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A contribution to the use of deep eutectic solvents (DES) and microwave-assisted extraction (MAE) was made for bioactive compounds recovery, especially those with lipophilic character, from tomato and carrot samples rich in carotenoids. For the first time, a novel deep eutectic solvent was synthesized, comprising tributyl phosphate (TBP) as a hydrogen bond acceptor and acetic acid (AcOH) as a hydrogen bond donor. The total antioxidant capacity (TAC) of tomato and carrot extracts obtained by MAE, in which optimization of operational parameters and modeling were made with the use of Box-Behnken design of the response surface methodology (RSM), was evaluated using the Cupric Reducing Antioxidant Capacity (CUPRAC) method. For the highest TAC, operational parameters that best suit the MAE procedure were set at 80 °C, 35 min, and 25 mL/2.0 g. The TAC values of extracts obtained by MAE using TBP:AcOH, 1:2 (mol/mol) were examined against those of extracts acquired by classical solvent extraction using a mixture of hexane, ethanol and acetone (H:E:A, 2:1:1 (v/v/v)) mixture. TAC of extracts in DES varied between 5.10 and 0.71 lycopene equivalents (mmol LYC kg -1 ). The highest extraction yield comparable to conventional organic solvents was obtained with TBP:AcOH (1:2). It was observed that, in addition to lipophilic antioxidants, some hydrophilic antioxidant compounds were partially extracted with the proposed DES. Moreover, the extracted antioxidant compounds were identified and quantified by HPLC analysis. The proposed DES and MAE process will find potential application for hydrophobic antioxidant extraction from tomatoes and carrots on an industrial scale after further studies., 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.)

Gambierones are sulfated polyethers produced by benthic dinoflagellates in the genera Gambierdiscus, Coolia and Fukuyoa. While relative toxicity data for gambierones suggests they are low compared with ciguatoxin analogues, gambierones have been suggested for use as marker compounds for environmental monitoring programs for the presence of Gambierdiscus in marine waters. The published structure of gambierone and analogues of it, including 44-methylgambierone (44-MeGAM), have been reported to possess 1,2- and 4,5-cis diols, while only the 1,2- diol unit has been shown to undergo periodate oxidation. An in-depth analysis of previously reported NMR data for 44-MeGAM in CD 3 OD showed that the C-4 stereochemistry of 44-MeGAM and other gamberiones was mis-assigned, that the 4-CH 2 -CHOH-CH 2 OH and OH groups are equatorially and axially oriented, respectively, rather than vice versa as previously reported. This re-examination of existing 44-MeGAM NMR data also showed that its C-12 and C-13 assignments (and those for other gambierones) should be reversed. In an effort to better understand the C-4 stereochemical and periodate reaction characteristics of gambierones (C-4 is an epimerizable hemiacetal carbon), additional NMR data was acquired in D 6 -DMSO. Unexpectedly, progressive conversion of 44-MeGAM to a long-term stable ring-A furanoid analogue was observed. A subsequent series of microscale stability trials identified several solvents that affected the solution-stability of 44-MeGAM, and these findings should be taken into consideration during isolation, handling, storage and bioassay evaluations of gambierones in future studies., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: J. Sam Murray reports financial support was provided by Ministry of Business Innovation and Employment. 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., (Crown Copyright © 2024. Published by Elsevier Ltd. All rights reserved.)

This study investigated the dissolution behavior of l-isoleucine and l-serine in an aqueous salt solution (ammonium chloride), examining how variations in temperature and electrolyte concentration affect their solubility. We conducted careful experiments and used mathematical calculations to explore interactions at a molecular level. We observed that the structure of these amino acids and salt concentration in the aqueous medium influence their interactions, which affects dissolution. In the presence of electrolytes, l-isoleucine demonstrated a salting-out effect whereas l-serine showed a salting-in effect. This work examines the solute-solvent interactions of these solutes in aqueous ammonium chloride solutions. l-isoleucine exhibits a nonspontaneous reaction with increasing salt concentrations whereas l-serine shows spontaneous behavior. Gibbs free energy analysis revealed greater stability of l-serine. The pH and conductance measurements showed how these factors influence solution properties. This insight helps us comprehend the nature and behavior of these molecules in different situations, which could be helpful in drug formulation or protein purification in the future., Competing Interests: Declaration of competing interest The authors did not disclose any potential conflict of interest. Data Availability All data generated or analysed during this study is fully presented in this article., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Cytochrome b 562 is a small redox-active heme protein that has served as an important model system for understanding biological electron transfer processes. Here, we present a comprehensive theoretical study of electron transport mechanisms in protein-metal junctions incorporating cytochrome b 562 using a multi-scale computational approach. Employing molecular dynamics (MD) simulations, we generated junction geometries for both vacuum-dried and solvated conditions, with the protein covalently bound to gold contacts in various configurations. Coherent tunneling, described by the Landauer-Buttiker formalism within the density functional theory (DFT) framework, is compared to the incoherent hopping charge transport mechanism captured by the semi-classical Marcus theory. The tunneling was identified as the dominant mechanism explaining the experimental data measured on the cytochrome b 562 junctions, exhibiting exponential yet very shallow distance dependence. While the structural orientations and protein contacts with the electrodes influence the junction conductance significantly, the solvation effects are relatively small, affecting the electronic properties mostly via the adsorption arrangement. On the other hand, the considerable temperature dependence of the conductance was found strong only for hopping, while the tunneling current magnitudes remain practically unaffected and are a good indicator of the coherent mechanism in this case.

Anaerobic bioremediation is rarely an effective strategy to treat chlorinated ethenes such as trichloroethene (TCE) in acidic aquifers because partial dechlorination typically results in accumulation of daughter products. Methanotrophs have the capability of oxidizing TCE and other chlorinated volatile organic compounds (CVOCs) to non-toxic products, but their occurrence, diversity, and biodegradation capabilities in acidic environments are largely unknown. This study investigated the impacts of different methane (CH 4 ) concentrations and the presence of CVOCs on the community of acidophilic methanotrophs in microcosms prepared from acidic aquifer samples collected upgradient and downgradient of a mulch barrier installed to promote in-situ anaerobic CVOC biodegradation in Maryland, USA. The ability of indigenous methanotrophs to biodegrade CVOCs was also evaluated. Results of stable isotope probing (SIP) and Next Generation Sequencing (NGS) showed that the microbial communities in the microcosms varied by location and were affected by both CH 4 concentration and the presence of different CVOCs, many of which were biodegraded by the indigenous methanotrophs. Data indicate the likelihood of aerobic cometabolic degradation of CVOCs downgradient of the mulch barrier designed for anaerobic treatment. The study extends the overall knowledge of acidophilic methanotrophs in groundwater and shows that these bacteria have significant potential for degrading CVOCs even at low CH 4 concentrations., Competing Interests: Declarations. Conflict of interest: The authors declare no competing interests., (© 2024. The Author(s), under exclusive licence to Springer Nature B.V.)

Levulinic acid, which can be obtained from biomass, has sparked great interest as a biologically-based chemical building block with wide versatility and potential. Its esterification with alcohols of different chain lengths is a promising valorization process for obtaining esters with various applications in the areas of biofuels/biolubricants, food and cosmetics, among others. In this work, the enzymatic esterification of levulinic acid and 1-octanol using a biocatalyst derived from Araujia sericifera latex was studied in systems with and without solvent. The influence of the molar ratio between alcohol and acid (ranging from 2:1-1:9), the biocatalyst loading (between 7.5 % and 17.5 % relative to the acid), the volume of n-heptane used as reaction solvent (from 0 to 4 ml), and the reaction time (6 hours) were investigated. The activity and stability of the biocatalyst in successive uses were also analyzed. A conversion of 49 % was achieved when the reaction was carried out in a solvent-free system, using an alcohol/acid molar ratio of 1:7 and after 5 h of reaction. On the other hand, the conversion was 65.1 % when the reaction was conducted in a system containing 1 ml of n-heptane as solvent, an alcohol/acid molar ratio of 1:8, and 5 h of reaction. In both cases, a temperature as low as 30 °C and an agitation speed of 300 RPM were used., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Daniel Sanchez reports financial support was provided by National Agency for the Promotion of Research Technological Development and Innovation. Gabriela Tonetto reports financial support was provided by National Scientific and Consejo Nacional de Investigaciones Científicas y Técnicas. Gabriela Tonetto reports financial support was provided by National University of the South Department of Chemical Engineering. 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.)

Context: This study investigates the antioxidant potential of alkyl gallates (C1-C10), focusing on the impact of alkyl chain length and solvent polarity on their antioxidant properties. Known for their biomedical relevance in mitigating oxidative stress, alkyl gallates' structure-activity relationships, particularly regarding chain length and environmental factors, still need to be explored. Key thermochemical parameters, including bond dissociation enthalpy (BDE), ionization potential (IP), proton affinity (PA), and electron transfer enthalpy (ETE), reveal that shorter alkyl chains (C1-C4) exhibit superior antioxidant activity. In contrast, longer chains (C5-C10) show reduced effectiveness due to steric hindrance and lower solubility in polar solvents. Molecular docking studies also demonstrated favorable binding interactions with vital biological targets, further reinforcing their antioxidant potential., Methods: Quantum chemical calculations were performed using Gaussian 16 with the B3LYP/6-311G(dp) basis set for geometry optimizations. Solvent effects were modeled using the integral equation formalism-polarized continuum model (IEF-PCM). Molecular docking studies were conducted using AutoDockTools 4.2, targeting Tyrosine Kinase Hck, Heme Oxygenase, and Human Serum Albumin to evaluate fundamental binding interactions. These computational methods provided insights into alkyl gallates' chemical reactivity and antioxidant efficiency, allowing for the rational design of more potent antioxidant compounds., Competing Interests: Declarations Competing interests The authors declare no competing interests., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Therapeutic deep eutectic solvents (THEDES) are a type of deep eutectics that can be used as active pharmaceutical ingredients (APIs) by enhancing the drug bioavailability, by increasing the solubility of APIs in aqueous solutions or by increasing their permeability through biological barriers. In this study, we demonstrate the utility of designer THEDES, based on Quillaja Saponin (SAP), a triterpene natural product to unravel the antimicrobial potential of such THEDES. THEDES were prepared by gently mixing and heating five different α- hydroxy acids- malic, citric, tartaric, glycolic, lactic acids and SAP with water as a third component in the THEDES. The antimicrobial assays were performed with the as-prepared SAP-THEDES and among the panel of bacterial strains, saponin-malic acid THEDES [SMA-THEDES] displayed potent activity in disassembling PA biofilms, demonstrating that the SMA-THEDES can serve as therapeutic antibacterial biomaterials. To further optimize, a Box-Behnken- response surface methodology (RSM) experimental design was done and at the optimum conditions of SAP (1.014 m.mol), Malic acid (1.003 m.mol), Water (0.117 m.mol), SMA-THEDES exhibited maximum MIC of P. aeruginosa with the minimum absorbance at 590 nm of 0.105. The effectiveness of SMA-THEDES as antibiofilm agents on P. aeruginosa with the mechanism studies have been explored. The colony count from the in vivo infection zebrafish model in the treatment group showed a decline of > 2 fold for SMA-THEDES. Toxicity studies did not reveal any abnormality in liver and brain enzyme levels. Liver morphology images show no severe cytological alterations when treated with SMA-THEDES and were almost similar to the normal liver., Competing Interests: Declarations Competing interests The authors declare no competing interests. Conflict of interest The authors declare no competing interests., (© 2024. The Author(s).)

Background: Exosomes, a subset of extracellular vesicles (EVs), are a type of membrane-secreted vesicle essential for intercellular communication. There is a great deal of interest in developing methods to isolate and quantify exosomes to study their role in intercellular processes and as potential therapeutic delivery systems. Polyester, capillary-channeled polymer fiber columns and spin-down tips are highly efficient, low-cost means of exosome isolation. As the methodology evolves, there remain questions as to the optimum elution solvent for specific end-uses of the recovered vesicles; fundamental biochemistry, clinical diagnostics, or therapeutic vectors., Results: While both acetonitrile and glycerol have been proven highly successful in terms of EV recoveries in the hydrophobic interaction chromatography workflow, many biological studies entail the use of the non-ionic detergent, Tween-20, as a working solvent. Here we evaluate the use of Tween-20 as the elution solvent for the recovery of exosomes. A novel 10-min, two-step gradient elution method, employing 0.1 % v/v Tween-20, efficiently isolated EVs at a concentration of ∼10 11  EV mL -1 from a 100 μL urine injection. Integration of absorbance and multi-angle light scattering detectors in standard HPLC instrumentation enables a comprehensive single-injection determination of eluted exosome concentration and sizes. Transmission electron microscopy verifies the retention of the vesicular structure of the exosomes. The micro-bicinchoninic acid protein quantification assay confirmed high-purity isolations of exosomes (∼99 % removal of background proteins) SIGNIFICANCE: The effective use of Tween-20 as an elution solvent for exosome isolation/purification using capillary-channeled polymer fiber columns adds greater versatility to the portfolio of the approach. The proposed method holds promise for a wide range of fundamental biochemistry, clinical diagnostics, and therapeutic applications, marking a significant advancement in EV-based methodologies., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: R. Kenneth Marcus reports financial support was provided by National Science Foundation. R. Kenneth Marcus reports financial support was provided by National Institutes of Health. 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.)

The removal of residual solvents from biodegradable poly(D,L-lactide-co-glycolide) (PLGA) microparticles by fluidized bed drying was investigated. Microparticles were prepared by the O/W solvent extraction/evaporation method and the influence of various process and formulation parameters on the secondary drying was studied. PLGA microparticles and films were characterized for residual organic solvent and water content, recrystallisation, surface morphology, drug loading and in-vitro release of the drugs dexamethasone and risperidone. While alcohol-free fluidized bed drying decreased the residual dichloromethane content only from about 7 % (w/w) to 6.4 % (w/w) (18 °C) or 3.2 % (w/w) (35 °C) within 24 h, 140 mg/L methanol vapor in purge gas facilitated almost complete removal of dichloromethane or ethyl acetate from microparticles (0-0.11 % (w/w) after 6 h). By controlling the alcohol concentration and temperature of the purge gas, the alcohol absorption and complete removal was controlled. Risperidone increased the methanol absorption enhancing the plasticization. A high initial residual water content was identified to promote aggregation and was eliminated by starting fluidized bed drying without alcohol. Alcohol vapor-assisted fluidized bed drying accelerated microparticle manufacturing without affecting the redispersibility, the drug loading and the in-vitro release of risperidone and dexamethasone., 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.)

Ethnopharmacological Relevance: In Mongolian medicine, Loulu flower (LLF), the dried inflorescence of Rhaponticum uniflorum (L.) DC. from the Compositae family, has been used to clear heat and relieve toxicity for millennia, particularly in the treatment of pneumonia., Aim of This Study: To reveal the effects of LLF on mice with lipopolysaccharide (LPS)-stimulated acute lung injury (ALI) and elucidate the underlying mechanisms., Materials and Methods: ALI was established in BALB/c mice via nasal drops administration of LPS (5 mg/kg). The mice were then orally administrated with various doses of LLF extracts and the positive drug dexamethasone (DEX, 5 mg/kg), once daily for seven consecutive days. Last day, after being stimulated with LPS for 6h, the mice were closed dislocation of cervical vertebra, the serum, bronchus alveolar lavage fluid (BALF) and lung tissue were put into the EP tube and stored at -80 °C for further analysis. The changes of histopathology were tested by hematoxylin and eosin stain (H&E), the levels of, IL-1β, IL-18, TNF-α and IL-4 in BALF and serum were measured by ELISA. The pathways related to the treatment of ALI were predicted by network pharmacology. The expression levels of TLR4/NF-κB and NLRP3 signaling pathway-associated proteins, COX-2 and ERK were tested by western blotting. The levels of P65 and NLRP3 in lung tissues were determined by immunofluorescence analysis., Results: LLF total extract and the extract parts could alleviate the inflammatory cell infiltration, thicken the alveolar walls in lung tissues, reduce the levels of IL-18, IL-1β in BALF, the TNF-α in both BALF and serum, meantime enhance the level of IL-4 in BALF and serum in mice with LPS-induced ALI. Our network pharmacology and comprehensive gene ontology analyses revealed the active constituents of LLF and the pathways, including TLR4/NF-κB, NLRP3 and MAPK signaling pathways, which play significant roles in ALI. Furthermore, both the total extract and its extraction portions suppressed the expressions of proteins related with the COX-2, p-ERK and TLR4/NF-κB signaling pathway (TLR4, p-IκB, p-p65), as well as the NLRP3 signaling pathway (NLRP3, cleaved caspase-1, caspase-1, IL-1β)., Conclusion: LLF could improve the pathological changes and reducing inflammatory reactions in mice induced by LPS. The mechanism may be related to the modulation of the TLR4/NLRP3 signaling pathways., 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.)

This research introduces a novel approach for detecting sartan antihypertensive drug adulteration in herbal oral liquids using cotton fiber-supported liquid extraction (CF-SLE) combined with high-performance liquid chromatography-fluorescence detection (HPLC-FLD). Optimal extraction parameters were determined through systematic method development, establishing a sample solution with a pH of 3.0, using 200 mg of cotton fiber, ethyl acetate as the extraction solvent, and a solvent volume of 4 mL. These conditions demonstrated robust extraction efficiency and were further validated for precision and accuracy, with intra- and inter-day relative standard deviations consistently below 7.5 % and relative recoveries ranging from 88.5 % to 106.1 %. The method exhibited excellent linearity for sartans, with R² values greater than 0.993 across a concentration range of 10-2000 ng/mL. Detection limits were effectively established in the range of 2.6-3.1 ng/mL, indicating that the method's sensitivity is adequate for the intended screening purposes. This validated method was then applied to real sample analysis, confirming its potential for routine use in detecting illegal additives within complex herbal matrices, thereby ensuring consumer safety and supporting regulatory compliance., 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.)

Expanding the family of fluorescent metal clusters beyond gold, silver, and copper has always been an issue for researchers to solve. In this study, a novel type of cysteine-capped nickel nanoclusters (Cys-Ni NCs) with bright turquoise emission was developed. The as-synthesized Ni NCs showed aggregation-induced emission enhancement (AIEE) properties across Cd 2+ and various polar organic solvents. Concurrently, solvents with different viscosities were used to explore the principle of solvent-induced AIEE of Cys-Ni NCs, revealing a positive correlation between fluorescence intensity and solution viscosity. In addition, the concentration of Cd 2+ that induced the AIEE effect was reduced by nearly two orders of magnitude in highly viscous solvents, indicating the possibility of Cys-Ni NCs as a promising nanomaterial platform for Cd 2+ sensing analysis. Moreover, we propose a novel fluorescent sensing method for rapid detection of Cu 2+ based on the carboxyl group of Cys-Ni NCs coupling with Cu 2+ . Further, validation of Cu 2+ detecting methodologies in environmental water samples with the accuracy up to 93.94% underscores their potential as robust and efficient sensing platforms. This study expands the repertoire of fluorescent metal nanoclusters for highly sensitive and selective sensing of hazardous ions and paves the way for further exploration and wide applications in Cu 2+ detection in biological and medicine fields., 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.)

Dunaliella salina is a promising source of β-carotene, widely employed in the food industry. This study aimed to evaluate the sequential application of the Ionic Liquid (IL) cholinium oleate as an extraction solvent for D. salina β-carotene recovery and, sequentially, as emulsifier for emulsion-based products obtained therefrom. The IL was evaluated regarding its ability to permeabilize the cells and recover β-carotene at different temperatures (25-65 °C) and IL concentrations (0-46%). The use of the IL as solvent greatly improved β-carotene recovery (>84%). The IL already present in the obtained extracts loaded with recovered β-carotene was sequentially used as emulsifier in the production of nanoemulsions (NE). NE presented a β-carotene entrapment efficiency of 100% and were kinetically stable for 30 days and presented droplet size, size distribution, and ζ-potential of 220 nm, 0.21, and -67 mV, respectively. These results indicate that using IL sequential as solvent and emulsifier has potential applications in the food 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 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The increasing prevalence of multidrug-resistant pathogens is a critical public health issue, necessitating the development of alternative antibacterial agents. Examples of these pathogens are methicillin-resistant Staphylococcus aureus (MRSA) and the emergence of "pan-resistant" Gram-negative strains, such as Pseudomonas aeruginosa and Acinetobacter baumannii, which occurred more recently. This review examines various emerging materials with significant antibacterial activities. Among these are nanomaterials such as quantum dots, carbon quantum dots, metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and layered double hydroxides, all of which demonstrate excellent antibacterial properties. Interestingly, including antibacterial agents within the structure of these materials can help avoid bacterial resistance and improve the long-term efficacy of the materials. Additionally, the antibacterial potential of liquid solvents, including ionic liquids and both deep eutectic solvents and natural deep eutectic solvents, is explored. The review discusses the synthesis methods, advantages, and antibacterial efficacy of these new materials. By providing a comprehensive overview of these innovative materials, this review aims to contribute to the ongoing search for effective solutions to combat antibiotic resistance. Key studies demonstrating antibacterial effects against pathogens like Escherichia coli, Staphylococcus aureus, and multidrug-resistant strains are summarized. MOFs have exhibited antibacterial properties through controlled ion release and surface interactions. COFs have enhanced the efficacy of encapsulated antibiotics and displayed intrinsic antibacterial activity. Other nanomaterials, such as quantum dots, have generated reactive oxygen species, leading to microbial inactivation. This review aims to provide insights into these new classes of antibacterial materials and highlight them for addressing the global crisis of antibiotic resistance. KEY POINTS: • Nanomaterials show strong antibacterial effects against drug-resistant bacteria • Emerging solvents like ionic liquids offer novel solutions for bacterial resistance • MOFs and COFs enhance antibiotic efficacy, showing promise in combating resistance., Competing Interests: Declarations Ethical approval This article does not contain any studies with human participants or animals performed by any of the authors. Conflict of interest The authors declare no competing interests., (© 2024. The Author(s).)

Considering the nonideal antiresistance efficacy of our previously reported non-nucleoside reverse transcriptase inhibitor 7 , a series of novel piperidine-diarylpyrimidine derivatives were designed through expanding solvent/protein region occupation. The representative compound 15f proved to be exceptionally potent against Y188L (EC 50 = 23 nM), F227L + V106A (EC 50 = 15 nM) and RES056 (EC 50 = 45 nM), significantly better than 7 . This analog exerted strong inhibition against wild-type HIV-1 (EC 50 = 3 nM) and single mutant strains (L100I, K103N, Y181C, E138 K). Notably, its cytotoxicity and selectivity (CC 50 = 18.23 μM, SI = 6537) were 4-fold better than etravirine and rilpivirine. Additionally, it exhibited minimal suppression of CYP isoenzymes and hERG, indicating low potential for drug-drug interactions and cardiotoxicity. No significant acute toxicity and tissue damage at a dose of 2 g/kg were revealed. These findings lay the groundwork for the advancement of 15f as a highly potent, safe, and broad-spectrum NNRTI for HIV therapy.

The influence of polar, water-miscible organic solvents (POS) on protein structure, stability, and functional activity is a subject of significant interest and complexity. This study examines the effects of acetonitrile (ACN), a semipolar, aprotic solvent, on the solvation properties of blocked Ace-Gly-X-Gly-Nme tripeptides (where Ace and Nme stands for acetyl and N-methyl amide groups respectively and X is any amino acid) through extensive molecular dynamics simulations. Individual simulations were conducted for each peptide, encompassing five different ACN concentrations within the range of χ ACN  = 0.1-0.9. The preferential solvation parameter (Γ) calculated using the Kirkwood-Buff integral method was used for the assessment of peptide interactions with water/ACN. Additionally, weighted Voronoi tessellation was applied to obtain a three-way data set containing four time-averaged contact surface area types between peptide atoms and water/ACN atoms. A mathematical technique known as N-way Partial Least Squares (NPLS) was utilized to anticipate the preferential interactions between peptides and water/ACN from the contact surface areas. Furthermore, the temperature dependency of peptide-solvent interactions was investigated using a subset of 10 amino acids representing a range of hydrophobicities. MD simulations were conducted at five temperatures, spanning from 283 to 343 K, with subsequent analysis of data focusing on both preferential solvation and peptide-solvent contact surface areas. The results demonstrate the efficacy of utilizing contact surface areas between the peptide and solvent constituents for successfully predicting preferential interactions in water/ACN mixtures across various ACN concentrations and temperatures., Competing Interests: Declarations Competing interests The authors declare no competing interests. Ethical approval Not applicable. Consent for publication The authors give their consent for this manuscript to be published., (© 2024. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Humans have utilized plants for various purposes, including sustenance and medical treatment for millennia. Researchers have extensively investigated medicinal plants' potential in drug development, spurred by their rich array of chemical compounds. Curcumin, a valuable bioactive compound, is extracted from Turmeric, known by the scientific name Curcuma Longa L. Notably, curcumin boasts potent antioxidant and anti-inflammatory properties, making it a promising candidate for treating cancer and other microbial diseases. Therefore, the simulation study of the extraction of this important medicinal compound by water, which is a green solvent, was carried out. This study employed molecular dynamics simulation for the first time to explore the extraction of Curcuma Longa L. extract using subcritical water. The simulations were carried out at constant pressure and different temperatures, using the Compass force field in the Lammps simulation package. The findings revealed an increase in the amount of Curcuma longa extract with rising temperature, indicating a weakening of hydrogen bonds in water molecules. Water lost its polar state with increasing temperature and became a suitable non-polar solvent for extracting non-polar compounds. The average absolute relative deviation (AARD) for calculated and simulated density data was 6.45%., Competing Interests: Competing interests The authors declare no competing interests., (© 2024. The Author(s).)

Essential oils (EOs) are volatile secondary metabolites of natural plants with multitudinous pharmacological activities. However, limited by their properties, such as low solubility, high volatility, photothermal instability, irritation, release, etc., EOs encounter significant challenges in pharmaceutical applications. Deep eutectic solvents (DESs) have been developed for the transdermal delivery of biomolecules and lipid-soluble drugs. Herein, a series of DES carriers were synthesized to improve the undesirable properties of EOs. We first optimized the DESs according to solubilization and aqueous dispersity using Chimonanthus nitens Oliv. EO (COEO) as a model EO. Then, the EO-DES formulations were diluted to prepare optimal aqueous EO-DES nanoformulations (AqEDs). Mechanically, hydrogen bonding allowed the DES to dissolve the complex components in EOs; meanwhile, the interaction forces, such as π - π stacking and hydrogen bonding, drove the EO-DES to assemble into nanostructures in aqueous conditions, forming AqEDs. Lastly, a case study demonstrated that clove EO-AqEDscould effectively promote methicillin-resistant Staphylococcus aureus -infected wound healing in vivo , along with biocompatibility. This AqED strategy provides a generalized platform for solubilizing EOs and improving their transdermal/topical delivery.

Cosolvent molecular dynamics (MDs) are an increasingly popular form of simulations where small molecule cosolvents are added to water-solvated protein systems. These simulations can perform diverse target characterization tasks, including cryptic and allosteric pocket identification and pharmacophore profiling and supplement suites of enhanced sampling methods to explore protein conformational landscapes. The behavior of these systems is tied to the cosolvents used, so the ability to define diverse and complex mixtures is critical in dictating the outcome of the simulations. However, existing methods for preparing cosolvent simulations only support a limited number of predefined cosolvents and concentrations. Here, we present CosolvKit, a tool for the preparation and analysis of systems composed of user-defined cosolvents and concentrations. This tool is modular, supporting the creation of files for multiple MD engines, as well as direct access to OpenMM simulations, and offering access to a variety of generalizable small-molecule force fields. To the best of our knowledge, CosolvKit represents the first generalized approach for the construction of these simulations.

Considerable progress has been made in enhancing resolution in reversed-phase liquid chromatography for the analysis of complex samples, particularly within the field of natural products, through the application of global retention models using multi-linear gradients. Global models effectively differentiate solute retention effects from those originating from the column and solvent, offering predictive capabilities comparable to conventional individual retention models, without the requirement for standards for all compounds. While conventional individual models result in higher accuracy, they frequently demand standards that are unavailable for natural product samples. Moreover, the creation of individual models can be time-consuming due to the need for repetitive work for additional compounds. Experimental validation of global models has demonstrated that the accuracy is enough for the prediction of complex chromatograms. Through a carefully designed experimental work, this study reports the correct determination of global parameters for column and solvent, with excellent consistency across various medicinal plant samples. The successful transfer of predictions and optimisation of resolution across diverse plant species (lemon balm, peppermint, and pennyroyal) is confirmed. This highlights the applicability of predictions using global models across botanical varieties., 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.)

Solvent system selection based on polarity is a common strategy in a countercurrent chromatography (CCC) analysis. However, the solvent selectivity of solvent system is often ignored, despite its significant impact on the separation efficiency of CCC. In this study, the role of solvent in the overall properties of solvent system and the selective classification of solvent system were discussed to improve the solvent system selection based on polarity. Firstly, the mathematical relationship between logarithm of the partition coefficient (log K) of the template molecule and solvent composition of n-hexane/ethyl acetate/alcohol solvents (methanol, ethanol, and isopropanol)/water (HEAwat) system was analyzed and the optimal solvent system (K = 1) of the template molecules was determined. Then, the actual methanol concentration at the column inlet when the analyte peak in a HPLC analysis (B%) and the clustering results of the average polarity (P') of the optimal CCC solvent system were analyzed. Finally, the classification of HEAWat system in terms of its overall solvent properties by deducing equations of selectivity parameters (χ e , χ d , and χ n ) to explain the P' values clustering results. The results showed that HEAWat system was suitable for the separation of analytes with 55 % < B% < 100 %. However, the n-hexane/ethyl acetate/isopropanol/water (HEIWat) system proved more suitable for the separation of large polar compounds to other HEAWat system when the P' value decreased due to the change of alcohol solvents. The selected solvent systems were classified into group III and IV by Snyder's method. The solvent systems in group III were suitable for the separation of analytes with 85 % < B% < 100 %, and the distribution behavior of analytes was mainly influenced by the ratio of each solvent. The solvent systems in group IV were suitable for the separation of analytes with 55 % < B% < 85 %, and the distribution behavior of analytes was mainly influenced by the type of alcohol solvents., 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.)

Clindamycin phosphate (CP) exhibits good enantioselectivity for many basic drugs, but its separation effect for most amino alcohol drugs is not satisfactory. In this work, a deep eutectic solvent (DES) chiral selector based on CP was prepared for the first time and utilized as a single chiral selector in nonaqueous capillary electrophoresis (NACE) to separate twelve amino alcohol drugs. Compared with unmodified CP, the separations of model drugs in the DES chiral selector system were significantly improved. Most amino alcohol drugs could be completely separated, and the peak shapes were good. In addition, we used infrared spectroscopy and nuclear magnetic resonance method to study the specific separation mechanism and explored the reasons why DES chiral selector has better enantioselectivity. This work is the first to directly modify antibiotic chiral selector into DES, indicating a direction for us to develop novel chiral recognition 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.)

In this study, a simple, sensitive, and rapid method called green hydrophobic deep eutectic solvent-based liquid-liquid microextraction was developed to extract Brilliant Blue FCF dye from beverages. This method utilizes hydrophobic DES obtained by forming tetrabutylammonium bromide and 1-octanol in a 1:5 ratio as green extraction solvent. The transition of Brilliant Blue FCF to the DES phase occurred on its own, without the need for any reagents such as added salt or tetrahydrofuran. Several crucial factors were tried to get the best extraction efficiency, including species, DES volume and molar ratio, solution pH, ultrasonication, and centrifugation time. Under optimum conditions, extraction recoveries were achieved in the range of 95.1-101.3 % with the method developed for Brilliant Blue FCF. The detection and determination limits were observed to be 4.1 μg l -1 and 12.1 μg l -1 , respectively. In addition, the relative standard deviation values for the method's accuracy were found to be 2.23 % and 3.48 % within and between days, respectively. It has been established that the developed method is highly environmentally friendly thanks to the application of the Analytical GREENness (AGREE) and Green Analytical Procedure Index (GAPI) tools. This study shows that DES applications can be carried out without the use of emulsifiers and dispersants by prioritizing the use of hydrophobic DES compounds as environmentally friendly and green extraction solvents in food samples., 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.)

Polymeric micelles have widely been used as drug delivery carriers, and recently, single-chain nanoparticles (SCNPs) emerged as potential, smaller-sized, alternatives. In this work, we are comparing both NPs side by side and evaluate their ability to be internalized by breast cancer cells (MCF-7) and macrophages (RAW 264.7). To be able to generate these NPs on demand, the polymers were assembled by flow, followed by the stabilization of the structures by photocross-linking using blue light. The central aim of this work is to evaluate how the type of solvent affects self-assembly and ultimately the structure of the final NP. Therefore, a library of copolymers with different sequences, including block copolymers (AB, ABA, BAB), and statistical copolymers (rAB and rAC) was synthesized using PET-RAFT with A denoting poly(ethylene glycol) methyl ether acrylate (PEGMEA), B as 2-hydroxyethyl acrylate (HEA), and C as 4-hydroxybutyl acrylate (HBA). The polymers were conjugated with a quinoline derivative to enable the formation of cross-linked structures by photocross-linking during flow assembly. Using water as the dispersant for photocross-linking led to the preassembly of these amphiphilic polymers into compact SCNPs and cross-linked micelles, resulting in a quick photoreaction. In contrast, acetonitrile led to fully dissolved polymers but a low rate of the photoreaction. These intramolecularly cross-linked polymers were then placed in water to result in more dynamic micelles and looser SCNPs. Small-angle X-ray scattering (SAXS), dynamic light scattering (DLS), and size exclusion chromatography (SEC) coupled with a viscosity detector show that cross-linking in acetonitrile results in better-defined NPs with a shell rich in PEGMEA. Cross-linking in acetonitrile led to NPs with significantly higher cellular uptake. Interestingly, passive transport was identified as the main pathway for the delivery of our NPs on MCF-7 cells, confirmed by the uptake of NPs on cells treated with inhibitors and by red blood cells. This work underscored the importance of the polymer precursor's structure and the choice of solvent during intramolecular cross-linking in determining the drug delivery efficiency and biological behavior of SCNPs.

Liposomal drug delivery is a promising approach for delivering therapeutics effectively. While most liposomes are designed to be nanometer-sized for efficient cellular uptake, micron-sized liposomes are gaining interest due to their larger drug-loading capacity. When combined with macroscale structures, such as implants and hydrogels, they offer prolonged therapeutic delivery. This study investigates how solvents affect the production of micron-sized liposomes, with or without cholesterol, using the reverse-phase evaporation (RPE) method. Although the RPE method is established for producing micron-sized liposomes, the influence of solvents on liposome size and uniformity is not well understood. The study explores whether controlling the size of inverse micelles, an intermediate product, through the use of different organic solvents affects the final liposome size. Three solvents─diethyl ether, methanol, and acetone─were tested for their effect on the formation of inverse micelles and liposomes and their sizes. Results showed that without cholesterol, diethyl ether produced uniform inverse micelles, leading to mostly nanosized liposomes. Methanol and acetone resulted in phase separation, preventing uniform liposome formation, although some micron-sized liposomes appeared. The acetone sample yielded mostly oil droplets. The results showed that forming inverse micelles lead to nanosized liposomes. With cholesterol, phase separation was dominant in methanol, but micron-sized liposomes still formed. Across all cases, cholesterol reduced the liposome size. The findings reveal that inverse micelles are not always reliable predictors of the final liposome size and that the RPE method is highly sensitive to solvent polarity and lipid-solvent interactions. Overall, the findings of this study provide valuable insights into how the choice of solvent and lipid composition can influence the production of liposomes via the RPE method. These insights are critical for optimizing liposome production and influencing future designs of liposomal drug delivery systems.

Accurate water content detection is crucial for optimizing chemical reactions, ensuring product quality in pharmaceutical manufacturing, and maintaining food safety. In this study, nitrogen and sulfur co-doped graphene quantum dots (R-GQDs) were synthesized via a one-step hydrothermal method using o-phenylenediamine as the carbon source. The synthesis conditions, including reaction time, temperature, o-phenylenediamine concentration, and H 2 SO 4 /water ratio, were optimized using the Box-Behnken response surface methodology. The R-GQDs exhibited excellent fluorescence stability and distinct solvent-dependent characteristics, alongside a broad linear detection range and high sensitivity, making them highly suitable for dual-mode water content detection (colorimetric and fluorescent). To enhance the accuracy of visual detection, R-GQDs were incorporated into portable test strips with smartphone-assisted analysis, compensating for the human eye's limitations in distinguishing subtle color changes. The sensor's practical utility was validated through spiked recovery experiments in food samples, and the R-GQDs demonstrated good biocompatibility for in vivo imaging in shrimp. These findings highlight a novel strategy for developing portable, real-time water content sensors with potential applications in both portable detection systems and biological imaging.

Cortisol and testosterone are important biomarkers for diagnosing complex disorders, including polycystic ovary syndrome and Cushing's syndrome, where symptomatology usually overlaps with other prevalent disorders. This work proposes, for the first time, an analytical method based on a switchable hydrophilicity solvent as an extraction phase for the determination of cortisol and testosterone in oral fluid (OF) by high-performance liquid chromatography with diode-array detection. The optimized extraction conditions consisted of 1000 µL of OF, 100 µL of decanoic acid solution (65 mg/mL), 170 µL of Na 2 CO 3 , 900 µL of H 2 SO 4 and 150 µL of acetonitrile for dilution. The method was validated, and coefficients of determination higher than 0.9926, the limit of detection of 4.55 ng/mL and the limit of quantification of 15.00 ng/mL were obtained. Intra-day precision varied from 5.6% to 11.9%, inter-day precision ranged from 6.1% to 13.5%, and relative recoveries ranged from 98.9% to 104.6% for cortisol, and 89.1% to 103.9% for testosterone. This methodology was successfully applied to five OF samples from volunteers. Moreover, the greenness of this methodology was evaluated based on the sample preparation metric of sustainability achieving a global score of 7.37 which can be considered sustainable., (© 2024 Wiley‐VCH GmbH.)

Conductive pressure sensitive adhesives (PSA) used for wearable and smart electronic sensors have attracted a significant amount of attention recently. However, achieving multifunctional conductive PSA with the feature of temperature tolerance and sustainability via a convenient and environment-friendly approach still remains challenge. Herein, a novel cellulose-rosin based poly(esterimide) (PEI) was first prepared by esterification and imidization. Then, the cellulose-rosin based PEI was integrated with polymerizable deep eutectic solvents (PDES, 2-hydroxyethyl acrylate and triethanolamine as hydrogen bond donor, choline chloride as hydrogen bond receptor) and performed UV-induced polymerization for formation of the conductive PSA with dual network (DN). The DN structure and the existence of extensive hydrogen bonds endowed these cellulose-rosin based conductive PSA with excellent adhesion property (shear resistance more than 70 h, tack of 14.6 N and 180° peel strength of 148.1 N/m, are higher than that of some typical commercial PSA), exceptional UV-blocking, solvent-resistance (usable in low polar solvent) and temperature tolerance (perform well between -25 °C to 140 °C). Furthermore, these conductive PSA could be used as wearable sensor to monitor subtle movements and achieve real-time monitoring of interface adhesion states even under extreme environmental conditions. This work provides a green strategy for the next-generation of multifunctional PSA., 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 absence of solvent molecules in high-resolution protein crystal structure models deposited in the Protein Data Bank (PDB) contradicts the fact that, for proteins crystallized from aqueous media, water molecules are always expected to bind to the protein surface, as well as to some sites in the protein interior. An analysis of the contents of the PDB indicated that the expected ratio of the number of water molecules to the number of amino-acid residues exceeds 1.5 in atomic resolution structures, decreasing to 0.25 at around 2.5 Å resolution. Nevertheless, almost 800 protein crystal structures determined at a resolution of 2.5 Å or higher are found in the current release of the PDB without any water molecules, whereas some other depositions have unusually low or high occupancies of modeled solvent. Detailed analysis of these depositions revealed that the lack of solvent molecules might be an indication of problems with either the diffraction data, the refinement protocol, the deposition process or a combination of these factors. It is postulated that problems with solvent structure should be flagged by the PDB and addressed by the depositors., (open access.)

The environmental pollution caused by plastics and their chemical additives has drawn global attention. UV stabilizers are among the major plastic additives that were used to protect against discoloration and degradation under sunlight. They are recognized as harmful due to its persistence, bioaccumulation, adverse effects, and potential for long-range environmental transport via plastics. However, non-harmonized methodology to analysis UV stabilizers in plastics has brought remarkable challenge to compile data across studies and conduct further risk assessment. Especially, the extraction solvent was diverse, whereas their extract efficiency was unknown. To address this knowledge gap, this study assessed the extraction efficiency of three commonly used organic solvents (dichloromethane (DCM), methanol (MeOH) and toluene (PhMe)) for UV stabilizers in different type of plastics, including foil-based polymer (Polyethylene, Polypropylene, Polystyrene, and Polyethylene terephthalate), bio-based plastics (Polylactic acid) and tire rubber. A total of 8 UV stabilizers were detected with a concentration range between 0.01 and 257.94 μg/g. OC had the highest detection rate (100%) and concentration (0.21-257.94 μg/g). The extraction performance of the three extractants was further evaluated, and it was found that not only the extraction performance but also the stability, DCM performed significantly better than MeOH and PhMe., 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.)

This study presents a novel synthesis method of N,N,N-trimethyl chitosan (TMC) by using a non-nucleophilic base and optimizing the solvent system for enhanced scalability, while addressing critical factors such as viscosity management and stirring efficiency. The study objectives also included achieving high N,N,N-trimethylation without O-methylation while minimizing reagent use. Eight bases, three solvent systems, and varying levels of dilution were explored to mitigate viscosity challenges and gas evolution. 1 H NMR spectroscopy was used to characterize the TMC products. The integral values of the peaks at 3.3, 3.0, and 2.8 ppm, corresponding to trimethyl, dimethyl, and monomethyl groups, were used to quantify the methylation degrees. The most promising initial results were obtained with N,N-diisopropylethylamine (DIPEA) base, and DMF as solvent. Using 6 eq methyl iodide (MeI) relative to chitosan and DIPEA as base, up to 68 % DTM was achieved. Applying Design of Experiments (DoE), the method was further optimized under diluted conditions, crucial for industrial scalability and viscosity control. Results from a full factorial design (3 2 ) revealed that diluted medium effectively prevented viscosity concerns, achieving a notably low viscosity of 5.9 cP in the reaction mixture, a 16-fold decrease in viscosity, compared to initial experiments. It was also established that both the MeI reagent and the base addition are significant factors for the DTM response, with both factors showing quadratic effects. The DoE model demonstrated high significance (R = 0.97), high precision for future prediction (Q2 = 0.87), good model validity (0.84) and excellent reproducibility (0.96). The results mark a notable advancement in TMC synthesis, offering an efficient and practical method with significant implications for 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: Vivien Nagy reports financial support was provided by The Icelandic Centre for Research. Helene Liette Lauzon reports a relationship with Primex ehf. that includes: employment. Mar Masson has patent #Chitosan derivatives and methods for preparing the same issued to Primex ehf. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Background: The matrix effect is accepted as one of the critical factors that affect trueness, and it is especially important in the analysis of critical compounds, such as drugs, toxins and pesticides, in complex matrices. Ceftiofur (CEF) is a leading drug used in dairy industry for pulmonary infections. Because milk has a complex matrix, which is rich in fats, proteins and many other compounds, the determination of CEF in milk products deals with issues of trueness. On the other hand, pharmaceuticals also have a complex composition as they contain not only the active pharmaceutical ingredient but also many excipients, such as preservatives and pH modifiers. Due to its frequent use, its residues can be found in meat products or exist as an excreted compound in urine, milk and so on., Objective: The aim of this study was to investigate the effect of different calibration methods on quantitative estimation of CEF in milk and pharmaceutical samples., Methods: CEF was analysed using a new HPLC method, in which separation was achieved on a C 18 bonded fused-core silica particle column by using isocratic elution; the method was optimized by testing different chromatographic conditions and validated according to the ICH Q2(R1) and United States Pharmacopeia guidelines., Results: Interestingly, it was found that CEF signals in milk samples were higher than the ones at the same level prepared in calibration solutions with a ratio of 11.28:1., Conclusion: This finding reveals the necessity of matrix-matched calibration for accurate quantitative determination of CEF in milk samples. Moreover, the milk in the market and the most used pharmaceutical formulations were analysed using the current method., (© 2024 The Author(s). Veterinary Medicine and Science published by John Wiley & Sons Ltd.)

This study investigates the synthesis of flat sheet asymmetric Polysulfone (PSF) membranes using the Non-Solvent Induced Phase Separation (NIPS) method, enhanced by incorporating Deep Eutectic Solvents (DES) composed of Choline Chloride (ChCl) and DL-Malic Acid (MA). The research explores the individual and combined effects of ChCl and MA on membrane morphology and performance. Comprehensive characterization techniques, including Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy-Universal Attenuated Total Reflectance (FTIR-UATR), and Atomic Force Microscopy (AFM), were employed to analyze the structural and surface properties of the membranes. Key performance metrics such as Pure Water Permeability (PWP), protein and dye rejection, fouling behavior, porosity, surface hydrophilicity, and mechanical strength were evaluated. Results demonstrated that integrating DES into the PSF matrix significantly improved membrane properties. The 3% DES membrane exhibited the highest Pure Water Permeability (PWP) of 186.82 L/m 2 h/bar, the lowest water contact angle of 68.8°, and optimal balance in surface roughness parameters, leading to superior antifouling properties with high flux recovery ratio (FRR) and balanced reversible (Rr) and irreversible fouling (Rir) components. The ChCl (HBA) membrane displayed a notable PWP of 121.62 L/m 2 h/bar, large pore sizes (42.72 nm), and moderate surface roughness (R a of 3.32 nm). In contrast, the MA (HBD) membrane demonstrated the highest hydrophilicity with the lowest contact angle (70.7°) and a compact, robust structure, despite its smallest pore sizes and lack of permeability. The findings underscore the synergistic effect of DES formation in the membrane, improving overall performance for ultrafiltration applications. This study provides valuable insights into the distinct roles of ChCl as an HBA and MA as an HBD in DES-modified PSF membranes, revealing their individual contributions and the importance of optimizing DES components and concentrations for specific filtration 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 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Legumes are a widespread and cheap source of starch. However, legume starches are prone to retrogradation in applications. Therefore, enhancing the resistance to retrogradation is important to ensure the quality of starch products. In this study, the effects of amines, alcohols, and carboxylic acids deep eutectic solvents (DESs) on the retrogradation properties of pea starch (PS) were investigated. The results showed that the starches treated with carboxylic acid DESs for only 30 min exhibited low paste viscosity, high paste clarity and anti-retrogradation. The carboxylic acid DESs treatment resulted in holes or cracks appearing on the starch surface, a decrease in molecular ordering, relative crystallinity, and amylose content. The thermal enthalpy of starch as well as the pasting viscosity were substantially reduced after the treatment. The paste clarity and the resistance to retrogradation were significantly improved. Conversely, the structure, pasting and retrogradation properties of starch treated with amine and alcohol DESs exhibited only slight differences compared to PS. The carboxylic acid DESs took a short time for the starch modification, and the modified starch paste with low viscosity, high clarity, and resistance to retrogradation. The study could provide an environmentally-friendly and cost-effective method for the preparation of starch with well anti-retrogradation properties., 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.)

Dynamic nuclear polarization (DNP) enhanced magic angle spinning (MAS) solid-state NMR carried out at 25 K enables rapid acquisition of multi-dimensional 13 C- 15 N correlation spectra for protein structure studies and resonance assignment. Under commonly used DNP conditions, solvent deuteration reduces 1 H- 15 N cross polarization (CP) efficiencies, necessitates more careful optimization, and requires longer high-power 15 N radio-frequency pulses. The sensitivity of 2D heteronuclear correlation experiments is potentially impaired. Here we show that 2D 15 N- 13 C experiments based on 13 C- 15 N transferred echo double resonance (TEDOR) methods outperform 2D experiments based on CP transfers in a fully deuterated solvent, and are competitive with CP-based experiments when the solvent is only partially deuterated. Additionally, we show that optimization of TEDOR-based 2D experiments is simpler than optimization of CP-based experiments under 25 K MAS conditions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Published by Elsevier Inc.)

Lignocellulose (LC) is a natural polymer material that holds immense potential for various applications. However, extracting LC from biomass wastes with high-starch content has been challenging due to low selectivity and yield. In this study, LC was prepared from cassava residue (CR) via a combination of mechanical activation pretreatment and a citric acid (CA)-enhanced ternary deep eutectic solvent (TDES) consisting of choline chloride (ChCl), lactic acid (LA), and CA. The mechanical activation reduces the size of CR, greatly promoting the removal ability for starch, lignin and hemicellulose using TDES, and thus improving yield and selectivity of LC through this method. The CA esterified LC to prevent its excessive hydrolysis and increased a significantly higher LC content (82.52 wt%) compared to mechanical activation only and DES without CA, increasing by 6.97 times and 1.26 times, respectively. The extraction temperature significantly affected the structure, composition, thermal stability of LC and the properties of recovered TDES. The LC extracted at 90 °C (LC-90) had the highest cellulose content (82.52 wt%), crystallinity index (44.82 %), and higher degradation temperature (339.7 °C). The properties of the recovered TDES and extraction mechanism were analyzed. This study provides a strategy for the high-value utilization of biomass waste., 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 acceptance of nonconventional solvents as viable substitutes for traditional organic solvents has been widely recognized in order to comply with food-safety and sustainability regulations. Cyclodextrins (CDs), derived from starch, are cyclic oligosaccharides with the ability to form inclusion complexes with a variety of functional substances as the result of their distinctive structure, which enables them to effectively encapsulate bioactive compounds, rendering them highly sought after for use in food applications. In the implementing plan to achieve carbon-neutral emissions by 2050, the novel generation of supramolecular deep eutectic solvents (SUPRADES) has garnered increased attention and interest. The approach of utilizing SUPRADES as emerging solvents was just beginning to be applied to food studies. This review summarizes a revision of the current advances and critical evaluation of cyclodextrin-based SUPRADES (CD-based SUPRADES) as promising solvents for the enhancement of the extraction efficiency, solubilization and stability of bioactive compounds, adsorption and separation of food components, packaging materials, and modification of biopolymers. To meet the sustainable processing needs of the food industry, the emerging categories of CD-based SUPRADES need to be further fabricated. Herein, our review will sort out the potential application of CD-based SUPRADES in the food industry, aiming to provide a better understanding of CD-based SUPRADES within the viewpoint of food science. Formulation intricacies and scalability issues in real functional foods using CD-based SUPRADES as media need more efforts., (© 2024 Institute of Food Technologists®.)

Chitosan, recognized for its excellent biodegradability, biocompatibility, and antibacterial properties, has several potential applications, particularly in the biomedical field. However, its widespread use is hindered by inherent limitations such as low mechanical strength and safety concerns arising from a low degree of deacetylation and the presence of impurities. This study aimed to introduce an innovative purification method for chitosan via liquefied dimethyl ether (DME) extraction. The proposed technique effectively addresses the challenges associated with chitosan by facilitating deacetylation and impurity removal. Liquefied DME is emerging as the extraction solvent of choice owing to its advantages, such as low boiling point, safety, and environmental sustainability. The degree of deacetylation of chitosan was extensively evaluated using thermogravimetric-differential thermal analysis, Fourier transform infrared spectroscopy, X-ray diffraction, intrinsic viscosity measurements, solid-state nuclear magnetic resonance spectroscopy and X-ray photoelectron spectroscopy, and elemental analysis. The solubility of chitosan in liquefied DME was investigated using Hansen solubility parameters. This study contributes to the improvement of the safety profile of chitosan, thereby expanding its potential applications in various fields. The use of liquefied DME as an extraction solvent proved to be efficient in addressing the existing challenges and is consistent with the principles of safety and environmental sustainability., 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.)

This study investigates the production of cellulose nanofibers (CNF) from Barley straw using ultrasound-assisted deep eutectic solvent (US-DES) treatment for biomass fractionation and subsequent high-intensity ultrasonication (HIUS) for nano-fibrillation. Two deep eutectic solvents (DES), synthesized from choline chloride (ChCl) and oxalic acid dihydrate (OAD) at 1:1 and 2:1 M ratio, achieved solubilisation of over 80 % of lignin and hemicellulose under optimal conditions. The purification of these DES-treated materials resulted in cellulose with a purity >88 %. CNFs, characterized by a size of <100 nm, a polydispersity index under 0.5, and a zeta potential lower than -30 mV, were successfully isolated through a combination of wet grinding and HIUS treatment. SEM and XRD results showed the formation of a network of interconnected fibres with a Type I cellulose structure. This research highlights Barley straw's potential as a sustainable source of high-value CNF from agricultural waste., 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.)

The poor water solubility of nitrendipine (NT) results in low oral bioavailability, which hinders its practical application. Hydroxypropyl methylcellulose (HPMC) is a prominent drug carrier that has been applied in the biomedical field due to its significant characteristics, such as large surface area, biocompatibility and biodegradability. In this study, an efficient drug delivery system based on the preparation of NT/HPMC solid dispersion using supercritical antisolvent (SAS) technology was proposed. The effect of different operating parameters such as solvent, host guest ratio, concentration, temperature, and pressure on NT/HPMC was optimized to obtain dispersed particles with maximum solubility. The formed solid dispersion presents non-static spherical particles with a high surface area and small particle size. Importantly, in vitro drug release studies have demonstrated that the dissolution and solubility of NT in solid dispersion are significantly enhanced compared to pure drug. In vitro bioactivity experiments showed that the NT/HPMC solid dispersion has good biocompatibility and antibacterial performance. Thus, this study indicates that solid dispersion prepared using SAS technology are considered a promising drug delivery system., 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 conventional oil-absorbing materials utilized for addressing oil and organic solvent pollution are plagued by the issue of secondary pollution. In this study, biodegradable porous polylactic acid (PLA) fiber materials were prepared using centrifugal spinning technology, with PLA and polyvinyl butyral (PVB) as raw materials. PVB was utilized as a pore-forming agent to fabricate multi-layered porous PLA fiber materials. When the content of PVB in the spinning solution was 14 %, the porous PLA fibers exhibited the maximum specific surface area of 60.7 m 2 /g and a porosity of up to 85.4 %, interior of the fiber contained numerous mesopores. Additionally, the porous PLA fibers demonstrated excellent superhydrophobic oil absorption properties, with a water static contact angle of 137.8° and oil or organic solvent absorption capacities ranging from 10 to 17.7 g/g. Furthermore, porous PLA fiber materials exhibited outstanding biodegradability, with a degradation mass loss rate of 42.3-45.1 %. Therefore, superhydrophobic and oleophilic biomass-based PLA fiber materials prepared in centrifugal spinning show promising applications in the recovery of organic solvents and oily substances., 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.)

Hydrogels with remarkable flexibility have gained popularity as materials for current research. However, the unfavorable properties of short-term adhesion, susceptibility to damage, and freezing in low-temperature presented by conventional hydrogels have become bottlenecks for further applications. In this work, an anti-freezing hydrogel with excellent mechanical, adhesion, and self-healing properties were developed by constructing a persistent semiquinone/quinone-catechol redox equilibrium environment. The introduction of lignin-modified cellulose nanofibers (LCNFs) significantly improved the overall mechanical properties of the material, driven by strong hydrogen bond interactions. This enhancement was evident in the tensile properties (97.74 ± 1.72 kPa, 783 %) and compression properties (> 90 %). Within the internal network of the gel, the synergistic action of lignin and ammonium persulfate resulted in the production of catechol, which imparted the gel with excellent adhesion properties (28.26 ± 2.13 KPa) and broad adhesion applicability. In addition, the incorporation of ethylene glycol (EG) positively contributed to the strengthening of the gel while endowed with tunable anti-freezing properties. Given the exceptional advantages of the prepared hydrogels, they were used to assemble flexible strain sensors with outstanding sensitivity for monitoring human motions., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A endo-xylanase, of the glycoside hydrolase family 10 from Schizophyllum commune DB01, was expressed in P. pastoris. Recombinant xylanase (Scxyn5) retained above 80 % maximum activity in 10 % dimethyl sulfoxide and retained 90 % maximum activity in 5 M NaCl on the substrate of birchwood xylan. The effect of NaCl on the catalytic activity of Scxyn5 was significantly different toward various substrates, which was caused by the difference of monosaccharide composition and sturcture of the substrates. Furthermore, when corn fiber gum (CFG) was used as a substrate, the catalytic activity of Scxyn5 increased by 1.3-2.03 times in 1-5 M NaCl. Based on response surface methodology, the highest catalytic activity of Scxyn5 in hydrolyzing CFG were achieved with enzymatic temperature of 50 °C, pH value of 6.0, and 4 M NaCl. These properties of Scxyn5 suit the arabinoxylan-oligosaccharides (AXOs) preparation from CFG and some other potential applications in food 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 removal of organic solvents during the preparation of biodegradable poly(D,L-lactide-co-glycolide) (PLGA) microparticles by an O/W- solvent extraction/evaporation process was investigated and controlled by diafiltration. Emulsification and steady replacement of the aqueous phase were performed in parallel in a single-vessel setup. During the process, the solidification of the dispersed phase (drug:PLGA:solvent droplets) into microparticles was monitored with video-microscopy and focused beam reflectance measurement (FBRM) and the residual solvent content was analyzed with headspace gas chromatography (organic solvent) and coulometric Karl-Fischer titration (water). Microparticles containing dexamethasone or risperidone were characterized with regard to particle size, morphology, encapsulation efficiency and in-vitro release. Diafiltration-accelerated solvent extraction shortened the process time by accelerating solidification of dispersed phase but reduced the residual dichloromethane content only in combination with increased temperature. Increasing the diafiltration rate increased particle size, porosity, and the encapsulation efficiency of risperidone. The latter effect was particularly evident with increasing lipophilicity of PLGA. A slower and more uniform solidification of end-capped and increased lactide content PLGA grade was identified as the reason for an increased drug leaching. Accelerated solvent extraction by diafiltration did not affect the in-vitro release of risperidone from different PLGA grades. The initial burst release of dexamethasone was increased by diafiltration when encapsulated in concentrations above the percolation threshold. Both porosity and burst release could be reduced by increasing the process temperature during diafiltration. Residual water content was established as an indicator for porosity and correlated with the burst release of dexamethasone., 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.)

Electrospun polystyrene (PS) fibers are produced using a mixed solvent of chloroform and n,n-dimethylformamide (DMF) to investigate the influence of the solvent ratio on the fiber surface morphology and contact angle of the obtained mats. Electrospinning is a simple processing technique for producing fibers with diameters in the range of nanometers to a few micrometers. When using the different solvent ratios for this process, porous PS membranes are created due to nonsolvent and thermally induced phase separation (N-TIPS). The morphology of the fibers is analyzed through scanning electron microscopy (SEM), which showed that fibers have diameters between 200 nm and 6 µm. SEM also revealed that the pores present on the surface of the fibers vary from densely compacted and well-formed nanopores with diameters in the range of 20-50 nm to larger pores with sizes of ≈100-200 nm. The pore size varied with different solvent ratios. The surface area is analyzed using the Brunauer-Emmett-Teller (BET) method and found that the polymeric fibers have a high surface area (≈35 m 2  g -1 ). The fibers with such morphology are highly hydrophobic, with a contact angle higher than 143°. These materials are excellent candidates for applications in textiles, filtration, and biomedical fields., (© 2024 The Author(s). Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

Lignin is a complex biopolymer whose efficient extraction from biomass is crucial for various applications. Deep eutectic solvents (DES), particularly natural-origin DES (NADES), have emerged as promising systems for lignin fractionation and separation from other biomass components. While ternary DES offer enhanced fractionation performance, the role of each component in these mixtures remains unclear. In this study, the effects of adding tartaric acid (Tart) or citric acid (Cit) to a common binary DES mixture composed of lactic acid (Lact) and choline chloride (ChCl) were investigated for lignin extraction from acacia wood. Ternary Cit-based DES showed superior performance compared to Tart-based DES. Using a combined mixture-process D-Optimal experimental design, the Lact:Cit:ChCl DES composition and extraction temperature were optimized targeting maximum lignin yield and purity. The optimal conditions (i.e., Lact:Cit:ChCl, 0.6:0.3:0.1 molar ratio, 140 °C) resulted in a lignin extraction yield of 99.63 ± 1.24 % and a lignin purity of 91.45 ± 1.03 %. Furthermore, this DES exhibited feasible recyclability and reusability without sacrificing efficiency., 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.)

In this study, to investigate the potential for delivering bioactive substances, various cereal proteoglycan nanoparticles were prepared using anti-solvent precipitation for the delivery of oyster protein hydrolysate (OPH). The hydrogen bonding and hydrophobic interaction were the driving forces for OPH embedding. OPH-Loaded Zein/NaCas/Gum Arabic composite nanoparticles could self-assemble into spherical (191 nm) particles with strong stability, uniform distribution (about PDI = 0.2), and high negative charge (about -28 mV). The secondary structure of OPH-Loaded zein was converted from α-helix to random coil with heat treatment. The off-flavor, including (E, E)-2,4-heptadienal, octadecane, and 1-octanol in OPH-Loaded Zein nanoparticles significantly decreased. Furthermore, these nanoparticles containing OPH had excellent oxidation resistance, in vitro digestibility, and non-toxicity in Caco-2 and HT-29 cells. Overall, this work provides an efficient strategy for OPH delivery, suggesting that OPH could be ingested as a nutraceutical in powder form while also promoting the development of high-flavor-quality oyster products., 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.)

Gallium (Ga) recovery from the red mud, though important has never been successful due to several technical and economic reasons such as contaminant interference and the high cost of membranes due to their faster saturation resulting in the clogging of membranes with contaminants. This study demonstrated the recovery of Ga by a combination of HCl-based leaching, Fe/Al/Ti separation, and recovery of Ga using Cyphos IL 104-based solvent extraction and complexation of Ga with desferrioxamine B as a proof-of-principle of the GaLIophore technology. The main leaching parameters such as concentrations of acids, time and temperature of the reaction, and solid-to-liquid ratio have been systematically investigated. The optimal leaching conditions were determined as 4 mol/L HCl, 2 h time, 80 °C temperature, and solid-to-liquid ratio 1:20 (g/mL) attaining a more than 90% leaching of Ga. Subsequently, more than 99% Ga was extracted from the leachate using 0.05 mol/L Cyphos IL 104 at A:O ratio 1 and stripped by 0.01 mol/L H 2 SO 4 at O:A ratio 1 from the organic phase. Desferrioxamine B (DFOB) demonstrated selectivity by complexing with more than 90% Ga in a stripped solution. The interaction between extractable species of Ga and Cyphos IL 104 was studied by Density Functional Theory (DFT) calculations and infrared spectroscopy. The whole process demonstrated the recovery of Ga by more than 80% present in the red mud. Further, the preliminary economic analysis suggests that the process can be profitable when Fe, Al, Sc, and Ga are recovered at a minimum rate of 50, 50, 75, and 75%., 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 study explores an eco-friendly delignification technique for raw oil palm leaves (OPL), highlighting the optimized conditions of choline chloride-lactic acid deep eutectic solvent (DES)-mediated ball milling pretreatment to maximize the co-production yields of highly crystalline cellulose and lignin. Our five-level-four-factor Taguchi design identified the optimal reaction settings for cellulose production (85.83 % yield, 47.28 % crystallinity) as 90-minute milling, 1500 rpm, mill-ball size ratio of 30:10, ball-to-sample mass ratio of 20:1, DES-to-sample mass ratio of 3:1. Conversely, the maximal lignin extraction yield (35.23 %) occurred optimally at 120-minute milling, 600 rpm, mill-ball size ratio of 25:5, ball-to-sample mass ratio of 20:1 and DES-to-sample mass ratio of 9:1. Statistical results showed that milling frequency (p-value ≤ 0.0001) was highly significant in improving cellulose crystallinity and yield, while DES-to-sample mass ratio (p-value ≤ 0.0001) was the most impacting on lignin yield. The thermogravimetric method affirmed the elevated cellulose thermal stability, corroborating the enhanced cellulose content (40.14 % to 73.67 %) alongside elevated crystallinity and crystallite size (3.31 to 4.72 nm) shown by X-ray diffractograms. The increased surface roughness seen in micrographs mirrored the above-said post-treatment changes. In short, our optimized one-pot dual-action pretreatment effectively delignified the raw OPL to produce cellulose-rich material with enhanced crystallinity and lignin solidity., 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.)