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Inorganic chloramines are commonly used drinking water disinfectants intended to safeguard public health and curb regulated disinfection by-product formation. However, inorganic chloramines themselves produce by-products that are poorly characterized. We report chloronitramide anion (Cl-N-NO 2 - ) as a previously unidentified end product of inorganic chloramine decomposition. Analysis of chloraminated US drinking waters found Cl-N-NO 2 - in all samples tested ( n = 40), with a median concentration of 23 micrograms per liter and first and third quartiles of 1.3 and 92 micrograms per liter, respectively. Cl-N-NO 2 - warrants occurrence and toxicity studies in chloraminated water systems that serve more than 113 million people in the US alone.

Dressings should protect wounds, promote healing, absorb fluids, and maintain moisture. Bacterial cellulose is a biopolymer that stands out in biomaterials due to its high biocompatibility in several applications. In the area of dressings, it is already marketed as an alternative to traditional dressings. However, it lacks any intrinsic activity; among these, the need for antimicrobial activity in infected wounds stands out. We developed a cationic cellulose film by modifying cellulose with 1-(5-carboxypentyl)pyridin-1-ium bromide, enhancing its wettability (contact angle: 26.6°) and water retention capacity (2714.37 %). This modified film effectively retained oxacillin compared to the unmodified control. Liposomal encapsulation further prolonged oxacillin release up to 11 days. Both oxacillin-loaded films and liposomal formulations demonstrated antimicrobial activity against Staphylococcus aureus. Our findings demonstrate the potential of chemically modified cellulose as a platform for controlled anionic antibiotics and/or their formulations delivery in wound care., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: [Renato Ribeiro Viana, Karina Andressa Sedans, Bruna Conceição Costa Silva, Cesar Augusto Tischer and Luis Fernando Cabeça have patent pending to BR10202202711. 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.)

This study evaluated the effects of post-calcination on the charge properties and active sites of Mg/Al layered double hydroxide-decorated spent coffee ground biochars (LDH MgAl @SCGB) governing adsorption behaviors and mechanisms of arsenic (As V ) and antimony (Sb V ) anions from aqueous phases. Post-calcinated LDH MgAl @SCGB (PLDH MgAl @SCGB) exhibited higher adsorption capacities for As V and Sb V compared to spent coffee ground biochars (SCGB) and LDH MgAl @SCGB as post-calcination of LDH MgAl @SCGB enhanced the charge properties (surface zeta potential at pH 7.0: SCGB = -21.8 mV, LDH MgAl @SCGB = 28.5 mV, and PLDH MgAl @SCGB = 34.4 mV) and increased active sites by eliminating the anions (i.e., Cl - ions) and water molecules at its interlayers. The calculated kinetic, intra-particle diffusion, and isotherm parameters indicated that the chemisorption and intra-particle diffusion were mainly responsible for the adsorption of As V and Sb V by SCGB, LDH MgAl @SCGB, and PLDH MgAl @SCGB. Moreover, post-calcination of LDH MgAl @SCGB enhanced its selectivity toward As V and Sb V by reinforcing the electrostatic surface complexation via its improvement of charge properties. Since PLDH MgAl @SCGB exhibited the excellent reusability for the adsorption of As V (reuse efficiency >63.6%) and Sb V (reuse efficiency >52.1%), it can be concluded that post-calcination of LDH MgAl @SCGB is a promising method for improving the adsorption capacities for As V and Sb V in real water matrices., 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.)

Environmental factors, including mechanical stress and surrounding lipids, can influence the response of GPCRs, such as the mechanosensitive angiotensin II type 1 receptor (AT1). To investigate the impact of these factors on AT1 activation, we developed a steered molecular dynamics simulations protocol based on quaternion formalism. In this protocol, a pulling force was applied to the N-terminus of transmembrane helix 6 (TM6) to induce the TM6 opening characteristic of activation. Subsequently, the simulations were continued without constraints to allow the receptor to relax around the novel TM6 conformation under different conditions. We analyzed the responses of AT1 to membrane stretching, modeled by applying surface tension, in different bilayers. In phosphocholine bilayers without surface tension, we could observe a transient atypical structure of AT1, with an outward TM7 conformation, at the beginning of the activation process. This atypical structure then evolved toward a pre-active structure with outward TM6 and inward TM7. Strikingly, the presence of anionic phosphoglycerol lipids and application of surface tension synergistically favored the atypical structure, which led to an increase in the cross-section area of the receptor intracellular domain. Lipid internalization and H-bonds between lipid heads and the receptor C-terminus increased in phosphoglycerol vs phosphocholine bilayers, but did not depend on surface tension. The difference in the cross-section area of the atypical and pre-active conformations makes the conformational transition sensitive to lateral pressure, and favors the atypical conformation upon surface tension. Anionic lipids act as allosteric modulators of the conformational transition, by stabilizing the atypical conformation. These findings contribute to decipher the mechanisms underlying AT1 activation, highlighting the influence of environmental factors on GPCR responses. Moreover, our results reveal the existence of intermediary conformations that depend on receptor environment and could be targeted in drug design efforts., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Ben Boubaker et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

Fungal lipolytic enzymes play crucial roles in various lipid bio-industry processes. Here, we elucidated the biochemical and structural characteristics of an unexplored fungal lipolytic enzyme (TaLip) from Thermoascus aurantiacus var. levisporus, a strain renowned for its significant industrial relevance in carbohydrate-active enzyme production. TaLip belongs to a poorly understood phylogenetic branch within the class 3 lipase family and prefers to hydrolyze mainly short-chain esters. Nonetheless, it also displays activity against natural long-chain triacylglycerols. Furthermore, our analyses revealed that the surfactant sodium dodecyl sulfate (SDS) enhances the hydrolytic activity of TaLip on pNP butyrate by up to 5.0-fold. Biophysical studies suggest that interactions with SDS may prevent TaLip aggregation, thereby preserving the integrity and stability of its monomeric form and improving its performance. These findings highlight the resilience of TaLip as a lipolytic enzyme capable of functioning in tandem with surfactants, offering an intriguing enzymatic model for further exploration of surfactant tolerance and activation in biotechnological applications., 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.)

Therapeutic oligonucleotides are becoming an important class of therapeutics. Their manufacturing processes can result in the formation of impurities, particularly truncated species. To ensure the quality and safety of the product, it is crucial to evaluate the presence of these species. Liquid chromatography analysis enables such purity determination. In this context, a recently described weak anion exchange chromatography method was optimized to allow the effective separation of different impurities. The optimization addressed the complexity and instability of the mobile phases, which contained salts and organic compounds. Adjustments were made to the mobile phase composition and gradient to meet the requirements of QC laboratories. Additionally, to ensure the method's reliability, a robustness study was conducted based on a risk assessment. Five factors were considered potential risks and were assessed experimentally on different chromatographic outputs. This led to the definition of a robust space, ensuring the method's reliability for the purity determination of oligonucleotides., 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.)

Neurodegenerative diseases, such as Alzheimer's, Parkinson's, and Huntington's, affect millions worldwide and share a common feature: the aggregation of intrinsically disordered proteins into toxic oligomers that interact with cell membranes. In Alzheimer's disease (AD), amyloid-beta (Aβ) peptides accumulate and bind to plasma membranes, potentially disrupting cellular function. The complex interplay between amyloidogenic peptides and lipid membranes, particularly the role of anionic lipids, is crucial in disease pathogenesis but challenging to characterize experimentally. The literature presents conflicting results on the influence of anionic lipids on peptide aggregation kinetics, highlighting a knowledge gap. To address this, we used coarse-grained molecular dynamics (CG-MD) simulations to study interactions between a model amyloidogenic peptide, amyloid-β's K 16 LVFFAE 22 fragment (Aβ 16-22 ), and mixed lipid bilayers. We used phosphatidylserine (PS) and phosphatidylcholine (PC) as representative anionic and zwitterionic lipids, respectively, examining the mixed bilayer compositions of 0% PS-100% PC, 10% PS-90% PC, and 30% PS-70% PC. Our simulations revealed that membranes enriched in anionic lipids enhance peptide adsorption and interaction kinetics. The aggregation dynamics was modulated by two competing factors: increased local peptide concentration near negatively charged membranes, which promoted aggregation, and peptide-lipid interactions, which slowed it down. Higher percentages of anionic lipids led to smaller and more ordered aggregates and enhanced lipid demixing, leading to the formation of PS clusters. These findings contribute to understanding membrane-mediated peptide aggregation in neurodegenerative disorders, potentially guiding new therapeutic strategies targeting the early stages of protein aggregation in various neurodegenerative diseases.

The adsorption efficiency of Cr(VI) and anionic textile dyes onto MgAl-layered double hydroxides (LDHs) and MgAl-LDH coated on bio-silica (b-SiO 2 ) nanoparticles (MgAl-LDH@SiO 2 ) derived from waste rice husks was studied in this work. The material was characterized using field-emission scanning electron microscopy (FE-SEM/EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopic (XPS) techniques. The adsorption capacities of MgAl-LDH@SiO 2 were increased by 12.2%, 11.7%, 10.6%, and 10.0% in the processes of Cr(VI), Acid Blue 225 (AB-225), Acid Violet 109 (AV-109), and Acid Green 40 (AG-40) dye removal versus MgAl-LDH. The obtained results indicated the contribution of b-SiO 2 to the development of active surface functionalities of MgAl-LDH. A kinetic study indicated lower intraparticle diffusional transport resistance. Physisorption is the dominant mechanism for dye removal, while surface complexation dominates in the processes of Cr(VI) removal. The disposal of effluent water after five adsorption/desorption cycles was attained using enzymatic decolorization, photocatalytic degradation of the dyes, and chromate reduction, satisfying the prescribed national legislation. Under optimal conditions and using immobilized horseradish peroxidase (HRP), efficient decolorization of effluent solutions containing AB-225 and AV-109 dyes was achieved. Exhausted MgAl-LDH@SiO 2 was processed by dissolution/precipitation of Mg and Al hydroxides, while residual silica was used as a reinforcing filler in polyester composites. The fire-proofing properties of composites with Mg and Al hydroxides were also improved, which provides a closed loop with zero waste generation. The development of wastewater treatment technologies and the production of potentially marketable composites led to the successful achievement of both low environmental impacts and circular economy implementation.

A hybrid receptor-sensor for anions originating from the merging of positively charged ammonium moieties for electrostatic attraction/stronger binding of azacrowns with directionality of calixpyrrole hydrogen bond donors for selectivity is investigated. As demonstrated this hybrid receptor-sensor shows a remarkable selectivity for orthophosphate even in the presence of other phosphates and anions found in cellular materials (K assoc H 2 PO 4 - >H 2 P 2 O 7 2- >AMP - ≫ADP 2- or ATP 3- over halides, nitrate, or hydrogen sulfate; all Na + salts in water) but also cellular polyphosphate or phospholipids. This selectivity is harnessed in a real-time monitoring of cell lysis by lysozyme, which releases orthophosphate and other phosphates and anions from the cells. This sensitive (LOD 0.4 μM) fluorescence-based microscale method compares favorably with the state-of-the-art techniques but can easily be practiced in a high-throughput screening (HTS) manner. The anion binding and selectivity in aqueous solutions were investigated by NMR and put in context with phosphate binding of the parent calix[4]pyrrole. The microscopic understanding of anion binding by the hybrid receptor was then obtained from a combination of density functional theory (DFT), classical molecular dynamics (MD) with explicit water solvation, and ab initio MD (AIMD) simulations. Correlating the NMR and fluorescence binding data with studies of solvation of the receptor, phosphate anion, and the resulting complex confirms the binding is largely driven by entropic component (TΔS) associated with receptor and anion desolvation., (© 2024 Oak Ridge National Laboratory and The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH on behalf of Chemistry Europe.)

Glucosinolates, a crucial group of secondary metabolites in Brassica vegetables, present significant chromatographic separation challenges due to their anionic form, structure diversities, and co-existence of other phenolic compounds. This study comparatively investigated the retention and separation of seven glucosinolates using a mixed-mode reversed-phase/weak anion-exchange column and a conventional reversed-phase C18 column. Separation factors for each glucosinolate with its adjacent peaks were over 1.0 on the mixed-mode column, while co-eluting was observed on the C18 column. The effects of mobile phase additives and pH on the separation and retention of glucosinolates were also investigated. Results showed that glucosinolate retention was inversely related to both buffer concentration and pH. The optimized method for the mix-mode column was applied to the complex Brassica vegetable samples. In addition to the 17 well-resolved glucosinolate peaks, 34 peaks for phenolic compounds were identified in broccoli microgreen, suggesting the successful application scenarios for qualitative analysis in comparison with the single mode reverse phase C18 column. This study demonstrates that the mixed-mode reversed-phase/weak anion-exchange column can be used as a promising separation tool for organic anions in a complex sample matrix., (© 2024 Wiley‐VCH GmbH. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.)

Ficin fully immobilized on Asp-agarose beads at pH 7 but not on an aminated support. This made enzyme adsorption plus glutaraldehyde modification non-viable for this enzyme. Modifying glyoxyl-agarose beads with mixtures of Asp and 1,6-hexamethylenediamine (HA) at different ratios, mixed anion/cation exchanger supports were built. Only if HA greatly exceed Asp in the support, immobilization did not work. While only using the Asp-agarose support immobilized enzyme molecules were only ionically adsorbed after glutaraldehyde treatment (visualized in SDS-PAGE analysis), the mixed supports gave covalent immobilization. The glutaraldehyde modification of these biocatalysts permitted to establish covalent bonds with the support, and this was more effective when using higher amounts of HA in the support. When around 60 % of the groups in the support were HA, the treatment with glutaraldehyde fully suppressed enzyme release from the support after boiling in SDS. The glutaraldehyde treated biocatalysts were more stable than just the adsorbed enzymes or the enzyme adsorbed only on Asp supports and then treated with glutaraldehyde (the optimal biocatalyst retained 90 % of the initial activity while the just adsorbed ficin retained 50 % of the initial activity). This strategy can be utilized to immobilize other proteins with high isoelectric points following this immobilization strategy., 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.)

Hyaluronic acid (HA) is a glycosaminoglycan essential for cellular processes and finding increasingly applications in medicine, pharmaceuticals, and cosmetics. While membrane-integrated Class I hyaluronan synthase (HAS) catalyzes HA synthesis in most organisms, the molecular mechanisms by which HAS-lipid interactions impact HAS catalysis remain unclear. This study employed coarse-grained molecular dynamics simulation combined with dimensionality reduction to uncover the interplay between lipids and Streptococcus equisimilis HAS (SeHAS). A minimum of 67 % cardiolipin is necessary for HA synthesis, as determined through simulations using gradient-composed membranes. The anionic cardiolipin stabilizes the cationic transmembrane regions of SeHAS and thereby maintains its conformation. Moreover, the highly dynamic cardiolipin is required to modulate the catalysis-relevant motions in HAS and thus facilitate HA synthesis. These findings provide molecular insights essential not only for understanding the physiological functions of HAS, but also for the development of cell factories and enzyme catalysts for HA production., Competing Interests: Declaration of competing interest The authors declare that they have no conflicts of interest with the contents of this article., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Background: Interaction of β 2 -glycoprotein I (β 2 GPI) with anionic membranes is crucial in antiphospholipid syndrome (APS), implicating the role of its membrane-binding domain, domain V (DV). The mechanism of DV binding to anionic lipids is not fully understood., Objectives: This study aimed to elucidate the molecular details of β 2 GPI DV binding to anionic membranes., Methods: We utilized molecular dynamics simulations to investigate the structural basis of anionic lipid recognition by DV. To corroborate the membrane-binding mode identified in the highly mobile membrane mimetic simulations, we conducted additional simulations using a full membrane model., Results: The study identified critical regions in DV, namely the lysine-rich loop and the hydrophobic loop, which are essential for membrane association via electrostatic and hydrophobic interactions, respectively. A novel lysine pair contributing to membrane binding was also discovered, providing new insights into β 2 GPI's membrane interaction. Simulations revealed 2 distinct binding modes of DV to the membrane, with mode 1 characterized by the insertion of the hydrophobic loop into the lipid bilayer, suggesting a dominant mechanism for membrane association. This interaction is pivotal for the pathogenesis of APS, as it facilitates the recognition of β 2 GPI by antiphospholipid antibodies., Conclusion: The study advances our understanding of the molecular interactions between β 2 GPI's DV and anionic membranes, which are crucial for APS pathogenesis. It highlights the importance of specific regions in DV for membrane binding and reveals a predominant binding mode. These findings have significant implications for APS diagnostics and therapeutics, offering a deeper insight into the molecular basis of the syndrome., Competing Interests: Declaration of competing interests There are no competing interests to disclose., (Copyright © 2024 The Author(s). Published by Elsevier Inc. All rights reserved.)

Biochar, a waste biomass-derived adsorbent, holds promise for decentralised wastewater treatment. However, limited research exists on its efficacy in adsorbing anionic surfactants in wastewater. To address this, the adsorption of sodium dodecyl sulphate (SDS), a common anionic surfactant, was studied using various biochar types: rice husk biochar (RH-550 and RH-700), wheat straw biochar (WS-550 and WS-700) produced at 550°C and 700°C, wood-based biochar (OB), and activated carbon (AC) as a control. The study investigated the impact of pH (3-9), adsorbent loading (1-10 g/L), adsorbent size (<0.5-2.5 mm), contact time (5-180 min), and initial concentration (50-200 mg/L) on SDS removal. Under optimised conditions (100 mg/L SDS, 4 g/L adsorbent, 1-2 mm particle size, pH 8.3, and 180 min contact time), maximum SDS removals were RH-550 (78%), RH-700 (82.4%), WS-550 (89.5%), WS-700 (90.4%), AC (97%), and OB (88.4%). Among the tested adsorbent materials, WS-550 exhibited the highest SDS adsorption capacity at 66.23 mg/g compared to AC (80.65 mg/g), followed by RH-550 (49.75 mg/g), OB (45.87 mg/g), RH-700 (43.67 mg/g), and WS-700 (42.74 mg/g). SDS adsorption followed a pseudo-second-order kinetic model, indicating chemisorption on the adsorbent surface. The Freundlich isotherm model exhibited a better fit for the experimental data on SDS adsorption using all tested adsorbents except for RH-550. This study showed that biochars produced from agricultural and forestry residues are effective adsorbents for SDS in aqueous solutions and can be a promising sustainable and low-cost material for the treatment of greywater containing anionic surfactants (e.g. handwashing, laundry, kitchen, and bathroom greywaters).

We report the design, synthesis and characterization of a perylene diimide-hydroxyphenyl benzothiazole (BT-PDI) dyad as a new class for the formation of radical anion (BT-PDI˙ - ) and dianion (BT-PDI 2- ) in aqueous medium using H 2 S. We demonstrate the applications of BT-PDI˙ - for (i) the detection of H 2 O 2 ; (ii) the detection of glucose in blood serum using a biochemical assay and (iii) the reduction of Ag + to Ag 0 .

Electrolyte additives are investigated to resolve dendrite growth, hydrogen evolution reaction, and corrosion of Zn metal. In particular, the electrostatic shielding cationic strategy is considered an effective method to regulate deposition morphology. However, it is very difficult for such a simple cationic modification to avoid competitive hydrogen evolution reactions, corrosion, and interfacial pH fluctuations. Herein, multifunctional additives of potassium hydrogen phthalate (KHP) based on the synergistic design of cationic shielding and anionic chemistry for ultrastable Zn||I 2 full batteries are demonstrated. K cations, acting as electrostatic shielding cations, constructed the smooth deposition morphology. HP anions can enter the first solvation shell of Zn 2+ for the reduced activities of H 2 O, while they remain in the primary solvation shell and are finally involved in the formation of SEI, thus accelerating the charge transfer kinetics. Furthermore, by in situ monitoring the near-surface pH of the Zn electrode, the KHP additives can effectively inhibit the accumulation of OH - and the formation of by-products. Consequently, the symmetric cells achieve a high stripping-plating reversibility of over 4500 and 2600 h at 1.0 and 5 mA cm -2 , respectively. The Zn||I 2 full cells deliver an ultralong term stability of over 1400 cycles with a high-capacity retention of 78.5%., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Antifouling properties are crucial for enhancing the longevity and functionality of biomedical implants, drug delivery systems, and biosensors. Zwitterionic polymers are renowned for their exceptional surface hydration and charge neutrality, which effectively resist biomolecular adsorption and protein attachment. We propose an innovative approach to develop zwitterion-like antifouling surfaces by chelating divalent cations with anionic poly(3,4-ethylenedioxythiophene) (PEDOT) films, specifically PEDOT-PO 4 and PEDOT-COOH. The chelation behavior of these films was systematically evaluated using Na + , Mg 2+ , and Ca 2+ ions. Divalent ions, particularly Ca 2+ and Mg 2+ , exhibit a strong affinity for the anionic groups, leading to significant antifouling properties. These modified surfaces effectively repelled both negatively charged bovine serum albumin (BSA) and positively charged lysozyme (LYZ) proteins across various pH environments. This study offers valuable insights into the antifouling characteristics of charged surfaces, enhancing our understanding of how ion-mediated surface modifications influence protein adsorption and interactions.

Macrocyclic receptors have emerged as versatile and efficient molecular tools for the recognition and sensing of anions, playing a pivotal role in molecular recognition and supramolecular chemistry. The following review provides an overview of the recent advances in the design, synthesis, and applications of macrocyclic receptors specifically tailored for anion recognition. The unique structural features of macrocycles, such as their well-defined structures and pre-organised binding sites, contribute to their exceptional anion-binding capabilities that have led to their application across a broad range of the chemical and biological sciences.

Hypothesis: Nonionic surfactants can counter the deleterious effect that anionic surfactants have on proteins, where the folded states are retrieved from a previously unfolded state. However, further studies are required to refine our understanding of the underlying mechanism of the refolding process. While interactions between nonionic surfactants and tightly folded proteins are not anticipated, we hypothesized that intermediate stages of surfactant-induced unfolding could define new interaction mechanisms by which nonionic surfactants can further alter protein conformation., Experiments: In this work, the behavior of three model proteins (human growth hormone, bovine serum albumin, and β-lactoglobulin) was investigated in the presence of the anionic surfactant sodium dodecylsulfate, the nonionic surfactant β-dodecylmaltoside, and mixtures of both surfactants. The transitions occurring to the proteins were determined using intrinsic fluorescence spectroscopy and far-UV circular dichroism. Based on these results, we developed a detailed interaction model for human growth hormone. Using nuclear magnetic resonance and contrast-variation small-angle neutron scattering, we studied the amino acid environment and the conformational state of the protein., Findings: The results demonstrate the key role of surfactant cooperation in defining the conformational state of the proteins, which can shift away or toward the folded state depending on the nonionic-to-ionic surfactant ratio. Dodecylmaltoside, initially a non-interacting surfactant, can unexpectedly associate with sodium dodecylsulfate-unfolded proteins to further impact their conformation at low nonionic-to-ionic surfactant ratio. When this ratio increases, the protein begins to retrieve the folded state. However, the native conformation cannot be fully recovered due to remnant surfactant molecules still adsorbed to the protein. This study demonstrates that the conformational landscape of the protein depends on a delicate interplay between the surfactants, ultimately controlled by the ratio between them, resulting in unpredictable changes in the protein conformation., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: [Adrian Sanchez-Fernandez reports financial support was provided by Sweden’s Innovation Agency. 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 Author(s). Published by Elsevier Inc. All rights reserved.)

Large synthetic oligonucleotides such as guide ribonucleic acid (gRNA), a critical reagent in clustered regularly interspaced short palindromic repeats (CRISPR)/Cas9 genome editing, have complex higher order structures (HOS) inherent in their design. In this study, we first developed a generic anion exchange chromatography (AEX) method for the comprehensive analysis of a 100mer single guide ribonucleic acid (sgRNA) impurity profiling. AEX demonstrated superior resolution compared to other common chromatographic methods employed for sgRNA analysis, such as Ion-Pairing Reversed Phase Liquid Chromatography (IP-RPLC) and Hydrophilic Interaction Chromatography (HILIC). Moreover, we discovered AEX's potential in probing the HOS of RNAs by adjusting the temperature and using organic additives. Our study also highlighted that sgRNA possesses a unique HOS distinctly different from other therapeutic nucleic acids, such as antisense oligonucleotides and messenger RNAs., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Bingchuan Wei reports financial support was provided by Genentech Inc., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The structure of zwitterion has great impact on the separation properties of zwitterionic hydrophilic stationary phases. To better understand the role of anionic groups of zwitterions, a novel carboxybetaine-based zwitterionic monolithic column was first prepared through thermo-initiated copolymerization of functional monomer (3-acrylamidopropyl)-dimethyl-(2-carboxymethyl) ammonium (CBAA) and crosslinker ethylene dimethacrylate (EDMA) within 100 μm ID capillary. The optimal poly(CBAA-co-EDMA) monolithic column exhibited satisfactory mechanical and chemical stability, good repeatability, high column efficiency (96,000 plates/m), and excellent separation performance for different classes of polar compounds (i.e., phenols, monophosphate nucleotides, urea and allantoin). A comparative study was then performed among three zwitterionic hydrophilic stationary phases containing different anionic groups, i.e. poly(CBAA-co-EDMA) (carboxybetaine), poly(2-{2-(methacryloyloxy) ethyldimethylammonium}ethyl n-butyl phosphate-co-EDMA) (phosphocholine), and poly(N,N-dimethyl-N-(3-methacrylamidopropyl)-N-(3-sulfopropyl) ammonium betaine-co-EDMA) (sulfobetaine) using benzoic acid derivatives, amine compounds, nucleobases and nucleosides as model analytes. The carboxybetaine-based monolithic column exhibited much higher positive zeta-potential and hydrophilicity, which endows it with a stronger retention capacity for acidic and neutral compounds, but sulfobetaine-based monolithic column exhibited much higher selectivity and retention capacity for the amines. Moreover, their enrichment efficiencies for N-glycopeptides were also evaluated based on their different hydrophilicity, and it was observed that the poly(CBAA-co-EDMA) monolithic material captured 4-8 times more N-glycopeptides compared to the other two materials., 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.)

Tau, an intrinsically disordered neuronal protein and polyampholyte with an overall positive charge, is a microtubule (MT) associated protein that binds to anionic domains of MTs and suppresses their dynamic instability. Aberrant tau-MT interactions are implicated in Alzheimer's and other neurodegenerative diseases. Here, we studied the interactions between full-length human protein tau and other negatively charged binding substrates, as revealed by differential interference contrast (DIC) and fluorescence microscopy. As a binding substrate, we chose anionic liposomes (ALs) containing either 1,2-dioleoyl- sn -glycero-3-phosphatidylserine (DOPS, -1e) or 1,2-dioleoyl- sn -glycero-3-phosphatidylglycerol (DOPG, -1e) mixed with zwitterionic 1,2-dioleoyl- sn -glycero-3-phosphatidylcholine (DOPC) to mimic anionic plasma membranes of axons where tau resides. At low salt concentrations (0 to 10 mM KCl or NaCl) with minimal charge screening, reaction mixtures of tau and ALs resulted in the formation of distinct states of AL-tau complexes coexisting with liquid-liquid phase-separated tau self-coacervates arising from the polyampholytic nature of tau containing cationic and anionic domains. AL-tau complexes (i.e. tau-lipoplexes) exhibited distinct types of morphologies. This included large ∼20-30 μm tau-decorated giant vesicles with additional smaller liposomes with bound tau attached to the giant vesicles and tau-mediated finite-size assemblies of small liposomes. As the salt concentration was increased to near and above 150 mM for 1:1 electrolytes, AL-tau complexes remained stable, while tau self-coacervate droplets were found to dissolve, indicative of the breaking of (anionic/cationic) electrostatic bonds between tau chains due to increased charge screening. The findings are consistent with the hypothesis that distinct cationic domains of tau may interact with anionic lipid domains of the lumen-facing monolayer of the axon's plasma membrane, suggesting the possibility of transient yet robust interactions near relevant ionic strengths found in neurons.

Anticancer drugs inhibit DNA replication by intercalating between DNA base pairs, forming covalent bonds with nucleotide bases, or binding to the DNA groove. To develop safer drugs, novel molecular structures with alternative binding mechanisms are essential. Stable boron hydrides offer a promising alternative for cancer therapy, opening up additional options like boron neutron capture therapy based on 10 B and thermal neutron beams or proton boron fusion therapy using 11 B and proton beams. These therapies are more efficient when the boron compound is ideally located inside cancer cells, particularly in the nucleus. Current cancer treatments often utilize small, polycyclic, aromatic, planar molecules that intercalate between ds-DNA base pairs, requiring only a spacing of approximately 0.34 nm. In this paper, we demonstrate another type of intercalation. Notably, [3,3'-Fe(1,2-C 2 B 9 H 11 ) 2 ] - , ([ o -FESAN] - ), a compact 3D molecule measuring 1.1 nm × 0.6 nm, can as well intercalate by strong non-bonding interactions preferentially with guanine. Unlike known intercalators, which are positive or neutral, [ o -FESAN] - is a negative species and when an [ o -FESAN] - molecule approaches the negatively charged DNA phosphate chain an anion-anion interaction consistently anti-electrostatic via C cluster -H⋯O-P bonds occurs. Then, when more molecules approach, an elongated outstandingly self-assembled structure of [ o -FESAN] - -[ o -FESAN] - forms moving anions towards the interthread region to interact with base pairs and form aggregates of four [ o -FESAN] - anions per base pair. These aggregates, in this environment, are generated by C cluster -H⋯O-C, N-H⋯H-B and C cluster -H⋯H-B interactions. The ferrabis(dicarbollide) boron-rich small molecules not only effectively penetrate the nucleus but also intercalate with ds-DNA, making them promising for cancer treatment. This amphiphilic anionic molecule, used as a carrier-free drug, can enhance radiotherapy in a multimodal perspective, providing healthcare professionals with improved tools for cancer treatment. This work demonstrates these findings with a plethora of techniques.

This work developed a novel sustainable adsorbent (PF-Aq) prepared by the amino-functionalization of palm oil fibers (PF). XPS, SEM/EDS, TGA/DSC, and FT-IR techniques proved the successful functionalization of the PF with the amino group. The PF-Aq adsorbent presents a high adsorption capacity for phosphate and Cr(VI) ions. Adsorption kinetics of the ions onto the PF-Aq followed the general-order models, with 240- and 300-min equilibrium times for phosphate and Cr(VI), respectively. The Freundlich equilibrium model can explain the adsorption of phosphate and Cr(VI) on the PF-Aq. Besides, the maximum adsorption capacities were 151.07 mg g -1 for phosphate and 206.08 mg g -1 for Cr(VI). The best pH for the adsorption of both ions on PF-Aq was 4.0. Interestingly, adsorption was exothermic for phosphate and endothermic for Cr(VI). The adsorption capacities were reduced by 16% for phosphate and 10% for Cr(VI) after 5 adsorption-desorption cycles, demonstrating the good recyclability of the PF-Aq. It can be concluded that PF-Aq is a relevant adsorbent to uptake phosphate and Cr(VI) from water due to its high adsorption capacity, low cost, recyclability, availability, and fast kinetics. Finally, the excellent adsorption potential results from inserting amino groups in the PF, allowing electrostatic interactions between adsorbent and adsorbate., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The study of metal ion's role in the biological processes of Alzheimer's disease has spurred investigations into the coordination chemistry of amyloid beta peptide and its fragments. Nano-electrospray ionization mass spectrometry (nESI-MS) has been utilized to examine the stabilization of bound anions on multiprotein complexes without bulk solvent. However, the effects of anions on metal ion binding interactions with amyloid beta peptide have not been explored. This study directly examined metal-peptide complexes using nESI-MS and investigated the effects of various anions on the binding ratio and stability of these complexes from ammonium salt solutions. The results indicate that different anions have distinct effects on the binding ratio and stability of various metal-peptide complexes. Of these, the bicarbonate ion exhibits the highest binding ratios for metal-peptide complexes, while binding ratios for these complexes in phosphate are comparatively low. Our results suggest that acetate, formate, bicarbonate, and phosphate have weak affinities and act as weak stabilizers of the metal-peptide complex structure in the gas phase. Intriguingly, chloride and sulfate act as stabilizers of the metal-peptide complex in the gas phase. The rank order determined from these data is substantially different from the Hofmeister salt series in solution. Although this outcome was anticipated due to the reduced influence of anions and water solvation, our findings correlate well with expected anion binding in solution and emphasize the importance of both hydration layer and anion-metal-peptide binding effects for Hofmeister-type stabilization in solution. This approach proved useful in examining the interactions between metal ions and amyloid beta peptide, which are relevant to Alzheimer's disease, using direct ESI-MS., (© 2024 The Author(s). Journal of Mass Spectrometry published by John Wiley & Sons Ltd.)

Microbial rhodopsins are photoreceptive membrane proteins found in microorganisms with an all-trans-retinal chromophore. The function of many microbial rhodopsins is determined by three residues in the third transmembrane helix called motif residues. Here, we report a group of microbial rhodopsins with a novel Thr-Thr-Gly (TTG) motif. The ion-transport assay revealed that they function as light-driven inward anion pumps similar to halorhodopsins previously found in archaea and bacteria. Based on the characteristic glycine residue in their motif and light-driven anion-pumping function, these new rhodopsins are called glycylhalorhodopsins (GHRs). X-ray crystallographic analysis found large cavities on the cytoplasmic side, which are produced by the small side-chain volume of the glycine residue in the motif. The opened structure of GHR on the cytoplasmic side is related to the anion releasing process to the cytoplasm during the photoreaction compared to canonical halorhodopsin from Natronomonas pharaonis (NpHR). GHR also transports SO 4 2- and the extracellular glutamate residue plays an essential role in extracellular SO 4 2- uptake. In summary, we have identified TTG motif-containing microbial rhodopsins that display an anion-releasing mechanism., Competing Interests: Conflict of interest The authors declare that they have no conflicts of interest with the contents of this article., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Due to their prevalence in the lithosphere and their high capability of sorbing pollutants, smectite clays play a foreground role in environmental pollution studies, waste management, and soil science. In complementarity with existing approaches at the molecular or macroscopic scales, real microstructures have been employed to investigate ionic transport by diffusion through montmorillonite and water-saturated Wyoming bentonite at intermediate scales ranging between the nanometer and the micrometer. The coupled solute transport and electrostatic phenomena investigated at the nanopore scale are upscaled using the homogenization of porous media approach. Homogenization computations rely on a hierarchical description of bentonite that acknowledges the existence of pores networks at different scales. At the scale of montmorillonite layers, digitized TEM images have been employed to simulate the diffusion of ionic solutes by considering electrostatic interactions in the vicinity of the negatively charged clay platelets' surface. Finite element microstructures are created after extraction of the contours of the layers using dedicated image processing algorithms. Local electric potential distribution, anion exclusion, and cation inclusion are displayed by ion distribution maps. The effective diffusion tensor and the transport equation obtained through volume averaging are then used to simulate diffusion at the scale of a Wyoming bentonite sample composed of clay gels of variable density, solid grains, and micropores. Qualitative comparisons were made with existing diffusion data, and a particular attention is given to the anisotropy of the diffusion tensors at both the mesoscopic and macroscopic scales., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Poly(ethylene glycol) (PEG) or oligo (ethylene glycol) (OEG) grafted anion exchange membranes (AEMs) exhibit improved ionic conductivity, high alkaline stability, and subsequent boosted AEM fuel cell performance, but too much PEG/OEG side chains may can result in a reduction in the ion exchange capacity (IEC), which can have adverse effects on ion transport. Here, a series of partially PEG-grafted poly(terphenyl piperidinium) with different side chain length are synthesized using simple postpolymerization modification to produce AEMs with balanced properties. The polar and flexible PEG side chains are responsible for the controlled water uptake and swelling, superior hydroxide conductivity (122 mS cm -1 at 80 °C with an IEC of 1.99 mmol g -1 ), and enhanced alkaline stability compared to the reference sample without PEG grafts (PTP). More importantly, the performance of AEM fuel cell (AEMFC) with the membrane containing partial PEG side chains surpasses that with PTP membrane, demonstrating a highest peak power density of 1110 mW cm -2 at 80 °C under optimized conditions. This work provides a novel approach to the fabrication of high-performance AEM materials with balanced properties for alkaline fuel cell application., (© 2024 Wiley‐VCH GmbH.)

Organic anionic dyes are major water pollutants due to their low degradability caused by complex aromatic structures. Not only do they exert toxic, mutagenic, teratogenic, tumorigenic, and genotoxic effects, but they also decrease fertility and cause irritation to the skin and respiratory system in humans. This long-term toxicity has detrimental effects on aquatic organisms and their surroundings, resulting in an imbalanced ecosystem. In this study, a Cs@Fe 3 O 4 magnetic biosorbent was synthesised to uptake three anionic dyes and characterised for FTIR, BET/BJH, XRD, TGA, VSM, and FESEM analyses. The biosorbent average surface area was confirmed to be 52.6524 m 2 /g, with average pore sizes of 7.3606 nm and 6.9823 nm for adsorption-desorption processes, respectively. Batch adsorption studies pH values, contact times, temperature, initial dye concentrations, and adsorbent dosages were examined. Several isotherm and kinetic models were studied to determine the adsorption mechanism. The adsorption data of these dyes at equilibrium was observed to match Langmuir's isotherm and pseudo-second-order kinetic models. The thermodynamic study revealed that the adsorption process for these dyes was an exothermic reaction. Maximum adsorption capacities for congo red, methyl orange, and metanil yellow were 117.77 mg/g, 137.77 mg/g, and 155.57 mg/g, respectively. The reusability of recovered Cs@Fe 3 O 4 after dye adsorption was evaluated up to five continuous adsorption-desorption cycles for its possible industrial applications., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: NINIE SUHANA BT ABDUL MANAN reports financial support was provided by Malaysia Ministry of Higher Education. 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.)

Mineralized bio-tissues achieve exceptional mechanical properties through the assembly of rigid inorganic minerals and soft organic matrices, providing abundant inspiration for synthetic materials. Hydrogels, serving as an ideal candidate to mimic the organic matrix in bio-tissues, can be strengthened by the direct introduction of minerals. However, this enhancement often comes at the expense of toughness due to interfacial mismatch. This study reveals that extreme toughening of hydrogels can be realized through simultaneous in situ mineralization and salting-out, without the need for special chemical modification or additional reinforcements. The key to this strategy lies in harnessing the kosmotropic and precipitation behavior of specific anions as they penetrate a hydrogel system containing both anion-sensitive polymers and multivalent cations. The resulting mineralized hydrogels demonstrate significant improvements in fracture stress, fracture energy, and fatigue threshold due to a multiscale energy dissipation mechanism, with optimal values reaching 12 MPa, 49 kJ m -2 , and 2.98 kJ m -2 . This simple strategy also proves to be generalizable to other anions, resulting in tough hydrogels with osteoconductivity for promoting in vitro mineralization of human adipose-derived mesenchymal stem cells. This work introduces a universal route to toughen hydrogels without compromising other parameters, holding promise for biological applications demanding integrated mechanical properties., (© 2024 Wiley‐VCH GmbH.)

Five types of sulfobutylether-β-cyclodextrin (SBE-β-CD) and carboxymethyl-β-cyclodextrin (CM-β-CD) with different degrees of substitution were synthesized, and six and five racemates were respectively chosen to study the influence of the degree of substitution on the enantioseparation factor. The synthesized SBE-β-CD and CM-β-CD were characterized using 1 H NMR spectroscopy and mass spectrometry. The results indicated that the influence of the degree of substitution on enantioseparation for distinct racemates exhibited significant variability. Increasing the degree of substitution of CM-β-CD led to an increasing enantioseparation factor, while SBE-β-CD with a specific degree of substitution provided the optimum enantioseparation factor for some racemates. The optimum enantioseparation factors of N-methyl duloxetine and duloxetine were obtained when a relatively low degree of substitution (DS = 3.5) was selected. And the optimum enantioseparation factor was obtained with a relatively high degree of substitution (DS = 7.5). SBE-β-CD with a low substitution degree of 3.5 was chosen to optimize the countercurrent chromatographic enantioseparation of N-methyl-duloxetine, which resulted in a significant improvement in peak resolution from 0.51 to 0.83. Molecular docking was used to construct three SBE-β-CDs with different degrees and distributions of substitution, and a good agreement was found between the docking results and the experimental results., 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.)

The effect of anions on the positive electrospray ionization (ESI) of proteins in different strong acids with varying pH values from 3 to 1 is studied using high-pressure ESI. Reducing the pH from ∼2 to 1 caused a drastic shift in charge state from a high-charge-state distribution (HCSD) to a narrow low-charge-state distribution (LCSD). The shift in charge state was consistent with the circular dichroism result that showed a conformational change due to the "acid-induced folding" of proteins from an unfolding state to a compact molten globule state. Acids of different anions produced noticeable differences in the average charge for HCSD and LCSD. For HCSD, the average charge was lower than the value typically observed using formic and acetic acids. As for LCSD, the average charge was lower than the "native" charge. The high abundance of acid anion that induces the protein compaction was believed to play a role in charge reduction. The effectiveness of anions to " refold " a highly unfolded protein to a compact state and the propensity to reduce the charge of HCSD for proteins appeared to follow the selectivity series of anions towards the stationary phase in ion chromatography. However, the propensity of anions to reduce the charge for LCSD follows quite an opposite trend. The presence of ammonium salt in the acidic solution was found to increase the charge of LCSD. The simple mass spectrum with a narrow distribution of charge state obtained with perchloric acid at pH 1 was demonstrated to facilitate the counting of basic sites.

Anionic polyelectrolytes, such as DNA, are attracted to anionic surfaces in the presence of multivalent cations. A major barrier toward molecular-level understanding of these attractive interactions is the paucity of measurements of the binding strength. Here, atomic force microscopy-based single molecule force spectroscopy was used to quantify the binding free energy of double-stranded DNA to an anionic surface, with complementary density functional theory calculations of the binding energies of metal ion-ligand complexes. The results support both electrostatic attraction and ion-specific binding. Our study suggests that the correlated interactions between counterions are responsible for attraction between DNA and an anionic surface, but the strength of this attraction is modulated by the identity of the metal ion. We propose a mechanism in which the strength of metal-ligand binding, as well as the preference for particular binding sites, influence both the concentration dependence and the strength of the DNA-surface interactions.

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.

Channelrhodopsins are light-gated ion channels with a retinal chromophore found in microbes and are widely used in optogenetics, a field of neuroscience that utilizes light to regulate neuronal activity. Gt ACR1, an anion conducting channelrhodopsin derived from Guillardia theta , has attracted attention for its application as a neuronal silencer in optogenetics because of its high conductivity and selectivity. However, atomistic mechanisms of channel photoactivation and ion conduction have not yet been elucidated. In the present study, we investigated the molecular characteristics of Gt ACR1 and its photoactivation processes by molecular simulations. The QM/MM RWFE-SCF method which combines highly accurate quantum chemistry calculations with long-time molecular dynamics (MD) simulations were used to model protein structures of the wild-type and mutants with different protonation states of key groups and to calculate absorption energies for verification of the models. The QM/MM modeling together with MD simulations of free-energy calculations favors protonation of a key counterion carboxyl group of Asp234 with a strong binding of a chloride ion in the extracellular pocket in the dark state. A channel open state was also successfully modeled by the QM/MM RWFE-SCF free-energy optimizations, providing atomistic insights into the channel activation mechanism.

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 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.

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.

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.)

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.

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.)