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Annexins (ANXAs), calcium-sensitive phospholipid-binding proteins, are pivotal for cellular membrane repair, which is crucial for eukaryotic cell survival under membrane stress. With their unique trimeric arrangements and crystalline arrays on the membrane surface, ANXA4 and ANXA5 induce membrane curvature and rapidly orchestrate plasma membrane resealing. However, the influence of cholesterol and anionic lipid headgroups on annexin-induced membrane curvature remains poorly understood at the molecular level. Using all-atom molecular dynamics simulations, we measured the local curvature-induced underneath ANXA4 and ANXA5 monomers and trimers when they bind to lipid bilayers of distinct lipid compositions: PSPC (20% POPS, 80% POPC), PAPC (20% POPA, 80% POPC), and PSPCCHL (14% POPS, 56% POPC, 30% cholesterol). Laser injury experiments were conducted on MCF7 cells transfected to transiently express fluorescently labeled ANXA4 or ANXA5 to facilitate the examination of protein and lipid accumulation at the damage site. Annexin trimers induce higher curvature than monomers, particularly with cholesterol present. Annexin trimers induce similar curvatures on both PAPC and PSPC membranes. Notably, among monomers, ANXA5 induces the highest curvature on PAPC, suggesting more efficient recruitment of ANXA5 compared with ANXA4 in the early stages of membrane repair near a lesion. Laser injury experiments confirm rapid coaccumulation of phosphatidic acid lipids with ANXA4 and ANXA5 at repair sites, potentially enhancing the accumulation of annexins in the early stages of membrane repair.

Polysaccharide-based hydrogels are suitable for use in the field of flexible bioelectronics due to their benign mechanical properties and biocompatibility. However, the preparation of hydrogel sensors with high performance without affecting their physicochemical properties (e.g., flexibility, toughness, self-healing, and antibacterial activity) remains a challenge and needs to be solved. Herein, a metal ion cross-linking reinforced, double network hydrogel was formed from a 2-acrylamide-2-methylpropanesulfonic acid (AMPS) copolymer interpenetrating κ-carrageenan (CAR), followed by immersing the gel in a Cu 2+ ion solution to obtain an antibacterial CAR/P(AM- co -AMPS)-Cu 2+ conductive hydrogel. LiCl was added as the electrolyte. The presence of the LiCl electrolyte and sulfonated molecular chain units not only gives the hydrogel good electrical conductivity (conductivity up to 2.68 S/m) but also improves the sensitivity of the hydrogel as a stress-strain sensor, with a hydrogel sensitivity GF of up to 3.76 in the 20%-100% strain range and response time of up to 280 ms. The CAR double-helical structure and sol-gel properties and the interaction of multiple noncovalent bonds between polymers provide the hydrogel with excellent self-healing, with a self-healing efficiency of 68%. In addition, the electrostatic interaction of Cu 2+ with Escherichia coli cells can inhibit their growth, exhibiting good antibacterial properties with an inhibition circle diameter of 20.5 mm. This work could provide an effective strategy for antibacterial multifunctional CAR-based bionic sensors.

Introducing kosmotropic salts enhances protein stability and reduces solubility by withdrawing water from the protein surface, leading to 'salting out', a phenomenon we have mimicked in supramolecular polymers (SPs). Under the guidance of Ag + , folic acid (FA) self-assembled in water through slipped-stacking and hydrophobic interactions into elongated, robust one-dimensional SPs, resulting in thermo-stable supergels. The SPs exhibited temperature and dilution tolerance, attributed to the stability of the FA-Ag + complex and its hydrophobic stacking. Importantly, FA-Ag + SP's stability has been augmented by the kosmotropic anions, such as SO 4 2- , strengthening hydrophobic interactions in the SP, evident from the enhanced J-band, causing improvement of gel's mechanical property. Interestingly, higher kosmotrope concentrations caused a significant decrease in SP's solubility, leading to precipitation of the reinforced SPs─a 'salting out' effect. Conversely, chaotropes like ClO 4 - slightly destabilized hydrophobic stacking and promoted an extended conformation of individual SP chain with enhanced solubility, resembling a 'salting in' effect.

Background: Food safety has become an essential aspect of public concern and there are lots of detection means. Liquid chromatography plays a dominating role in food safety inspection because of its high separation efficiency and reproducibility. However, with the increasing complexity of real samples and monitoring requirements, conventional single-mode chromatography would require frequent column replacement and cannot separate different kinds of analytes on a single column simultaneously, which is costly and time-consuming. There is a great need for fabricating mixed-mode stationary phases and validating the feasibility of employing mixed-mode stationary phases for food safety inspection., Results: This work fabricated multifunctional stationary phases for liquid chromatography to determine diverse food additives under the mixed mode of RPLC/HILIC/IEC. Two dicationic ionic liquid silanes were synthesized and bonded onto the silica gel surface. The functionalized silica was characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and elemental analysis. Both columns provide satisfactory separation performance towards 6 hydrophilic nucleosides, 4 hydrophobic polycyclic aromatic hydrocarbons, and 5 anions. Great repeatability of retention (RSD <0.1 %) and column efficiency (100330 plate/m) were obtained. Thermomechanical analysis and linear solvation energy relationship investigated the retention mechanism. Finally, the better in two prepared columns was employed to separate and determine the contents of NO 2 - and NO 3 - in vegetables(highest 4906 mg kg -1 NO 3 - in spinach), preservatives in bottled beverages (180.8 mg kg -1 sodium benzoate in soft drink), and melamine in milk with satisfactory performance and recovery rates ranging from 96.4 % to 105.6 %., Significance: This work developed a novel scheme for preparing mixed-mode stationary phases by dicationic ionic liquid which provides great separation selectivity. Most importantly, this work proved the superiority of employing mixed-mode stationary phases for food safety inspection, which might avoid high-cost and frequent changes of columns and chromatography systems in the near future., 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.)

This review provides an in-depth examination of recent progress in the development of chemosensors, with a particular emphasis on colorimetric and fluorescent probes. It systematically explores various sensing mechanisms, including metal-to-ligand charge transfer (MLCT), ligand-to-metal charge transfer (LMCT), photoinduced electron transfer (PET), intramolecular charge transfer (ICT), and fluorescence resonance energy transfer (FRET), and elucidates the mechanism of action for cation and anion chemosensors. Special attention is given to phenothiazine-based fluorescence probes, highlighting their exceptional sensitivity and rapid detection abilities for a broad spectrum of analytes, including cations, anions, and small molecules. Phenothiazine chemosensors have emerged as versatile tools widely employed in a multitude of applications, spanning environmental and biomedical fields. Furthermore, it addresses existing challenges and offers insights into future research directions, aiming to facilitate the continued advancement of phenothiazine-based fluorescent probes., (© 2024. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

The increasing need for mass spectrometric analysis of RNA molecules calls for a better understanding of their gas-phase fragmentation behaviors. In this study, we investigate the effect of terminal phosphate groups on the fragmentation spectra of RNA oligonucleotides (oligos) using high-resolution mass spectrometry (MS). Negative-ion mode collision-induced dissociation (CID) and higher-energy collisional dissociation (HCD) were carried out on RNA oligos containing a terminal phosphate group on either end, both ends, or neither end. We find that terminal phosphate groups affect the fragmentation behavior of RNA oligos in a way that is dependent on the precursor charge state and the oligo length. Specifically, for precursor ions of RNA oligos of the same sequence, those with 5'- or 3'-phosphate, or both, have a higher charge state distribution and lose the phosphate group(s) in the form of a neutral (H 3 PO 4 or HPO 3 ) or an anion ([H 2 PO 4 ] - or [PO 3 ] - ) upon CID or HCD. Such a neutral or charged loss is most conspicuous for precursor ions of an intermediate charge state, e.g., 3 - for 4-nt oligos or 4 - and 5 - for 8-nt oligos. This decreases the intensity of sequencing ions ( a- , a-B , b- , c- , d- , w- , x- , y- , z- ions) and hence is unfavorable for sequencing by CID or HCD. Removal of terminal phosphate groups by calf intestinal alkaline phosphatase improved MS analysis of RNA oligos. Additionally, the intensity of a fragment ion at m / z 158.925, which we identified as a dehydrated pyrophosphate anion ([HP 2 O 6 ] - ), is markedly increased by the presence of a terminal phosphate group. These findings expand the knowledge base necessary for software development for MS analysis of RNA.

This study examines pharmaceutically acceptable inorganic salts of memantine, specifically focusing on hydrogen sulfate, sulfate, and dihydrogen phosphate salts, with the aim of finding alternatives to the commonly used chloride salt in the treatment of Alzheimer's disease. Through comprehensive solid-state characterization, including powder X-ray diffraction, thermal analysis, and solubility testing, we unveil complex polymorphic behaviors, reversible solid-state transitions, and significant differences in solubility and stability among the salts. Notably, the hydrogen sulfate salt emerges as a promising candidate for drug formulations, offering improved solubility, nonhygroscopic nature, and favorable morphological characteristics compared to the existing chloride salt. This work establishes a foundation for further investigation into memantine salts as potential therapeutics with improved efficacy.

This study is focused on the utilization of naturally occurring salicylic acid and nicotinamide (vitamin B 3 ) in the development of novel sustainable Active Pharmaceutical Ingredients (APIs) with significant potential for treating acne vulgaris. The study highlights how the chemical structure of the cation significantly influences surface activity, lipophilicity, and solubility in aqueous media. Furthermore, the new ionic forms of APIs, the synthesis of which was assessed with Green Chemistry metrics, exhibited very good antibacterial properties against common pathogens that contribute to the development of acne, resulting in remarkable enhancement of biological activity ranging from 200 to as much as 2000 times when compared to salicylic acid alone. The molecular docking studies also revealed the excellent anti-inflammatory activity of N -alkylnicotinamide salicylates comparable to commonly used drugs (indomethacin, ibuprofen, and acetylsalicylic acid) and were even characterized by better IC 50 values than common anti-inflammatory drugs in some cases. The derivative, featuring a decyl substituent in the pyridinium ring of nicotinamide, exhibited efficacy against Cutibacterium acnes while displaying favorable water solubility and improved wettability on hydrophobic surfaces, marking it as particularly promising. To investigate the impact of the APIs on the biosphere, the EC 50 parameter was determined against a model representative of crustaceans─ Artemia franciscana . The majority of compounds (with the exception of the salt containing the dodecyl substituent) could be classified as "Relatively Harmless" or "Practically Nontoxic", indicating their potential low environmental impact, which is essential in the context of modern drug development.

Near UV and visible light photodegradation can target therapeutic proteins during manufacturing and storage. While the underlying photodegradation pathways are frequently not well-understood, one important aspect of consideration is the formulation, specifically the formulation buffer. Citrate is a common buffer for biopharmaceutical formulations, which can complex with transition metals, such as Fe(III). In an aqueous solution, the exposure of such complexes to light leads to the formation of the carbon dioxide radical anion ( • CO 2 - ), a powerful reductant. However, few studies have characterized such processes in solid formulations. Here, we show that solid citrate formulations containing Fe(III) lead to the photochemical formation of • CO 2 - , identified through DMPO spin trapping and HPLC-MS/MS analysis. Factors such as buffers, the availability of oxygen, excipients, and manufacturing processes of solid formulations were evaluated for their effect on the formation of • CO 2 - and other radicals such as • OH.

Concurrent heavy metals remediation in natural environments poses significant challenges due to factors like metal speciation and interactions with soil moisture. This review focuses on strategies for immobilizing both anionic and cationic metals simultaneously in soil-crop systems. Key approaches include water management, biochar utilization, stabilizing agents, nanotechnology, fertilization, and bioremediation. Sprinkler or intermittent irrigation combined with soil amendments/biochar effectively immobilizes As/Cd/Pb simultaneously. This immobilization occurs through continuous adsorption-desorption, oxidation-reduction, and precipitation mechanisms influenced by soil pH, redox reactions, and Fe-oxides. Biochar from sources like wine lees, sewage sludge, spent coffee, and Fe-nanoparticles can immobilize As/Cd/Pb/Cr/Co/Cu/Zn together via precipitation. In addition, biochar from rice, wheat, corn straw, rice husk, sawdust, and wood chips, modified with chemicals or nanoparticles, simultaneously immobilizes As and Cd, containing higher Fe 3 O 4 , Fe-oxide, and OH groups. Ligand exchange immobilizes As, while ion exchange immobilizes Cd. Furthermore, combining biochar especially with iron, hydroxyapatite, magnetite, goethite, silicon, graphene, alginate, compost, and microbes-can achieve simultaneous immobilization. Other effective amendments are selenium fertilizer, Ge-nanocomposites, Fe-Si materials, ash, hormone, and sterilization. Notably, combining nano-biochar with microbes and/or fertilizers with Fe-containing higher adsorption sites, metal-binding cores, and maintaining a neutral pH could stimulate simultaneous immobilization. The amendments have a positive impact on soil physio-chemical improvement and crop development. Crops enhance production of growth metabolites, hormones, and xylem tissue thickening, forming a protective barrier by root Fe-plaque containing higher Fe-oxide, restricting upward metal movement. Therefore, a holistic immobilization mechanism reduces plant oxidative damage, improves soil and crop quality, and reduces food contamination., Competing Interests: Declaration of competing interest The authors declare that there are no known competing personal, professional, financial, and work-related issues that could appear as a negative influence in future before and after publication., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

In recent studies we have reported on the near-UV light-induced degradation of iron complexes of various pharmaceutical excipients, such as Fe(III)-citrate and Fe(III)-amino acid complexes. Mechanistic studies revealed a common photo-degradation pattern, i.e. the formation of carbon dioxide radical anion, a potent reducing agent, via an alkoxyl/amino radical intermediate generated by light-induced ligand-to-metal charge transfer (LMCT) involving α-hydroxycarboxylates or amino acids. Herein, we confirm the proposed general photo-degradation pathways through the study of the iron complexes of other α-hydroxycarboxylates that may be present in protein formulations, such as lactate and glycolate. The results indicate that lactate generates even higher yields of • CO 2 - as compared to citrate, suggesting a significant potential of lactate for the promotion of photo-degradation in pharmaceutical formulations., 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 American Pharmacists Association. Published by Elsevier Inc. All rights reserved.)

The interactions of anionic sodium dodecyl sulphate (SDS), cationic cetyltrimethylammonium bromide (CTAB) and nonionic triton X-100 (TX-100) surfactants with lysozyme at pH = 2.4 have been studied individually as well as in combination with 2,2,2-trifluoroetanol (TFE). Urea has also been used in combination with surfactants. By using these combinations, efforts have been made to obtain partially folded conformations of the protein in the presence of surfactants and effect of α-helix inducer 2,2,2-trifluoroethanol on these intermediate states. Thermodynamic analysis of all these interactions has been done employing a combination of UV-visible, fluorescence and circular dichroism spectroscopies. The results have been correlated with each other and characterized qualitatively as well as quantitatively. At lower concentration of surfactant, the thermodynamic parameters indicated the destabilizing effect of SDS, stabilizing effect of CTAB and unappreciable destabilizing impact of TX-100 on lysozyme. The enhancement in destabilization effect or reduction in stabilization effect of surfactants on lysozyme in the presence of TFE and urea has also been indicated.Communicated by Ramaswamy H. Sarma.

Ionic liquids (ILs) have found diverse applications in research and industry. Biocompatible ILs, a subset considered less toxic than traditional ILs, have expanded their applications into biomedical fields. However, there is limited understanding of the toxicity profiles, safe concentrations, and underlying factors driving their toxicity. In this study, we investigated the cytotoxicity of 13 choline-based ILs using four different cell lines: Human dermal fibroblasts (HDF), epidermoid carcinoma cells (A431), cervical cancer cells (HeLa), and gastric cancer cells (AGS). Additionally, we explored the haemolytic activity of these ILs. Our findings showed that the cytotoxic and haemolytic activities of ILs can be attributed to the hydrophobicity of the anions and the pH of the IL solutions. Furthermore, utilising quartz crystal microbalance with dissipation (QCM-D), we delved into the interaction of selected ILs, including choline acetate [Cho][Ac] and choline geranate [Cho][Ge], with model cell membranes composed of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). The QCM-D data showed that ILs with higher toxicities exhibited more pronounced interactions with membranes. Increased variations in frequency and dissipation reflected substantial changes in membrane fluidity and mass following the addition of the more toxic ILs. Furthermore, total internal reflection fluorescence microscopy study revealed that [Cho][Ac] could cause lipid rearrangements and pore formation in the membrane, while [Cho][Ge] disrupted the bilayer packing. This study advances our understanding of the cellular toxicities associated with choline-based ILs and provides valuable insights into their mechanisms of action concerning IL-membrane interactions. These findings have significant implications for the safe and informed utilisation of biocompatible ILs in the realm of drug delivery and biotechnology., 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.)

This paper discusses the development of an analytical method by an alternative separation approach, sequential elution liquid chromatography (SE-LC), to separate permanently charged ions (anions), weak acids, and neutral compounds using anion exchange and reversed-phase columns in tandem. SE-LC separates classes of compounds by group by employing two or more elution modes. Advantages to using SE-LC over conventional HPLC are a greater peak capacity and a reduced separation disorder. Importantly, the same HPLC as used for a conventional HPLC separation may be used to afford a successful SE-LC separation. Mobile phase selection and gradient optimization are integral for a successful SE-LC class separation of permanent anions, weak acids, and neutral compounds and will be discussed in detail in this paper. The most successful (best resolution and repeatability) SE-LC separation was achieved by applying isocratic elution at low pH to elute the weak acids, followed by an acetonitrile gradient to elute the neutral compounds, and last a sodium methanesulfonate gradient to elute the anionic compounds using a superficially porous C18 column coupled with a strong anion exchange (SAX) column. Repeatability (RSD) in the retention times and peak areas of the analytes was less than 0.25 % and 1.5 %, respectively., 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.)

Silver nanoparticles (AgNPs) with different sizes have been extensively adopted in various commercial products, causing ecological concerns because of the inevitable release of AgNPs into the environment. Hence, understanding the interaction of different-sized AgNPs with environmental substances is important for assessing the environmental risk and fate of AgNPs. In this work, we investigated the impact of anions (NO 3 - , SO 4 2- , HCO 3 - /CO 3 2- , Cl - ) in aquatic environments on the physicochemical properties and antibacterial activity of different-sized AgNPs (20, 40 and 57 nm). The results showed that the anions whose corresponding silver-based products had lower solubility were more likely to decrease the zeta potential (more negative) of particles, inhibit the dissolution of AgNPs and reduce their antibacterial activity. This should be attributed to the easier generation of coating layers on the surface of AgNPs during the incubation process with such anions. Additionally, the generation of coating layers was also found to be particle-size dependent. The anions were more prone to adsorbing onto larger-sized AgNPs, promoting the formation of coating layers, subsequently resulting in more pronounced variations in the physicochemical properties and antibacterial activity of the larger-sized AgNPs. Therefore, larger-sized AgNPs were more prone to experiencing specific effects from the anions.

Mitochondrial uncoupling by small molecule protonophores is a promising strategy for developing novel anticancer agents. Recently, aryl urea substituted fatty acids (aryl ureas) were identified as a new class of protonophoric anticancer agents. To mediate proton transport these molecules self-assemble into membrane-permeable anionic dimers in which intermolecular hydrogen bonds between the carboxylate and aryl-urea anion receptor delocalise the negative charge across the aromatic π-system. In this work, we extend the aromatic π-system by introducing a second phenyl substituent to the aryl urea scaffold and compare the proton transport mechanisms and mitochondrial uncoupling actions of these compounds to their monoaryl analogues. It was found that incorporation of meta-linked phenyl substituents into the aryl urea scaffold enhanced proton transport in vesicles and demonstrated superior capacity to depolarise mitochondria, inhibit ATP production and reduce the viability of MDA-MB-231 breast cancer cells. In contrast, diphenyl ureas linked through a 1,4-distribution across the phenyl ring displayed diminished proton transport activity, despite both diphenyl urea isomers possessing similar binding affinities for carboxylates. Mechanistic studies suggest that inclusion of a second aryl ring changes the proton transport mechanism, presumably due to steric factors that impose higher energy penalties for dimer formation., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The present study utilizes molecular dynamics simulations to examine how different anions compete for protein solvation in aqueous solutions of ionic liquids (ILs). Ubiquitin is used as model protein and studied in IL mixtures sharing the same cation, 1-ethyl-3-methylimidazolium (EMIM), and two different anions in the same solution, from combinations of dicyanamide (DCA), chloride (Cl), nitrate (NO 3 ), and tetrafluoroborate (BF 4 ). Our findings reveal that specific interactions between anions and the protein are paramount in IL solvation, but that combinations of anions are not additive. For example, DCA exhibits a remarkable ability to form hydrogen bonds with the protein, resulting in a significantly stronger preferential binding to the protein than other anions. However, the combination of DCA with NO 3 , which also forms hydrogen bonds with the protein, results in a smaller preferential solvation of the protein than the combination of DCA with chloride ions, which are weaker binders. Thus, combining anions with varying affinities for the protein surface modulates the overall ion accumulation through nonadditive mechanisms, highlighting the importance of the understanding of competition for specific interaction sites, cooperative binding, bulk-solution affinity, and overall charge compensations, on the overall solvation capacity of the solution. Such knowledge may allow for the design of novel IL-based processes in biotechnology and material science, where fine-tuning protein solvation is crucial for optimizing performance and functionality.

Compact polyelectrolyte complexes (CoPECs) can exhibit mechanical properties similar to those of biological tissues and other interesting properties, such as self-healing. To date, a variety of CoPECs prepared from synthetic polyelectrolytes have been investigated, but there are very few examples based entirely on biopolymers. We describe here an investigation of CoPECs based on poly(l-lysine) (PLL) with sodium hyaluronate (HA) and alginate (Alg). A 2:1 ratio of cation:anion and 0.25 M NaBr was beneficial for the formation of viscoelastic PLL-HA CoPECs, with the favorable ratio attributed to the spacing of carboxylates on HA being one every two saccharide units. In contrast, 1.0 M NaBr and a 1:1 ratio were better for PLL-Alg CoPECs. Both CoPECs swelled or retained a constant volume when immersed in hypertonic media, but contracted in hypotonic media. The loading of molecules into the PLL-HA (2:1) CoPECs was investigated. Higher loadings were achieved for anionic molecules compared to cations, presumably due to the excess cationic binding sites on the networks. The times required for full release of the molecules ranged from less than 2 h for neutral paracetamol to about 48 h for crystal violet and diclofenac.

Cytochrome P450 (P450, CYP) 19A1 is the steroid aromatase, the enzyme responsible for the 3-step conversion of androgens (androstenedione or testosterone) to estrogens. The final step is C-C bond scission (removing the 19-oxo group as formic acid) that proceeds via a historically controversial reaction mechanism. The two competing mechanistic possibilities involve a ferric peroxide anion (Fe 3+ O 2 - , Compound 0) and a perferryl oxy species (FeO 3+ , Compound I). One approach to discern the role of each species in the reaction is with the use of oxygen-18 labeling, i.e., from 18 O 2 and H 2 18 O of the reaction product formic acid. We applied this approach, using several technical improvements, to study the deformylation of 19-oxo-androstenedione by human P450 19A1 and of a model secosteroid, 3-oxodecaline-4-ene-10-carboxaldehyde (ODEC), by rabbit P450 2B4. Both aldehyde substrates were sensitive to non-enzymatic acid-catalyzed deformylation, yielding 19-norsteroids, and conditions were established to avoid issues with artifactual generation of formic acid. The Compound 0 reaction pathway predominated (i.e., Fe 3+ O 2 - ) in both P450 19A1 oxidation of 19-oxo-androstenedione and P450 2B4 oxidation of ODEC. The P450 19A1 results contrast with our prior conclusions (J. Am. Chem. Soc. 2014, 136, 15016-16025), attributed to several technical modifications., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Control of phosphate capture and release is vital in environmental, biological, and pharmaceutical contexts. However, the binding of trivalent phosphate (PO 4 3- ) in water is exceptionally difficult due to its high hydration energy. Based on the anion coordination chemistry of phosphate, in this study, four charge-neutral tripodal hexaurea receptors (L 1 -L 4 ), which were equipped with morpholine and polyethylene glycol terminal groups to enhance their solubility in water, were synthesized to enable the pH-triggered phosphate binding and release in aqueous solutions. Encouragingly, the receptors were found to bind PO 4 3- anion in a 1 : 1 ratio via hydrogen bonds in 100 % water solutions, with L 1 exhibiting the highest binding constant (1.2×10 3  M -1 ). These represent the first neutral anion ligands to bind phosphate in 100 % water and demonstrate the potential for phosphate capture and release in water through pH-triggered mechanisms, mimicking native phosphate binding proteins. Furthermore, L 1 can also bind multiple bioavailable phosphate species, which may serve as model systems for probing and modulating phosphate homeostasis in biological and biomedical researches., (© 2024 Wiley-VCH GmbH.)

Progress in the development of biodegradable or biobased ionic liquids (ILs) has led to the design of green compounds for several applications. Herein, four biocompatible dicationic ionic liquids (DILs) with ammonium-phosphonium cations and amino acid anions were synthesized and investigated their environmental impact. The structures of the DILs were confirmed by spectral analyses ( 1 H, 13 C and 31 P NMR). Furthermore, physicochemical properties such as density, viscosity and refractive index were determined. Water content, bromide content and solubility were thereafter determined as the parameters needed for further studies. Subsequently, their antifeedant activity towards economically important pests of grain in storage warehouses: the granary weevil, the confused flour beetle, and the khapra beetle was examined, showing the dependence on structure. Moreover, selected DILs were investigated for toxicity towards white mustard, Daphnia magna, and Artemia franciscana to specify the environmental impact. These studies were complemented by understand the biodegradation of DILs by bacterial communities derived from soil at the agricultural land. The result was DILs with limited environmental footprints that have great potential for further application studies., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests. Damian K. Kaczmarek reports financial support was provided by National Science Centre Poland. Damian Krystian Kaczmarek has patent pending to P.443203. 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.)

Sample multiplexing-based proteomic strategies rely on fractionation to improve proteome coverage. Tandem mass tag (TMT) experiments, for example, can currently accommodate up to 18 samples with proteins spanning several orders of magnitude, thus necessitating fractionation to achieve reasonable proteome coverage. Here, we present a simple yet effective peptide fractionation strategy that partitions a pooled TMT sample with a two-step elution using a strong anion-exchange (SAX) spin column prior to gradient-based basic pH reversed-phase (BPRP) fractionation. We highlight our strategy with a TMTpro18-plex experiment using nine diverse human cell lines in biological duplicate. We collected three data sets, one using only BPRP fractionation and two others of each SAX-partition followed by BPRP. The three data sets quantified a similar number of proteins and peptides, and the data highlight noticeable differences in the distribution of peptide charge and isoelectric point between the SAX partitions. The combined SAX partition data set contributed 10% more proteins and 20% more unique peptides that were not quantified by BPRP fractionation alone. In addition to this improved fractionation strategy, we provide an online resource of relative abundance profiles for over 11,000 proteins across the nine human cell lines, as well as two additional experiments using ovarian and pancreatic cancer cell lines.

In this study, a novel adsorbent, A-PEI/CS-Cu 2+ , was developed by crosslinking polyethyleneimine/chitosan hydrogel with acrolein and loading it with copper ions. The adsorption process of A-PEI/CS-Cu 2+ on the anionic dye acid yellow 36 (AY36) was investigated by kinetic, isothermal and thermodynamic modeling. It was noteworthy that A-PEI/CS-Cu 2+ exhibited rapid adsorption with a 90 % removal rate achieved within just 5 min, which was much faster than the adsorption rate of A-PEI/CS without load of copper ions and showed its potential for rapid adsorption applications. The maximum adsorption capacity for AY36 could reach up to 3114 mg g -1 . In addition, the high concentration of saline wastewater was found to have almost no effect on the adsorption reaction in the salt effect test experiment. In five desorption-regeneration cycle experiments, the sample exhibited good recyclability and regeneration performance. The driving force of the adsorption process mainly originated from the electrostatic interaction, hydrogen bonding, and intermolecular interaction, in which the addition of copper ions led to the enhancement of the electrostatic interaction and chelation between A-PEI/CS-Cu 2+ and AY36. Overall, the findings suggest the excellent potential of A-PEI/CS-Cu 2+ for rapid and efficient adsorption, as well as its suitability for practical applications in wastewater treatment., 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.)

In the present study, one mononuclear Cu(II) [CuL(SCN)] (1) and one mononuclear Co(II) [CoLN 3 ] (2) complexes, with a Schiff base ligand (HL) formed by condensation of 2-picolylamine and salicylaldehyde, have been successfully developed and structurally characterized. The square planer geometry of both complexes is fulfilled by the coordination of one deprotonated ligand and one ancillary ligand SCN - (1) or N 3 - (2) to the metal centre. Binding affinities of both complexes with deoxyribonucleic acid (DNA) and human serum albumin (HSA) are investigated using several biophysical and spectroscopic techniques. High values of the macromolecule-complex binding constants and other results confirm the effectiveness of both complexes towards binding with DNA and HSA. The determined values of the thermodynamic parameters support spontaneous interactions of both complexes with HSA, while fluorescence displacement and DNA melting studies establish groove-binding interactions with DNA for both complexes 1 and 2. The molecular modelling study validates the experimental findings. Both complexes are subjected to an MTT test establishing the anticancer property of complex 1 with lower risk to normal cells, confirmed by the IC50 values of the complex for HeLa cancer cells and HEK normal cells. Finally, a nuclear staining analysis reveals that the complexes have caused apoptotic cell death., Competing Interests: Declaration of competing interest There are no conflicts of interest to mention., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The simultaneous removal of anionic and cationic heavy metals presents a challenge for adsorbents. In this study, acetate (Ac-) was utilized as the intercalating anion for layered double hydroxide (LDH) to prepare a novel biochar composite adsorbent (Ac-LB) designed for the adsorption of Pb(II), Cu(II), and As(V). By utilizing Ac- as the intercalating anion, the interlayer space of the LDH was enlarged from 0.803 nm to 0.869 nm, exposing more adsorption sites for the LDH and enhancing the affinity for heavy metals. The results of the adsorption experiments showed that the adsorption effect of Ac-LB on heavy metals was significantly improved compared to the original FeMg-LDH modified biochar composites (LB), and the maximum adsorption capacity of Pb(II), Cu(II), and As(V) were 402.70, 68.50, and 21.68 mg/g, respectively. Wastewater simulation tests further confirmed the promising application of Ac-LB for heavy metal adsorption. The analysis of the adsorption mechanism revealed that surface complexation, electrostatic adsorption, and chemical deposition were the main mechanisms of action between heavy metals (Pb(II) and Cu(II)) and Ac-LB. Additionally, Cu(II) ions underwent a homogeneous substitution reaction with Ac-LB. The adsorption process of As(V) by Ac-LB mainly relied on complexation and ion-exchange reactions. Lastly, the modification of the LDH structure by Ac - as an intercalating anion, thereby increasing the affinity for heavy metals, was further illustrated using density-functional theory (DFT) calculations., 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 applications of polysaccharides as emulsifiers are limited due to the lack of hydrophobicity. However, traditional hydrophobic modification methods used for polysaccharides are complicated and involve significant mechanical and thermal losses. In this study, soy hull polysaccharide (SHP) and terminally aminopropylated polydimethylsiloxane (NPN) were selected to investigate the feasibility of a simple and green interfacial membrane strengthening strategy based on the interfacial polymerization of anionic polysaccharides and fat-soluble alkaline ligands. Our results show that deprotonated SHP and protonated NPN can be complexed at the water/oil (W/O) interface, reduce interfacial tension, and form a strong membrane structure. Moreover, they can quickly form a membrane at the W/O interface upon the moment of contact to produce stable all-liquid printing products with complex patterns. However, the molecular weight of NPN affects the complexation reaction. Consequently, this study has long-term implications to expanding the areas of application for anionic polysaccharides., Competing Interests: Declaration of competing interest The authors have declared no conflict of interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The oxidation of tetraselenatetracene (TSeT) by tetracyanoquinodimethane in the presence of dysprosium(III) tris(hexafluoroacetylacetonate), Dy III (hfac) 3 , produces black crystals of {TSeT 1.5 } ●+ [Dy III (hfac) 4 ] - ( 1 ) salt, which combines conducting and magnetic sublattices. It contains one-dimensional stacks composed of partially oxidized TSeT molecules (formal averaged charge is +2/3). Dimers and monomers can be outlined within these stacks with charge and spin density redistribution. The spin triplet state of the dimers is populated above 128 K with an estimated singlet-triplet energy gap of 542 K, whereas spins localized on the monomers show paramagnetic behavior. A semiconducting behavior is observed for 1 with the activation energy of 91 meV (measured by the four-probe technique for an oriented single crystal). The Dy III ions coordinate four hfac - anions in [Dy III (hfac) 4 ] - , providing D 2d symmetry. Slow magnetic relaxation is observed for Dy III under an applied static magnetic field of 1000 Oe, and 1 is a single-ion magnet (SIM) with spin reversal barrier U eff = 40.2 K and magnetic hysteresis at 2 K. Contributions from Dy III and TSeT ●+ paramagnetic species are seen in EPR. The Dy III ion rarely manifests EPR signals, but such signal is observed in 1 . It appears due to narrowing below 30 K and has g 4 = 6.1871 and g 5 = 2.1778 at 5.4 K.

The new water-soluble di-anionic bi-sodium salt of tetracycline (TC), an antibiotic in clinical use, with the formula {[TC] 2- [Na + (MeOH)(H 2 O)] [Na + ]·(H 2 O)} n (TCNa) was synthesized. The compound was characterized by m.p., attenuated total reflectance-Fourier transform infra-red (ATR-FTIR) spectroscopy, and ultraviolet (UV) and proton nuclear magnetic resonance ( 1 H NMR) spectroscopy in the solid state and in solution. The molecular weight (MW) was determined by cryoscopy. The crystal structure of TCNa was also determined by X-ray crystallography. The antibacterial activity of TCNa was evaluated against the bacterial species Pseudomonas aeruginosa ( P. aeruginosa ), Escherichia coli ( E. coli ), Staphylococcus epidermidis ( S. epidermidis ) and Staphylococcus aureus ( S. aureus ) by means of minimum inhibitory concentration (MIC), minimum bactericidal concentration (MBC) and inhibition zones (IZs). Moreover, the ability of the compound to eradicate biofilm formation was also evaluated. The results are compared with those obtained for the commercially available drug TCH2. The in vitro and in vivo toxicities of TCNa were tested against human corneal epithelial cells (HCECs) and Artemia salina .

The expanding horizon of diagnostic and therapeutic applications involving nucleic acids (NA) requires novel tools for purification, including minimal sample preparation. In this work, thin-film microextraction devices featuring five poly ionic sorbents were examined as anion exchange extraction phases for the rapid purification of NAs. Each sorbent is composed of a nonionic cross-linker and a methacrylate monomer containing a core tetra-alkyl ammonium moiety with an alkyl, anionic, or cationic residue. Extraction devices were produced through the application of the prepolymer sorbent mixture onto a functionalized nitinol metal support followed by photoinduced free-radical polymerization. The miniaturized extraction devices (10 mm × 3.5 mm) were directly immersed into aqueous samples to isolate NAs via electrostatic interactions with the polycation. The ammonium methacrylate (AMA) monomer containing a propyl trimethylammonium group (AMA-C 3 N(CH 3 ) 3 ) exhibited the highest affinity for DNA, with 80 ± 10% of DNA being isolated. Recovery of DNA from the sorbents required the introduction of ions in an aqueous solution to exchange the anionic biopolymer from the polycationic moiety. An investigation of three anion species revealed that the AMA-C 3 N(CH 3 ) 3 sorbent showed the highest recoveries, with the perchlorate anion producing a preconcentration factor of 4.36 ± 0.86 while requiring only 250 mM NaClO 4 . A directly compatible quantitative polymerase chain reaction assay was developed to quantify the recovery of spiked DNA with lengths of 830, 204, and 98 base pairs in heat-treated human plasma. The AMA-C 3 N(CH 3 ) 3 sorbent was uninhibited by the complex human plasma matrix and enabled high preconcentration factors for the spiked DNA at a biologically relevant concentration of 10 pg/mL. While Qiagen's circulating cell-free DNA MinElute extraction kit enabled higher preconcentration of all analytes, the methodology described in this work requires fewer steps, less user intervention, and minimal equipment requirements to isolate DNA, making it more amenable for high-throughput and low resource applications.

Alzheimer's disease (AD) is a multifactorial and fatal neurodegenerative disorder. Acetylcholinesterase (AChE) plays a key role in the regulation of the cholinergic system and particularly in the formation of amyloid plaques; therefore, the inhibition of AChE has become one of the most promising strategies for the treatment of AD, particularly concerning AChE inhibitors that interact with the peripheral anionic site (PAS). Ceanothic acid isolated from the Chilean Rhamnaceae plants is an inhibitor of AChE through its interaction with PAS. In this study, six ceanothic acid derivatives were prepared, and all showed inhibitory activity against AChE. The structural modifications were performed starting from ceanothic acid by application of simple synthetic routes: esterification, reduction, and oxidation. AChE activity was determined by the Ellmann method for all compounds. Kinetic studies indicated that its inhibition was competitive and reversible. According to the molecular coupling and displacement studies of the propidium iodide test, the inhibitory effect of compounds would be produced by interaction with the PAS of AChE. In silico predictions of physicochemical properties, pharmacokinetics, drug-likeness, and medicinal chemistry friendliness of the ceanothane derivatives were performed using the Swiss ADME tool.

The effect of aqueous solution chemistry on the ionic hydration structure and its corresponding nanofiltration (NF) selectivity is a research gap concerning ion-selective transport. In this study, the hydration distribution of two typical monovalent anions (Cl - and NO 3 - ) under different aqueous solution chemical conditions and the corresponding transmembrane selectivity during NF were investigated by using in situ liquid time-of-flight secondary ion mass spectrometry in combination with molecular dynamics simulations. We demonstrate the inextricable link between the ion hydration structure and the pore steric effect and further find that ionic transmembrane transport can be regulated by breaking the balance between the hydrogen bond network (i.e., water-water) and ion hydration (i.e., ion-water) interactions of hydrated ion. For strongly hydrated (H 2 O) n Cl - with more intense ion-water interactions, a higher salt concentration and coexisting ion competition led to a larger hydrated size and, thus, a higher ion rejection by the NF membrane, whereas weakly hydrated (H 2 O) n NO 3 - takes the reverse under the same conditions. Stronger OH - -anion hydration competition resulted in a smaller hydrated size of (H 2 O) n Cl - and (H 2 O) n NO 3 - , showing a lower observed average hydration number at pH 10.5. This study deepens the long-overlooked understanding of NF separation mechanisms, concerning the hydration structure.

Conductive hydrogels play a crucial role in advancing technologies like implantable bioelectronics and wearable electronic devices, owing to their favorable conductivity and appropriate mechanical properties. Here, a novel bottom-up approach is reported for crafting conductive nanocomposite hydrogels to achieve enhancing conductive and mechanical properties. In this approach, new poly(ɛ-caprolactone)-based block copolymers with sulfonic groups are first synthesized and self-assembled into uniform polyanionic nanoplatelets. Subsequently, these negatively charged nanoplatelets, with sulfonic groups on the surface, are employed as nanoadditives for the polymerization of 3,4-ethylenedioxythiophene (EDOT), resulting in poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/nanoplatelet complex with 3.8 times enhanced electrical conductivity compared with their counterparts prepared using block copolymers (BCPs). Blending the (PEDOT:PSS)/nanoplatelet complex with calcium alginate, nanocomposite hydrogels are successfully prepared. In comparison with hydrogels with (PEDOT:PSS)/BCP complexes prepared by a top-down method, the nanocomposite hydrogels are found to show twice as strong mechanical strength and 1.6 times higher conductivity. This work provides valuable insights into the bottom-up construction of conductive hydrogels for bioelectronics using well-controlled polymeric nanoplatelets., (© 2024 Wiley‐VCH GmbH.)

Anthraquinones constitute an important class of compounds with wide applications. The solubility of derivatives at 298.15 K was discussed in ethanol-water solution and at atmospheric pressure, the solubility of 1-amino-4-hydroxy-9,10-anthraquinone (AHAQ) in binary solvents (ethanol-water combinations) was determined. Colour strength and fastening properties depend upon the kind and position of a hydrophobic group connected to the phenoxy ring of Anthraquinone moiety. There is a continuing interest in the creation of novel anthraquinone derivatives with biological activities since they have demonstrated potential for treating multiple sclerosis. For this purpose, by utilizing voltammetric and absorption studies, interactions of various derivatives with calf thymus DNA (ct-DNA) and the cationic surfactant cetyltrimethylammoniumbromide (CTAB) were examined. Here prominent Hydrophobic interaction and electron transfer resulting in binding to CTAB micelles were observed. The polarity index of the media was assessed and associated with the electrochemical parameters. The medicinal behaviour of Anthraquinone derivatives was a result of electron transfer reactions with DNA. UV-Visible and fluorescence properties were due to the transitions between n* and π* orbitals. Large absorption band with low dichroic ratio was characteristic of various derivatives of Anthraquinone. Presence of -NH group proves various derivatives remarkable calorimetric and anionic sensors., (© 2023. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Understanding oligomerization and aggregation of the amyloid-β protein is important to elucidate the pathological mechanisms of Alzheimer's disease, and lipid membranes play critical roles in this process. In addition to studies reported by other groups, our group has also reported that the negatively-charged lipid bilayers with a high positive curvature induced α-helix-to-β-sheet conformational transitions of amyloid-β-(1-40) upon increase in protein density on the membrane surface and promoted amyloid fibril formation of the protein. Herein, we investigated detailed mechanisms of the conformational transition and oligomer formation of the amyloid-β protein on the membrane surface. Changes in the fractions of the three protein conformers (free monomer, membrane-bound α-helix-rich conformation, and β-sheet-rich conformation) were determined from the fluorescent spectral changes of the tryptophan probe in the protein. The helix-to-sheet structural transition on the surface was described by a thermodynamic model of octamer formation driven by entropic forces including hydrophobic interactions. These findings provide useful information for understanding the self-assembly of amyloidogenic proteins on lipid membrane surfaces., 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 © 2023. Published by Elsevier B.V.)

Paper-based test film material is widely used in a variety of test instruments for different applications. The enzyme activity test paper sheet is one of the most popularly used test papers. Here we present a novel fabrication of paper-based enzyme activity test paper without cationic resin added in. The chemical pulping fibers were first beaten to different degrees (from 14.6 to 41.5°SR) with a PFI beater. After that, the fibers were modified with a cationic agent (3-chloro-2-hydroxypropyl trimethyl ammonium chloride) under the system of alkali and water solution. Finally, the test papers were made with the modified fiber by a regular paper former in lab. The results showed that beating is beneficial for the improvement of the cationization reaction which is indicated by the Zeta potential, FTIR and EDS. The main mechanisms involved are the destruction of crystalline zone, increase of free hydroxyl group and defibrillation. This hypothesis was supported by the SEM, XRD and fiber analyzer. Beating under the optimized condition, the wet strength and liquid absorbability of test paper can meet the application requirement, and the test results of enzyme activity are quite close to those of commercial test papers., 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.)

Dye wastewater poses a serious threat to the environment and human health, necessitating sustainable degradation methods. In this study, Na-based Montmorillonite (MMT) was exfoliated using different ionic liquids ([C16MIM][Cl], [C16MIM][BF 4 ], [C16MIM][PF 6 ]), and silver nanoparticles (Ag NPs) were green-synthesized using hydroxypropyl cellulose (HPC). The HPC significantly enhanced the dispersion of MMT in the hydrogel. By introducing lauryl methacrylate (LMA), a hydrophobic associative network was constructed in PAM/LMA/HPC/MMT@ILs&Ag NPs hydrogel. This hydrogel demonstrated outstanding mechanical properties, with a stress of 833.21 kPa, strain of 3300 %, and toughness of 14.36 MJ/m 3 . It also exhibited excellent catalytic activity, with a rate constant of 0.83 min -1 for 4-nitrophenol degradation at 28 °C. The effects of temperature and catalyst concentration on the catalytic reaction were systematically investigated. This study presents a simple green synthesis approach for Ag NPs using HPC, achieving superior mechanical performance and stable MMT dispersion in aqueous solutions., 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., (Copyright © 2024. Published by Elsevier B.V.)

In this work, a novel magnetic covalent organic framework (COF (TpPa-NH 2 ) @ Fe 3 O 4 ) was prepared via two step by simple solvent method for the extraction of anionic azo dye residues in food. The as-prepared COF (TpPa-NH 2 ) @ Fe 3 O 4 nanocomposite was characterised by scanning electron microscope, transmission electron microscope, Fourier transform-infrared spectroscopy, X-ray diffraction and vibrating sample magnetometer. Before high-performance liquid chromatography with ultraviolet detection (HPLC-UV) determination, it was used as magnetic adsorbent for magnetic solid-phase extraction (MSPE) to extract and pre-concentrate three anionic azo dyes in carbonated beverage samples. The several key extraction and desorption parameters affecting the extraction recovery rate were investigated, including extraction time, pH of the solution, amount of material, adsorption time, elution solvent, pH of elution solvent, type of elution solvent, elution volume and elution time. Under optimised conditions, this method has good linearity between 5 and 500 μg L -1 (correlation coefficient > 0.9986). The limit of detection was 2.3-3.4 μg L -1 . The recoveries of the samples were between 87.5 and 96.9%, and the relative standard deviation lower than 4.6%. The developed method has broad application prospects for the analysis of anionic azo dyes in carbonated beverages., (© 2024. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry 2024.)

Epinephrine (EP) is an essential catecholamine in the human body. Currently, most EP detection methods are not suitable for in vivo detection due to material limitations. An organic small molecule fluorescent probe based on a chemical cascade reaction for the detection of EP was designed. Anionic heptamethine cyanine dye was selected as a fluorescent dye because of its NIR fluorescence emission with excellent biocompatibility. The secondary amine of EP nucleophilically attacks the carbonate of the probe with its stronger nucleophilicity and further undergoes intramolecular nucleophilic cyclization to release the fluorophore. Other substances containing only primary amines or no β-OH lack reaction competitiveness due to their weaker nucleophilicity or inability to undergo further cyclization. The fluorescence recovery of the probe was linearly related to the EP concentration of 2-75 μmol/L. The detection limit was 0.4 μmol/L. The recovery rate was 94.78-111.32%. Finally, we successfully achieved bioimaging of EP in living cells and EP analogue in nematodes.

The simultaneous discrimination and detection of multiple anions in an aqueous solution has been a major challenge due to their structural similarity and low charge radii. In this study, we have constructed a supramolecular fluorescence sensor array based on three host-guest complexes to distinguish five anions (F - , Cl - , Br - , I - , and ClO - ) in an aqueous solution using anionic-induced fluorescence quenching combined with linear discriminant analysis. Due to the different affinities of the three host-guest complexes for each anion the anion quenching efficiency for each host-guest complex was likewise different, and the five anions were well recognized. The fluorescence sensor array not only distinguished anions at different concentrations (0.5, 10, and 50 µM) with 100% accuracy but also showed good linearity within a certain concentration range. The limit of detection (LOD) was < 0.5 µM. Our interference study showed that the developed sensor array had good anti-interference ability. The practicability of the developed sensor array was also verified by the identification and differentiation of toothpaste brands with different fluoride content and the prediction of the iodine concentration in urine combined with machine learning., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

The existence of microplastics (MPs) in water is a significant global concern since they have the potential to pose a threat to human health. Therefore, there is a need to develop a sustainable treatment technology for MPs removal, as the conventional methods are inadequate to address this problem. Coagulation is a typical process in treatment plants that can capture MPs before releasing them into the environment. In this work, the removal behaviors of polyamide (PA), polystyrene (PS), and polyethylene (PE) MPs were systematically investigated through coagulation processes using aluminum sulfate (Al 2 (SO 4 ) 3 ) and Moringa oleifera (MO) seeds extract. Subsequently, the coagulation performance of Al 2 (SO 4 ) 3 was improved by the separate addition of anionic polyacrylamide (APAM) and naturally derived MO. Results showed that Al 2 (SO 4 ) 3 in combination with APAM had better performance than Al 2 (SO 4 ) 3 or MO alone. In the Al 2 (SO 4 ) 3 +APAM system, the removal efficiencies were 93.47%, 81.25%, and 29.48% for PA, PS, and PE MPs, respectively. Furthermore, the effectiveness of the Al 2 (SO 4 ) 3 and MO blended system was approximately similar to the Al 2 (SO 4 ) 3 +APAM system. However, the required amount of Al 2 (SO 4 ) 3 was decreased to 50% in the Al 2 (SO 4 ) 3 +MO system compared to the optimal dosage in the Al 2 (SO 4 ) 3 system alone. The combination of 40 mg/L of Al 2 (SO 4 ) 3 and 60 mg/L of MO resulted in removal efficiencies of 92.99%, 80.48%, and 28.94% for PA, PS, and PE MPs, respectively. The high efficacy of these enhanced methods was due to the synergic effects of charge neutralization and agglomeration adsorption, which were validated through zeta potential assessments and visual analysis using scanning electron microscopy (SEM) images. In the case of experimental conditions, initial pH had little impact on removal efficiency, while NaCl salinity and stirring speed directly affected MPs removal. Consequently, this research took a step toward finding a green strategy to remove MPs from water systems., 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.)

Generally, the pH of fluorinated groundwater or many industrial wastewater is neutral, while the majority of metal-modified adsorbents can work efficiently only under acidic conditions. In this study, we synthesized a novel hybrid adsorbent, Mg-Zr-D213, by loading nano-Mg/Zr binary metal (hydrogen) oxides in a strong-base anion exchanger, D213, to enhance the adsorption of fluoride from neutral water. Mg-Zr-D213 exhibited a better fluoride-removal capacity in neutral water than monometallic modified resins. Under the interference of competing anions and coexisting organic acids, Mg-Zr-D213 exhibited superior selectivity. The Langmuir model indicated that the fitted maximum sorption capacity of Mg-Zr-D213 was 41.38 mg/g. The results of column experiments showed that the effective treatment volume of Mg-Zr-D213 was 8-16-times higher than that of D213 for both synthetic groundwater and actual industrial wastewater, and that NaOH-NaCl eluent could effectively recover more than 95% of fluoride. Adsorption experiments with Mg/Zr metal (hydrogen) oxide particles and D213 separately demonstrated a synergistic effect between -N + (CH 3 ) 3 and Mg/Zr metal (hydrogen) oxide particles. The ligand exchange or metal-ligand interaction of Mg/Zr metal (hydrogen) oxide particles on fluoride was further demonstrated via X-ray photoelectron spectroscopy. Overall, Mg-Zr-D213 has great potential for enhanced fluoride removal in neutral 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., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Targeting the homeostasis of anions and iron has emerged as a promising therapeutic approach for the treatment of cancers. However, single-targeted agents often fall short of achieving optimal treatment efficacy. Herein we designed and synthesized a series of novel dual-functional squaramide-hydroxamic acid conjugates that are capable of synergistically modulating the homeostasis of anions and iron. Among them, compound 16 exhibited the most potent antiproliferative activity against a panel of selected cancer cell lines, and strong in vivo anti-tumor efficacy. This compound effectively elevated lysosomal pH through anion transport, and reduced the levels of intracellular iron. Compound 16 could disturb autophagy in A549 cells and trigger robust apoptosis. This compound caused cell cycle arrest at the G1/S phase, altered the mitochondrial function and elevated ROS levels. The present findings clearly demonstrated that synergistic modulation of anion and iron homeostasis has high potentials in the development of promising chemotherapeutic agents with dual action against cancers., 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.)

Eco-friendly and renewable sodium alginate, as a potential alternative to fossil resources, has attracted considerable attention in wastewater treatment field. Herein, we develop a SA/PEI/PEG (sodium alginate/polyethyleneimine/polyethylene glycol diglycidyl ether) adsorbent in which SA was functionalized by PEI/PEG via a facile but effective strategy of one-pot gelation of aqueous SA/PEI/PEG solution. Systematic investigations were accomplished to explore the effects of adsorbent factors on the adsorption performances of the adsorbent towards the anionic dyes CR (congo red), AB-10B (amido black-10B), and AB-25 (acid blue-25). Strikingly, the SA/PEI/PEG exhibited exceptional adsorption performance to CR (2782 mg g -1 , 90.6 %), AB-10B (1369 mg g -1 , 90.9 %) and AB-25 (4221 mg g -1 , 92.6 %) at 30 °C, pH = 3, 200 r min -1 and oscillated 24 h, and demonstrating exceptional reusability after six cycles of adsorption-desorption cycles. Furthermore, the three kinetic, four isothermic and one thermodynamic models were used to investigate the adsorption behaviors of the adsorbent towards these dyes. The possible adsorption mechanism is suggested: Hydrogen bond interactions and electrostatic attractions between SA/PEI/PEG and the dyes primarily contribute to exceptional adsorption capacity. The SA/PEI/PEG adsorbent endowed with easy fabrication, extraordinary adsorption capacity and excellent reusability promises potential application prospects in wastewater purification industry., 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.)

The development of bifunctional hybrid materials based on natural clays and layered double hydroxide (LDH) and their application on the simultaneous adsorption of Cd(II) and As(V) was investigated in this work. Two different synthesis routes, in situ and assembly, were employed to obtain the hybrid materials. Three types of natural clays, namely bentonite (B), halloysite (H), and sepiolite (S), were used in the study. These clays are characterized by a laminar, tubular, and fibrous structural arrangement, respectively. The physicochemical characterization results indicate that the hybrid materials were formed through interactions between the Al-OH and Si-OH groups present in the natural clays, and the Mg-OH and Al-OH groups present in the LDH for both synthesis routes. However, the "in situ" route yields a more homogenous material because the LDH formation is performed on the natural clay surface. The hybrid materials showed an anion and cation exchange capacity up to 200.7 meq/100 g and an isoelectric point near 7. The arrangement of natural clay has no impact on the properties of hybrid material but influences the adsorption capacity. The adsorption of Cd(II) onto hybrid materials was enhanced in comparison with natural clays, obtaining adsorption capacities of 80, 74, 65, and 30 mg/g for 15:1 (LDH:H) INSITU , 1:1 (LDH:S) INSITU , 1:1 (LDH:B) INSITU , and 1:1 (LDH:H) INSITU , respectively. The adsorption capacities of hybrid materials to adsorb As(V) were between 20 and 60 μg/g. The 15:1 (LDH:H) INSITU sample showed the best adsorption capacity being ten folds greater than halloysite and LDH. In all cases, the hybrid materials showed a synergistic effect for Cd(II) and As(V) adsorption. The adsorption study of Cd(II) onto hybrid materials showed that the primary adsorption mechanism is cation exchange between the interlayer cations in natural clay and Cd(II) in the aqueous solution. The adsorption of As(V) showed that the adsorption mechanism is attributed to anion exchange between CO 2 3- in the interlayer space of LDH and H 2 ASO 4 - in the solution. The simultaneous adsorption of As (V) and Cd (II) shows that, during the As(V) adsorption, there is no competition by the adsorption sites. Still, the adsorption capacity towards Cd(II) was enhanced 1.2-folds. This study ultimately revealed that the arrangement of clay has a significant influence on the adsorption capacity of the hybrid material. This can be attributed to the similar morphology between the hybrid material and natural clays, as well as the important diffusion effects observed in the system., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Hollow vesicles are promising in water treatment due to their unique structure of the membrane and inner cavity. However, the adsorption capacity needs to be improved for targeted pollutants. Herein, millimeter-scale hollow vesicles were prepared with a one-step process of sequential stirring and grafting using chitosan, diallyldimethylammonium chloride, and sodium alginate as raw materials with the purpose of efficient removal of anionic dyes from wastewater. The composite vesicles were characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. The hollow vesicles showed the structure of the cationic membrane and the inner cavity, facilitating the dye adsorption. The adsorption capacity for the anionic dye Reactive Black 5 reached 698.1 mg/g, more than twice that of the binary composite vesicles without graft. The adsorption kinetics and isotherm data coincided with the pseudo-second-order and Langmuir models, respectively, and the adsorption mechanism was monolayer chemisorption. Moreover, the vesicles worked well in wide ranges of environment pH, temperature, and co-existing pollutants. They also possessed excellent cyclic regeneration performance, in which 93 % of the initial adsorption capacity was maintained after four cycles. These results indicate that the millimeter-scale hollow vesicles exhibit broad application prospects for wastewater purification., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Xuejun Wang reports financial support was provided by Department of Science & Technology, Shandong Province, China. 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 Elsevier B.V. All rights reserved.)

Nowadays, dye water pollution is becoming increasingly severe. Composite of MXene, ZnS, and chitosan-cellulose material (MX/ZnS/CC) was developed to remove anionic dyes through the synergistic effect of adsorption and photocatalytic degradation. MXene was introduced as the cocatalyst to form Schottky heterostructure with ZnS for improving the separation efficiency of photocarriers and photocatalytic performance. Chitosan-cellulose material mainly served as the dye adsorbent, while also could improve material stability and assist in generation of free radicals for dye degradation. The physics and chemistry properties of MX/ZnS/CC composite were systematically inspected through various characterizations. MX/ZnS/CC composite exhibited good adsorption ability to anionic dyes with adsorption capacity up to 1.29 g/g, and excellent synergistic effects of adsorption and photodegradation with synergistic removal capacity up to 5.63 g/g. MX/ZnS/CC composite performed higher synergistic removal ability and better optical and electrical properties than pure MXene, ZnS, chitosan-cellulose material, and MXene/ZnS. After compounding, the synergistic removal percentage of dyes increased by a maximum of 309 %. MX/ZnS/CC composite mainly adsorbs anionic dyes through electrostatic interactions and catalyzes the generation of •O 2 - , h + , and •OH to degrade dyes, which has been successfully used to remove anionic dyes from environmental water, achieving a 100 % removal of 50 mg/L dye., 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.)

In this study, chitosan nanoparticles (ChNs) were used as an adsorbent for single and simultaneous uptake of cationic (methylene blue (MB)) and anionic (methyl orange (MO)) dyes. ChNs were prepared based on the ionic gelation method using sodium tripolyphosphate (TPP) and characterized by zetasizer, FTIR, BET, SEM, XRD, and pH PZC . The studied parameters that affect removal efficiency included pH, time, and dyes' concentration. The results showed that in single-adsorption mode, the removal of MB is better in alkaline pH, contrary to MO uptake which presents higher removal efficiency in acidic media. The simultaneous removal of MB and MO from the mixture solution by ChNs could be achieved under neutral conditions. The adsorption kinetic results showed that adsorption of MB and MO for both single-adsorption and binary adsorption systems comply with the pseudo-second-order model. Langmuir, Freundlich, and Redlich-Peterson isotherms were used for the mathematical description of single-adsorption equilibrium, while non-modified Langmuir and extended Freundlich isotherms were used to fit the co-adsorption equilibrium results. The maximum adsorption capacities of MB and MO in a single dye adsorption system were 315.01 and 257.05 mg/g for MB and MO, respectively. On the other hand, and for binary adsorption system, the adsorption capacities were 49.05 and 137.03 mg/g, respectively. The adsorption capacity of MB decreases in solution containing MO and vice versa, suggesting an antagonistic behavior of MB and MO on ChNs. Overall, ChNs could be a candidate for single and binary removal of MB and MO in dye-containing wastewater., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Since the potential carcinogenic, toxic and non-degradable dyes trigger serious environmental contamination by improper treatment, developing novel adsorbents remains a major challenge. A novel high efficiency and biopolymer-based environmental-friendly adsorbent, chitosan‑sodium tripolyphosphate-melamine sponge (CTS-STPP-MS) composite, was prepared for Orange II removing with chitosan as raw material, sodium tripolyphosphate as cross-linking agent. The composite was carefully characterized by SEM, EDS, FT-IR and XPS. The influence of crosslinking conditions, dosage, pH, initial concentration, contacting time and temperature on adsorption were tested through batch adsorption experiments. CTS-STPP-MS adsorption process was exothermic, spontaneous and agreed with Sips isotherm model accompanying the maximum adsorption capacity as 948 mg∙g -1 (pH = 3). Notably, the adsorption performance was outstanding for high concentration solutions, with a removal rate of 97 % in up to 2000 mg∙L -1 OII solution (100 mg sorbent dosage, 50 mL OII solution, pH = 3, 289.15 K). In addition, the adsorption efficiency yet remained 97.85 % after 5 repeated adsorption-desorption cycles. The driving force of adsorption was attributed to electrostatic attraction and hydrogen bonds which was proved by adsorption results coupled with XPS. Owing to the excellent properties of high-effective, environmental-friendly, easy to separate and regenerable, CTS-STPP-MS composite turned out to be a promising adsorbent in contamination treatment., 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.)

The structural stability and therapeutic activity of Stem Bromelain (BM) have been explored by unravelling the interaction of stem BM in presence of two different types of anionic surfactants namely, bile salts, NaC and NaDC and the conventional anionic surfactants, SDDS and SDBS, below, at and above the critical micelle concentration (cmc) in aqueous phosphate buffer of pH 7. Different physicochemical parameters like, surface excess (Γ cmc ), minimum area of surfactants at air water interface (A min ) etc. are calculated from tensiometry both in absence and presence of BM. Several inflection points (C 1 , C 2 and C 3 ) have been found in tensiometry profile of surfactants in presence of BM due to the conformational change of BM assisted by surfactants. Similar observation also found in isothermal titration calorimetry (ITC) profiles where the enthalpy of micellization (ΔH 0 obs ) of surfactants in absence and presence of BM have calculated. Further, steady state absorption and fluorescence spectra monitoring the tryptophan (Trp) emission of free BM and in presence of all the surfactants at three different temperatures (288.15 K, 298.15 K, and 308.15 K) reveal the nature of fluorescence quenching of BM in presence of bile salts/surfactants. Time resolved fluorescence studies at room temperature also support to determine the several quenching parameters. The binding constant (K b ) of BM with all the surfactants and free energy of binding (∆G 0 of bile salts/surfactants with BM at different temperatures have been calculated exploiting steady state fluorescence technique. It is observed that, the binding of NaC with BM is greater as compared to other surfactants while Stern-Volmer quenching constant (K SV ) is found greater in presence of SDBS as compared with others which supports the surface tension and ITC data with the fact that surface activity of surfactant(s) is decreasing with the binding of the surfactants at the core or binding pocket of BM. Circular Dichroism (CD) study shows the stability of secondary structure of BM in presence of NaC and NaDC below C 3 , while BM lost its structural stability even at very low surfactant concentration of SDDS and SDBS which also supports the more involvement of bile salts in binding rather than surfactants. The molecular docking studies have also been substantiated for better understanding the several experimental investigations interaction of BM with the bile salts/surfactants., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Biomass chitosan has garnered considerable interest for alkaline anion exchange membranes (AEMs) due to its eco-friendly and sustainable characteristics, low reactant permeability and easily modifiable nature, but it still faces the trade-off between high hydroxide conductivity and sufficient mechanical properties. Herein, a novel functionalized attapulgite clay (f-ATP) with a unique ionic "chain-ball" surface structure was prepared and incorporated with quaternized chitosan (QCS)/polyvinyl alcohol (PVA) matrix to fabricate high-performance composite AEMs. Due to the strengthened interfacial bonding between f-ATP nanofillers and the QCS/PVA matrix, composite membranes are synergistically reinforced and toughened, achieving peak tensile strength and elongation at break of 24.62 MPa and 33.8 %. Meanwhile, abundant ion pairs on f-ATP surface facilitate ion transport in the composite AEMs, with the maximum OH - conductivity of 46 mS cm -1 at 80 °C and the highest residual IEC of 83 % after alkaline treatment for 120 h. Moreover, the assembled alkaline direct methanol fuel cell exhibits a remarkable power density of 49.3 mW cm -2 at 80 °C. This work provides a new strategy for fabricating high-performance anion exchange membranes., 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.)