blocked the function of the integrin LFA-1. This reduced the adhesion of NK cells to ICAM-1, explaining how NK cells are mobilized into the peripheral blood upon epinephrine release during acute stress or exercise. Additionally, epinephrine stimulation transiently reduced NK cell degranulation, serial killing, and cytokine production and affected metabolic changes upon NK cell activation via the cAMP-protein kinase A (PKA) pathway. Repeated exposure to β2AR agonists resulted in the desensitization of the β2AR via a PKA feedback loop-initiated G-protein switch. Therefore, acute epinephrine stimulation of chronically β2AR stimulated NK cells no longer resulted in inhibited signaling and reduced LFA-1 activity. Sustained stimulation by long-acting β2-agonists (LABA) not only inhibited NK cell functions but also resulted in desensitization of the β2AR. However, peripheral NK cells from LABA-treated asthma patients still reacted unchanged to epinephrine stimulation, demonstrating that local LABA administration does not result in detectable systemic effects on NK cells., (© 2024 The Author(s). European Journal of Immunology published by Wiley‐VCH GmbH.)

Current wastewater-based epidemiology (WBE) studies are predominantly focused on the analysis of urinary biomarkers present in the liquid phase of influent wastewater (IWW). This approach systematically underestimates less polar metabolites, such as cannabis biomarkers. These biomarkers can potentially sorb to and desorb from suspended particulate matter (SPM) present in IWW. This study investigates the bidirectional partitioning of THCCOOH between the liquid phase and SPM of IWW by performing multiple sorption experiments using THCCOOH-D 9 as a surrogate due to the unavailability of blank SPM and blank IWW. In addition, this study involves the analysis of IWW collected from eight wastewater treatment plants (WWTP) (n = 56) across four European countries, where raw IWW, the liquid phase and SPM were separately analysed to identify potential trends in the fraction of THCCOOH in the SPM between and withing the examined locations. Based on the performed sorption experiments, bidirectional partitioning of THCCOOH between the liquid phase and SPM was noted , showing partition between both phases when only one of the two phases was spiked. It was illustrated that the concentration of SPM had a notable influence on the THCCOOH partitioning between both phases. In addition to the inter location variability (average THCCOOH present in the SPM ranged 31-59 %), a substantial intra location variation was also observed, e.g., in one location ranged 17-58 %. While the determination of a correction factor for the amount of THCCOOH present in SPM would be ideal, this is challenging, since the amount of SPM is not fixed in all IWW samples. Although SPM has influence on the THCCOOH partition, no correlation (p value Spearman correlation = 0.3160) was observed between the SPM concentration and the fraction of THCCOOH in the solid phase. Moreover, the collection of homogenized samples is difficult, and the time required to reach an equilibration in partitioning of THCCOOH between both IWW phases remains unclear. Due to i) the large inter-and intra-location variation of THCCOOH present in the SPM, ii) the variability in SPM concentration in IWW samples, and iii) the time required to reach a partitioning equilibration, an analytical procedure based on liquid-liquid extraction (LLE) that considers both the liquid phase and SPM of IWW is recommended to reduce the overall uncertainty for THCCOOH measurement in IWW. It was illustrated that this extraction method is capable to recover the total concentration of THCCOOH in both phases., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Particulate organic matter (POM) plays a crucial role in the organic composition of lakes; however, its characteristics remain poorly understood. This study aimed to characterize the structure and composition of POM in Lake Baiyangdian using many kinds of techniques and investigate the effects of different extracted forms of POM on water quality. The suspended particulate matter in the lake had complex compositions, with its components primarily derived from aquatic plants and their detritus. The organic matter content of the suspended particulate matter was relatively high (organic carbon content 27.29-145.94 g/kg) for the sum of three extractable states (water-extracted organic matter [WEOM], humic acid, and fulvic acid) and one stable bound state (humin). Spatial distribution analysis revealed that the POM content in the water increased from west to east, which was consistent with the water flow pattern influenced by the Baiyangdian water diversion project. Fluorescence spectroscopy analysis of the WEOM showed three prominent peaks with excitation/emission wavelengths similar to those of dissolved organic matter peaks. These peaks were potentially initial products of POM conversion into dissolved organic matter. Furthermore, the intensity of the WEOM fluorescence peak (total fluorescence peak intensity) was negatively correlated with the inorganic nitrogen concentration in water (p < 0.01), while the intensity of the HA fluorescence peak showed a positive correlation with the inorganic nitrogen concentration (p < 0.01). This suggested that exogenous organic matter inputs led to the diffusion of alkaline dissolved nitrogen from sediment into water, while degradation processes of aquatic plant debris contributed to the decrease in inorganic nitrogen concentrations in the water column. These findings enhance our understanding of POM characteristics in shallow lakes and the role of POM in shallow lake ecosystems., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Aquatic ecosystems house a significant fraction of Earth's biosphere, yet most prokaryotes inhabiting these environments remain uncultivated. While recently developed genome-resolved metagenomics and single-cell genomics techniques have underscored the immense genetic breadth and metabolic potential residing in uncultivated Bacteria and Archaea, cultivation of these microorganisms is required to study their physiology via genetic systems, confirm predicted biochemical pathways, exploit biotechnological potential, and accurately appraise nutrient turnover. Over the past two decades, the limitations of culture-independent investigations highlighted the importance of cultivation in bridging this vast knowledge gap. Here, we collected more than 80 highly sought-after uncultivated lineages of aquatic Bacteria and Archaea with global ecological impact. In addition to fulfilling critical roles in global carbon, nitrogen, and sulfur cycling, many of these organisms are thought to partake in key symbiotic relationships. This review highlights the vital contributions of uncultured microbes in aquatic ecosystems, from lakes and groundwater to the surfaces and depths of the oceans and will guide current and future initiatives tasked with cultivating our planet's most elusive, yet highly consequential aquatic microflora., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Alexander J. Probst reports financial support was provided by Ministry of Culture and Science of the State of North Rhine-Westphalia. Alexander J. Probst reports financial support was provided by Federal Ministry of Education and Research Berlin Office. Alexander J. Probst reports financial support was provided by German Research Foundation. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Microbial biotransformation of trace organic chemicals (TOrCs) is an essential process in wastewater treatment to eliminate environmental pollution. Understanding TOrC biotransformation mechanisms, especially at their original concentrations, is important to optimize treatment performance, whereas our current knowledge is limited. Here, we investigated the biotransformation of seven TOrCs by 24 model communities. The genome-centric analyses unraveled potential biotransformation drivers concerning functional genes, enzymes, and responsible bacteria. We obtained efficient model communities for completely removing ibuprofen, caffeine, and atenolol, with transformation efficiencies between 0 % and 45 % for sulfamethoxazole, carbamazepine, trimethoprim, and gabapentin. Biotransformation performance was not fully reflected by the presence of known biotransformation genes and enzymes in the metagenomes of the communities. Functional similar homologs to existing biotransformation genes and enzymes (e.g., long-chain-fatty-acid-CoA ligase encoded by fadD and fadD13 gene) could play critical roles in TOrC metabolism. Finally, we identified previously undescribed degrading strains, e.g., Rhodococcus qingshengii for caffeine, carbamazepine, sulfamethoxazole, and ibuprofen biotransformation, and potential transformation enzymes, e.g., SDR family oxidoreductase targeting sulfamethoxazole and putative hypothetical proteins for caffeine, atenolol and gabapentin biotransformation. This study provides fundamental insights into naturally assembled low-complexity degrader communities that can help to identify and tackle the current research gaps on biotransformation., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Christian Wurzbacher reports financial support was provided by German Research Foundation. Lijia Cao reports financial support was provided by China Scholarship Council. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

The toxicity of PM 2.5 does not necessarily change synchronously with its mass concentration. In this study, the chemical composition (carbonaceous species, water-soluble ions, and metals) and oxidative potential (dithiothreitol assay, DTT) of PM 2.5 were investigated in 2017/2018 and 2022 in Xiamen, China. The decrease rate of volume-normalized DTT (DTT v ) (38%) was lower than that of PM 2.5 (55%) between the two sampling periods. However, the mass-normalized DTT (DTT m ) increased by 44%. Clear seasonal patterns with higher levels in winter were found for PM 2.5 , most chemical constituents and DTT v but not for DTT m . The large decrease in DTT activity (84%-92%) after the addition of EDTA suggested that water-soluble metals were the main contributors to DTT in Xiamen. The increased gap between the reconstructed and measured DTT v and the stronger correlations between the reconstructed/measured DTT ratio and carbonaceous species in 2022 were observed. The decrease rates of the hazard index (32.5%) and lifetime cancer risk (9.1%) differed from those of PM 2.5 and DTT v due to their different main contributors. The PMF-MLR model showed that the contributions (nmol/(min·m 3 )) of vehicle emission, coal + biomass burning, ship emission and secondary aerosol to DTT v in 2022 decreased by 63.0%, 65.2%, 66.5%, and 22.2%, respectively, compared to those in 2017/2018, which was consistent with the emission reduction of vehicle exhaust and coal consumption, the adoption of low-sulfur fuel oil used on board ships and the reduced production of WSOC. However, the contributions of dust + sea salt and industrial emission increased., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

It is of great significance but remains challenging to simultaneously development cost-effective and efficient non-noble metal electrocatalysts (NNMEs) for oxygen reduction reaction (ORR) in both alkaline and acidic solutions. In current work, a multi-component synergism system is developed, which is comprised of molybdenum phosphide (MoP) shell onto iron phosphide clusters anchored on carbon matrixes that embedded with numerous FeN 4 species (MoP/Fe 2 P-FeN 4 ). The optimized MoP/Fe 2 P-FeN 4 electrocatalyst delivers a synergistic enhancement in both alkaline and acidic ORR performances: E 1/2 : 0.885 V (0.1 M KOH electrolyte) and E 1/2 : 0.742 V (0.1 M HClO 4 electrolyte). Furthermore, the equipped zinc-air batteries (ZABs) of MoP/Fe 2 P-FeN 4 exhibit a power density of 140.6 mW cm -2 @219.6 mA cm -2 , which surpasses the corresponding Fe 2 P-FeN 4 and commercial Pt/C catalyst. The computational calculations reveal that MoP/Fe 2 P-FeN 4 shows a relative increase of d-band center closer to Fermin level than Fe 2 P-FeN 4 , tuning the rate-determining step to conversion of *O to *OOH intermediate, thus significant reducing the energy barrier and enhancing ORR activity. This strategy opens new opportunities to rational design of Fe-based nanocomposites for stimulated ORR and further ZAB activities., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Published by Elsevier Inc.)

We synthesized trigonal planar Cu(I) iodide complexes with 1,2-bis(methylpyridin-2-yl)disilane ligands L1 - L4 and investigated how the substitution position of the methyl group on the pyridine ring in σ-π conjugation affects their structure and physical properties. The structures were characterized by NMR, elemental analysis, and single-crystal X-ray diffraction. In the crystalline state, the methylpyridyl groups of CuIL1 - CuIL3 were coordinated with Cu(I) in an anticlinal conformation relative to the Si-Si σ bond, whereas those of CuIL4 were coordinated with Cu(I) in a synperiplanar conformation relative to the Si-Si σ bond. The conformational difference in the crystalline state was influenced by the N-Cu-N bite angle and the emission wavelength. CuIL1 - CuIL3 exhibited blue-green emission (λ em : 476-494 nm), and CuIL4 exhibited green-yellow emission (λ em : 512 nm) with high emission quantum yields (Φ: 0.59-0.86) in the crystalline state at 293 K. These Cu(I) complexes exhibited thermally activated delayed fluorescence from the S 1 state at 293 K and phosphorescence from the T 1 state at 77 K in the crystalline state. The optical properties in the crystalline state were discussed by DFT and TD-DFT calculations. These complexes also displayed aggregation-induced emission in THF-water solution ( f w > 80%), although they did not show emission in dehydrated THF.

Background: Toxic elements As and Hg in coastal waters affect human health through the food chain even at trace levels. The simultaneous determination of As and Hg in seawater using electrochemical vapor generation (ECVG) with atomic fluorescence spectrometer (AFS) currently has technical bottlenecks. One is the need for a simple and efficient chemical reaction cell and corresponding parameters to generate both AsH 3 and Hg vapors, and the other is a suitable preservation method of the mixed standard solutions., Results: A novel, efficient, online ECVG device was developed and interfaced with a laboratory-built multichannel AFS. The electrolytic cell adopted Sn-Pb alloy as the cathode material to generate both AsH 3 and Hg vapors by electrolysis, replacing the unstable reagent tetrahydroborate (THB) usually used in most traditional vapor generation methods. The AFS was equipped with a built-in H 2 generator for fuel supply, instead of the conventional acid-THB system. A mixed standard solution of As and Hg was prepared and preserved using thiourea-ascorbic acid as a fixing agent for Hg and a prereduction agent for As(V). The method detection limits (LOD, 3σ) were 0.005 and 0.003 μg/L for As and Hg, respectively. The relative standard deviations (RSD, n = 8) of the spiked samples were 2.8 % (0.50 μg/L As) and 3.1 % (0.05 μg/L Hg), respectively. The recoveries of standard spiked seawater samples with different salinities ranged from 86.1 % to 115.3 %., Significance: The system has been successfully applied to the simultaneous analysis of As and Hg in the seawater samples collected from the Xiamen coastal area. The study results provide a sensitive, accurate, and efficient method to promote the development and utilization of simultaneous analysis of multielement in seawaters., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Background: Previous studies have identified structurally diverse N-acyl amino acid methyl esters (NAMEs) in culture extracts of Roseovarius tolerans EL-164 (Roseobacteraceae). NAMEs are structural analogues of the common signaling compounds N-acyl homoserine lactones (AHLs), but do not participate in AHL-mediated signaling. NAMEs show minor antialgal and antimicrobial activity, but whether this activity serves as the primary ecological role remains unclear., Results: To enable dose-dependent bioactivity-testing, we have established a chromatographic method for quantification of NAMEs in bacterial culture extracts. The concentrations determined for the two major NAMEs produced by EL-164, C16:1-NAME and C17:1-NAME, ranged between 0.685 and 5.731 mg L - 1 (2.0-16.9 µM) and 5.3-86.4 µg L - 1 (15.0-244.3 nM), respectively. Co-quantification of the C14:1-AHL showed concentrations ranging between 17.5 and 58.7 mg L - 1 (56.6-189.7 µM). We observed distinct production patterns for NAMEs and AHLs, with a continuous NAME production during the entire incubation period. We conducted a spike-in experiment, using the determined metabolite concentrations. By comparing the transcriptomes of pre- and post-metabolite-spikes, we identified three clusters of differentially expressed genes with distinct temporal expression patterns. Expression levels of stress response genes differed between NAME- and AHL-spiked EL-164 cultures in the stationary phase., Conclusions: Our findings support previous studies suggesting an ecological role for C16:1-NAME as antibiotic, by proving that NAME concentrations in batch cultures were higher than the minimal inhibitory concentrations against Maribacter sp. 62 - 1 (Flavobacteriia) and Skeletonema costatum CCMP 1332 (Coscinodiscophyceae) reported in the literature. Our study further exemplified the broad application range of dose-dependent testing and highlighted the different biological activities of NAMEs and AHLs., Competing Interests: Declarations. Ethics approval and consent to participate: Not applicable. Consent for publication: Not applicable. Competing interests: The authors declare no competing interests., (© 2024. The Author(s).)

Nitroaromatics, as an important member and source of nitrogen-containing aromatics, is bringing enormous economic benefits in fields of pharmaceuticals, dyes, pesticides, functional materials, fertilizers, and explosives. Nonetheless, the notoriously polluting nitration industry, which suffers from excessive discharge of fumes and waste acids, poor functional group tolerance, and tremendous purification difficulty, renders mild, efficient, and environmentally friendly nitration a formidable challenge. Herein, we develop a visible-light-driven biocompatible arene C-H nitration strategy with good efficiency and regioselectivity, marvelous substrate applicability and functional group tolerance, and wide application in scale-up synthesis, total synthesis, and late-stage functionalization. A nitryl radical delivered through unusual β-homolysis of a photoexcited ferric-nitrate complex is proposed to be the key nitrification reagent in this system., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Halogenated volatile organic compounds (HVOCs) pose significant bioaccumulative and toxicological risks, necessitating effective strategies for their removal. Here, we show, through a computational study employing density functional theory and coupled cluster methods, the detailed mechanism and kinetic properties of Cl-initiated degradation reactions of 2-chloropropane (2-CP, (CH 3 ) 2 CHCl) and 2-methylpropanoyl halide ((CH 3 ) 2 CHCOX, X = Cl, Br, F). The reaction rate constants of all the channels were calculated by the canonical variational transition state theory (CVT) with the correction of the small curvature tunneling effect (SCT) at 200-1000 K. The subsequent transformation pathways of the major radical products of (CH 3 ) 2 CHCl and (CH 3 ) 2 CHCOCl in the presence of O 2 , NO, and HO 2 radical were investigated. The results elucidate the reaction pathways and rate constants, which are in excellent agreement with the experimental data at 296 K. We further explore the atmospheric implications of these reactions by assessing the atmospheric lifetime (τ) and ozone depletion potential (ODP). Additionally, we delve into the aquatic toxicity and bioaccumulation potential of the reactants and their transformation products. This study not only advances our knowledge of the atmospheric fate of halogenated hydrocarbons but also underscores the importance of considering the environmental and toxicological impacts in the development of HVOC mitigation strategies.

Herein, we report the structure-based selection via molecular docking of four N -heterocyclic bis-carbene gold(I) complexes, whose potential as ligands for the hTel23 G-quadruplex structure has been investigated using circular dichroism (CD) spectroscopy, CD melting, and polyacrylamide gel electrophoresis (PAGE). The complex containing a bis(1,2,3,4,6,7,8,9-octahydro-11 H -11 λ 3 -pyridazino[1,2-a]indazol-11-yl) scaffold induces a transition from the hybrid (3 + 1) topology to a prevalent parallel G-quadruplex conformation, whereas the complex featuring a bis(2-(2-acetamidoethyl)-3 λ 3 -imidazo[1,5-a]pyridin-3(2 H )-yl) moiety disrupted the original G-quadruplex structure. These results deserve particular attention in light of the recent findings on the pathological involvements of G-quadruplexes in neurodegenerative diseases.

Metal nanoclusters stabilized by N-heterocyclic carbene (NHC) ligands have attracted increasing interest for their special structures and diverse applications. However, developing synthetic strategies and extending the database of NHC-protected nanoclusters are still challenging tasks. In this work, a novel and rapid synthetic method is developed to prepare AuAg alloy nanocluster ligated by carbene based on the reactivity of nanoclusters. The rod-like carbene-capped bimetal nanocluster, [Au 13 Ag 12 (PPh 3 ) 8 (BMIm) 2 I 8 ]SbF 6 (Au 13 Ag 12  : BMIm), was achieved and characterized by a series of techniques. The alloy nanocluster consists of two vertex-sharing icosahedrons and carbene ligands, phosphine ligands, and I atoms. Interestingly, the introduced carbene ligands show strong coordination capabilities with Au, enhancing the interaction between metal core and ligands. To the best of our knowledge, the carbene-capped Au 13 Ag 12  : BMIm nanocluster is the first of its kind to show higher thermostability and higher sensitivity to light compared with the homogeneously capped analogue nanocluster ([Au 13 Ag 12 (PPh 3 ) 10 I 8 ]SbF 6 ). Density functional theory calculations attribute these properties to a unique delocalization of electrons within the frontier orbitals. Finally, the Au 13 Ag 12  : BMIm anchored on NiFe-LDH exhibits remarkable electrocatalytic activity in the electrosynthesis of urea from NO 3 - and CO 2 , achieving a urea production rate of 29.5 mmol g cat -1  h -1 with a Faradaic efficiency of 34 % at -0.5 V (vs. RHE)., (© 2024 Wiley-VCH GmbH.)