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Ex vivo penetration tests are important tools in cosmetic and pharmaceutical research. However, variability of experimental setups is challenging when reviewing literature. Different skin models, pre-treatments and experimental parameters render comparison difficult. Thus, our aim was to conduct ex vivo penetration tests using caffeine in different setups with varying incubation conditions (ambient vs. Franz cells, infinite vs. finite dose). Additionally, the impact of skin pre-treatment with different aggressors (surfactants, UVA irradiation) should be considered. Possible synergistic barrier damage of surfactants and UVA irradiation should be explored. Analysis was conducted using quantitative confocal Raman spectroscopy. Results showed that incubation time and extensive hydration (20 h in Franz cells) had the greatest impact on penetration behavior. Additional irradiation after pre-treatment with oil-in-water nanoemulsions showed no strong impact on caffeine penetration in general, irrespective of surfactant type. However, in case of sodium lauryl ether sulfate, a trend towards enhanced values was observed due to irradiation (1.3-fold). This suggests cumulative skin barrier damage of irritant surfactants and UVA irradiation, potentially due to stratum corneum alterations. Further studies using different irradiation regimens are planned to confirm this hypothesis., 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.)

Developing co-amorphous systems is a promising strategy to improve the water solubility of poorly water-soluble drugs. Most of the studies focused on the initial dissolution rate of the fresh co-amorphous systems, and only physical stability was investigated after storage. However, the maintenance of the enhanced dissolution rate of co-amorphous systems after storage is necessary for further product development. The maintenance of amorphous forms after storage does not always mean the maintenance of the dissolution rate. In this study, indomethacin, arginine, tryptophan, and phenylalanine were used as the model drug and the co-formers to prepare co-amorphous systems and then stored under dry condition and RH 60 ± 5 % condition. No recrystallization was observed after the storage for 40 d and 80 d. Interestingly, both intrinsic dissolution rate (IDR) decrease and unexpected increase after storage were confirmed. The further mixing of IND and the co-former at a molecular level and the moisture changes of the co-amorphous systems during storage were supposed to play important roles in the aging. This study reminds us that the possible dissolution changes (both dissolution decrease and increase) of co-amorphous systems during storage should be carefully considered, though these samples maintained amorphous forms., 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 curious chemistry observed in microdroplets has captivated chemists in recent years and has led to an investigation into their ability to drive seemingly impossible chemistries. One particularly interesting capability of these microdroplets is their ability to accelerate reactions by several orders of magnitude. While there have been many investigations into which reactions can be accelerated by confinement within microdroplets, no study has directly compared reaction acceleration at the liquid|liquid and gas|liquid interfaces. Here, we confine glucose oxidase, one of life's most important enzymes, to microdroplets and monitor the turnover rate of glucose by the electroactive cofactor, hexacyanoferrate (III). We use stochastic electrochemistry to monitor the collision of single femtoliter water droplets on an ultramicroelectrode. We also develop a measurement modality to robustly quantify reaction rates for femtoliter liquid aerosol droplets, where the majority of the interface is gas|liquid. We demonstrate that the gas|liquid interface accelerates enzyme turnover by over an order of magnitude over the liquid|liquid interface. This is the first apples-to-apples comparison of reaction acceleration at two distinct interfaces that indicates that the gas|liquid interface plays a central role in driving curious chemistry., Competing Interests: Competing interests statement:The authors declare no competing interest.

Rapid characterization of solid waste using near-infrared hyperspectral imaging (HSI) coupled with machine learning models has been increasingly investigated to replace the traditional time- and labor-intensive methods. However, contamination by waste-derived leachates or other fractions etc., can cause the spectra evolutions and significantly influences the identification performance, which has not been investigated before. The first attempt was made by using hyperspectral unmixing (HU) to extract the endmember components and demonstrate their contributions (abundance) to solid waste, taking the non-linear reflectance changes due to the O-H vibration of water and unclear variation associated with oil and leachates as an example. The HSI spectra of various solid waste components influenced by pure water, oil and three kinds of leachates were acquired. A novel method based on HU models, including multivariate curve resolution with alternating least squares and state-of-the-art autoencoder architectures (deep learning models), was developed to estimate the spectra of endmembers as well as their abundances in individual pixel. Their spatial distribution overview in solid waste was then yielded. The selected models were validated via an independent test data set, with lower spectral angle distance, 12.3° ± 6.5°, indicating the similarity of the predicted endmembers with real components. And the lowest root of mean square error on endmember distribution maps was 0.17. The non-linear liquid's effects by water and oil on spectra variations of solid waste were clearly illuminated. Additionally, the proposed method can extract information from mixed spectroscopic images and generate reconstructed spectra., 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.)

In the context of the air quality co-benefits of carbon neutrality, conventional strategies for the end-of-pipe control aimed at reducing volatile organic compounds (VOCs) to carbon dioxide (CO 2 ) require a more realistic revision. This study explored the synergetic removal of carbonyls with low carbon emission by amine-functionalized manganese dioxide (MnO 2 ), obtained through a method involving freezing-thawing cycles. Molecular-level characterization revealed that an ordered array of interfacial water dimers (H 5 O 2 + , a class of water-proton clusters) on the MnO 2 surface enhanced the robust bonding of metal sites with amino groups. Amine-functionalized MnO 2 can be negatively charged under environmental acidity to further interfacial proton-coupled electron transfers. This cooperativity in interfacial chemical processes promoted the selective conversion of carbonyl carbons to bicarbonated amides (NH 3 + HCO 3 - ), serving as a reservoir of CO 2 . In comparison to a commercially used 2,4-dinitrophenylhydrazine (DNPH) control, this approach achieved nearly complete removal of a priority carbonyl mixture containing formaldehyde, acetaldehyde, and acetone synergically. The formation of secondary organic compounds in the gas phase and CO 2 off-gas were suppressed., 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.)

This study presents a novel biotechnological approach for creating water vapor-resistant cryogels with improved integrity. Rice straw cellulose was transformed into nanofibrils through TEMPO-mediated oxidation and high-pressure homogenization. The resulting cryogels remained firm even when immersed in aqueous media, whose pores were used by live cell to deposit polyhydroxyalkanoate (PHA) particles inside them. This novel method allowed the compatibilization of PHA within the cellulosic fibers. As a consequence, the water sorption capacity was decreased by up to 6 times having just 4 % of PHA compared to untreated cryogels, preserving the cryogel density and elasticity. Additionally, this technique can be adapted to various bacterial strains and PHA types, allowing for further optimization. It was demonstrated that the amount and type of PHA (medium chain length and small chain length-PHA) used affects the properties for the cryogels, especially the water vapor sorption behavior and the compressive strength. Compared to traditional coating methods, this cell-mediated approach not only allows to distribute PHA on the surface of the cryogel, but also ensures polymer penetration throughout the cryogel due to bacterial self-movement. This study opens doors for creating cryogels with tunable water vapor sorption and other additional functionalities through the use of specialized PHA variants., 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.)

Perilla essential oil (PLEO) offers benefits for food preservation and healthcare, yet its instability restricts its applications. In this study, chitosan (CS) and TiO 2 used to prepare composite particles. TiO 2 , after being modified with sodium laurate (SL), was successfully introduced at 0.1 %-3 % into the CS matrix. The resulting CS-SL-TiO 2 composite particles can be formed by intertwining and rearranging through intramolecular and intermolecular interactions, and form an O/W interface with stability and viscoelasticity. The Pickering emulsions stabilized by these particles exhibit non-Newtonian pseudoplastic behavior, shear-thinning properties, and slow-release characteristics, along with antibacterial activity. Emulsions with 0.5 % and 1 % CS-SL-TiO 2 composites demonstrated superior antibacterial effects against Escherichia coli and Staphylococcus aureus. The study revealed that all emulsions undergo Fickian diffusion and a sustained release of PLEO, with the Ritger-Peppas model best describing this release mechanism. The slow-release behaviors positively correlates with interfacial pressure, composite particle size, composite particle potential, composite contact angle, emulsion particle size and emulsion potential, but negatively correlates with diffusion rate, penetration rate, release kinetics and release rate. The findings lay groundwork for developing slow-release antimicrobial emulsions within polysaccharide matrices, showcasing promise for antimicrobial packaging solutions and enhanced food preservation techniques., Competing Interests: Declaration of competing interest The authors declare that they have no conflicts of interest., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Liquid-liquid phase separation is a key phenomenon in the formation of membrane-less structures within the cell, appearing as liquid biomolecular condensates. Protein condensates are the most studied for their biological relevance, and their tendency to evolve, resulting in the formation of aggregates with a high level of order called amyloid. In this study, it is demonstrated that Human Insulin forms micrometric, round amyloid-like structures at room temperature within sub-microliter scale aqueous compartments. These distinctive particles feature a solid core enveloped by a fluid-like corona and form at the interface between the aqueous compartment and the glass coverslip upon which they are cast. Quantitative fluorescence microscopy is used to study in real-time the formation of amyloid-like superstructures. Their formation results driven by liquid-liquid phase separation process that arises from spatially heterogeneous distribution of nuclei at the glass-water interface. The proposed experimental setup allows modifying the surface-to-volume ratio of the aqueous compartments, which affects the aggregation rate and particle size, while also inducing fine alterations in the molecular structures of the final assemblies. These findings enhance the understanding of the factors governing amyloid structure formation, shedding light on the catalytic role of surfaces in this process., 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 Inc. All rights reserved.)

The development of innovative multi-emission sensors for the rapid and accurate detection of contaminants is both vital and challenging. In this study, utilizing two rigid ligands (H 3 ICA and H 4 BTEC), a series of water-stable bimetallic organic frameworks (EuTb-MOFs) were synthesized. Luminescent investigations have revealed that EuTb-MOF-1 exhibits prominent multiple emission peaks, attributed to the distinctive fluorescence characteristics of Eu(III) and Tb(III) ions. Therefore, EuTb-MOF-1 efficiently recognized various metal ions and pharmaceutical compounds through 2D decoded maps. Fe 3+ and Pb 2+ exhibited significant quenching effects on the luminescence of EuTb-MOF-1, which were attributed to the internal filtering effect and the interaction between Lewis basic sites within EuTb-MOF-1 and Pb 2+ ions, respectively. Furthermore, EuTb-MOF-1 demonstrated high sensitivity to sulfonamide antibiotics, with detection limits of 0.037 μM for SMZ and 0.041 μM for SDZ, respectively. In addition, EuTb-MOF-1 was immobilized to prepare MOF-based test strips, enabling direct visual detection of sulfonamides as a portable sensor. With excellent water stability, multi-responsive recognition capabilities, and high sensitivity to specific analytes, EuTb-MOF-1 is a promising candidate for environmental contaminant detection in aquatic systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The inhibitory effects of cold plasma-activated water (PAW) on the formation of AGEs and methylimidazoles in cookies was examined. The results showed that different PAW (parameters: 50 W-50 s, 50 W-100 s, 50 W-150 s, 100 W-50 s, 100 W-100 s, and 100 W-150 s) reduced the contents of AGEs and methylimidazoles, in which the maximum inhibition rates were 47.38% and 40.17% for free and bound AGEs and 44.16% and 40.31% for free and bound methylimidazoles, respectively. Moreover, the mechanisms associated with the elimination of carbonyl intermediates and free radicals was determined by electron paramagnetic resonance (EPR) and high performance liquid chromatography-ultraviolet/visible absorption detector (HPLC-UV/Vis). The results showed the quenching of total free radicals, alkyl free radicals, and HO· by PAW, leading to the suppression of glyoxal and methylglyoxal intermediates. These findings support PAW as a promising agent to enhance the safety of cookies., 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.)

Prepared dishes are becoming an increasingly important part of diets, while most studies focus on the flavor. In this study, the moisture loss induced by structure changes of precooked beef during freezing-thawing-reheating process was investigated. The myowater trapped and released by 'myenteric channels' and 'water reservoir' were observed by integrated multiple microstructure and water distribution visual analysis. X-ray results showed an increase in total porosity and the close porosity transfer to open porosity during freezing-thawing-reheating. The weight loss of frozen-reheated (FR) and frozen-thawed-reheated (FTR) samples was 6.34% and 7.69%, respectively. Although freezing-thawing did not significantly affect the moisture loss, magnetic resonance image (MRI) showed that the 'free water' temporarily existed in interfibrous spaces after thawing and leaked out during reheating. Directly reheating avoided the myowater redistribution and muscle extension mediated, which reduced moisture loss. These results provide a reference for quality control of prepared dishes during the industrial supply chain., 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 Ltd.)

A study on the absorption and fluorescence properties of the 8-anilino-1-naphthalenesulfonate (ANS) fluorescent probe was performed in order to (i) verify the validity of its classification as hydrophobic probe and (ii) to assess the reliability of the interpretation of the ANS fluorescence enhancement upon protein binding as the evidence for the existence of hydrophobic binding sites on the protein molecules. We observed an enhancement of the ANS fluorescence in hydrophilic media: DMSO, polyethylene glycol (PEG400) and glycerol to the values characteristic of ANS complexes with globular proteins, and all ANS fluorescence characteristics (except anisotropy) in PEG400 and in complex with bovine serum albumin are identical. We observed an increase in the ANS fluorescence with a nonzero anisotropy in an aqueous medium in the presence of an amphiphilic cetyltrimethylammonium cation as a result of the formation of the 1:1 complex with ANS. Water molecules quench the fluorescence of ANS. The enhancement of the ANS fluorescence in aqueous media in the presence of fluorescence enhancers is accounted for by their blocking the access of water molecules to the region close to the excited ANS molecule, which is critical for the fluorescence., 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.)

Understanding a biomaterial's structural and hydration dynamics is essential for its development and applications in tissue regeneration. In this study, collagen-hyaluronic acid (HA) scaffolds were analyzed utilizing Nuclear Magnetic Resonance (NMR) techniques to elucidate how different cross-linking conditions influence the internal architecture and interaction with solvents in these scaffolds. The scaffolds were fabricated using 3D printing and cross-linked with 1,4-butanediol diglycidyl ether (BDDGE), a process known to impact their mechanical properties. We gained insights into the microstructural organization and hydration behavior within the scaffolds when exposed to water and ethanol by employing proton relaxation and diffusion measurements. To better understand the system's performance, static and dynamic experiments were performed. Our results indicate that the degree of cross-linking affects the scaffold's ability to retain water, with higher cross-linking leading to more rigid structures. This also altered the hydration dynamics mainly due to a difference in the diffusion of water within the scaffold. In addition, the anisotropy of the collagen fibers also decreases with the cross-linking. Ethanol, a less polar solvent, provided a contrasting environment that further revealed the structural dependencies on the cross-linking density. The study's findings contribute to a deeper understanding of how the structure and morphology affect the functionality of collagen-HA scaffolds, offering critical information for optimizing their design for specific biomedical applications, such as soft tissue regeneration. Our experiments show how NMR is a valuable tool to provide information on dynamic processes not only in collagen-HA scaffolds but also in many biocompatible polymeric samples. The outcomes of this research provide a foundation for future work aimed at tailoring scaffold properties to enhance their performance in clinical settings, ultimately advancing the field of tissue engineering.

The succinate-ubiquinone oxidoreductase (SQR) complex connects two of the cell's most vital energy-producing metabolic processes: the tricarboxylic acid cycle and the electron transport chain. Hence, the SQR complex is essential in cell metabolism, and its malfunction leads to the progression of multiple metabolic disorders and other diseases, such as cancer. In the current study, we calculated the electron tunneling (ET) pathways between the different redox systems in the SQR complex, including the SQR ligands and the distant heme b redox center, using the broken-symmetry semi-empirical ZINDO method. Interestingly, we discovered a water channel running from the mitochondrial matrix, filling the space between Fe 3 S 4 and heme b redox centers. To investigate the physiological function of the water channel, we performed extensive molecular dynamics (MD) simulations of the membrane-embedded SQR complex in small and large water boxes, representing regular (MD A ) and extended (MD B ) volume states, respectively. We found that under regular volume conditions (MD A ), the ET reaction is conducted through both the iron-sulfur cluster chain ( i.e. , pathway A) and through heme b ( i.e. , pathway B). Hence, the SQR complex encompasses an internal interferometer similar to the Mach-Zender interferometer, such that the tunneling electron experiences a self-interference effect through pathways A and B, enhancing the SQR complex's overall ET thermodynamics and favoring the forward ET direction of oxidizing succinate to fumarate and reducing ubiquinone to ubiquinol. On the other hand, we found that under extended volume conditions (MD B ), the internal water channel of the SQR complex "senses" the expansion in the mitochondrial volume, pushing the heme b and Fe 4 S 3 redox centers apart and hence lowering the SQR equilibrium constant to almost unity. Therefore, the SQR complex could be driven to work in the reverse direction, catalyzing the production of ubiquinone molecules essential for the physiological function of respiratory complexes I and III and restoring the inner-mitochondrial membrane potential, which leads to restoring the function of the H-K anti-porter, pumping K + outward from the matrix and restoring the regular mitochondrial volume.

Accurate quantification of cisplatin (cDDP) in body fluids (blood, urine, and ascites) is crucial in monitoring therapeutic processes, assessing drug metabolism, and optimizing treatment schedules for cancer patients. Nonetheless, due to the inherent fluorescence and complexity of the body fluid matrix, along with the low cDDP concentrations in these fluids during treatment, using fluorescent sensors for fluid detection remains a subject of ongoing research. Herein, a series of water-soluble cDDP-activatable fluorescent sensors was rationally constructed by introducing thioether groups to the xanthene skeleton based on the chalcogenophilicity of platinum. These sensors exhibit excellent sensitivity and certain anti-interference capabilities for sensing cDDP in living cells, rat tissues, and zebrafish. Especially, with a simplified sample pretreatment procedure, for the first time, Rh3 and Rh4 have enabled quantitative detection of cDDP levels in diversiform body fluids from clinical ovarian and bladder cancer patients. These results are highly consistent with those obtained by ICP-MS detection. This work paves the way for utilizing fluorescent sensors in clinical body fluid analysis, thus potentially revolutionizing the monitoring methods of cDDP in clinic settings.

Short-peptide amyloid assembly and disassembly play crucial roles in various research fields, which range from addressing pathologies that lack therapeutic solutions to the development of innovative soft (bio)materials. Hydrogels from short peptides typically show thermo-reversible gel-to-sol transition, whereby fibrils disassemble upon heating, and re-assemble upon cooling down to room temperature (rt). Despite ongoing intense research studies in this area, the majority focus on peptide-peptide interaction and neglect the structuring role of water in peptide supramolecular behavior. This study describes an unprotected tetrapeptide gelator that forms highly stable fibrils which, upon heating, re-organize into plates that persist upon cooling to rt. All-atom molecular dynamics (MD) simulations and experimental methods reveal water as a key player in the thermodynamics that accompany this irreversible morphological transition, and advance our understanding of supramolecular structures.

In the field of medical implants, enhancing the wettability of artificial surfaces is crucial for improving biocompatibility. This study investigates the potential of ozone nanobubble water, an aqueous solution known for its strong oxidizing and sterilizing properties, to modify the surface of titanium dental implants. By immersing the implants in ozone nanobubble water for ∼10 min, we observed a significant transformation of their surface characteristics. Implant surfaces that had become hydrophobic over time, likely due to organic contaminants, became superhydrophilic, exhibiting a contact angle near zero. Fresh implant material is initially hydrophilic but becomes hydrophobic within a few days of drying. In sharp contrast, the hydrophilicity induced by ozone nanobubble water treatment persisted for more than one month. This durability suggests not only the removal of organic matter through cleaning but also a substantial alteration in the surface properties of the implants. The generation of ozone nanobubble water involved releasing ozone microbubbles into an aqueous solution containing trace amounts of iron and manganese, resulting in spherical particles with an average diameter of ∼10 nm. These particles could be bulk nanobubbles, a stabilized gas body surrounded by a solid shell composed of iron hydroxide. Termed "nanoshells" in our previous study, these particles demonstrated exceptional dispersibility without the need for stabilizing agents such as surfactants or capping agents, attributed to their inherent high wettability. The sustained hydrophilicity of the implant surfaces might be attributed to the adherence of these hydrophilic nanoshells to the implant's surface. This study highlights the potential of ozone nanobubble water for long-term surface modification of dental implants, offering a promising avenue for enhancing implant biocompatibility.

Hydrogen peroxide (H 2 O 2 ) electrosynthesis using metal-free carbon materials via the 2e - oxygen reduction pathway has sparked considerable research interest. However, the scalable preparation of carbon electrocatalysts to achieve satisfactory H 2 O 2 yield in acidic media remains a grand challenge. Here, we present the design of a carbon nanoreactor series that integrates precise O/N codoping alongside well-regulated geometric structures targeting high-efficiency electrosynthesis of H 2 O 2 . Theoretical computations reveal that strategic N/O codoping facilitates partial electron transfer from C sites to O sites, realizing electronic rearrangement that optimizes C-site adsorption of *OOH. Concurrently, the O-O bond in *OOH is strengthened by charge transfer from antibonding to π-orbitals, stabilizing the O-O bond and preventing its dissociation. The carbon nanoreactor with a hollow bowl geometry also facilitates the mass transport of O 2 and H 2 O 2 , achieving an H 2 O 2 selectivity of 96% in acidic media. Furthermore, a flow cell integrated with the refined nanoreactor catalyst achieves an impressive H 2 O 2 production rate of 2942.4 mg L -1 h -1 , coupled with stable operation of nearly 80 h, surpassing the state-of-the-art metal-free analogs. The feasibility of the electro-synthesized H 2 O 2 is further demonstrated to be highly efficient in wastewater remediation.

We report an instantaneous room-temperature phase separation of 1 mM bovine serum albumin solution in the presence of (20% acetic acid+0.2 M NaCl), a routinely used food preservative; an opaque liquid-like phase (L) coexists in equilibrium with a granular gel like phase (G). Interestingly, neither 20% acetic acid nor 0.2 M NaCl individually induces such a phase separation. Field emission scanning electron microscopy (FESEM) and high-resolution transmission electron microscopy (HRTEM) imaging show aggregated proteins to be dispersed in the upper phase, while the lower phase is composed of cross-linked fibrils (hydrogels). Mid-IR FTIR, Raman scattering, and circular dichroism (CD) experiments reveal a significant increase in the β-sheet content in BSA, which confirms the formation of amyloids in the presence of the excipient. Both L and G phases undergo distinct visual and microscopic changes upon incubation at 25 and 80 °C. It is evident that the added salt plays a pivotal role in bringing about this otherwise unique phase behavior. We divulge the explicit role of the ion associated hydration using THz-FTIR measurements in the 1.5-16.7 THz (50-550 cm -1 ) frequency window. Systematic alteration in the ion-induced THz-active mode of water envisions the key role of ions in shaping the various phases. Our study depicts an intriguing observation of severe amyloidosis of BSA upon the addition of a food preservative, even at room temperature, which is expected to add new insight into amyloid research. Considering the increasing number of individuals suffering from several neurodegenerative disorders (Alzheimer's, Parkinson's, type-2 diabetes, obesity, cancer, etc.), this study leads a caution toward critically revisiting the usage of known food preservatives.

Various sources associated with mining activities adversely affect water quality in aquatic ecosystems. This study aimed to estimate the sources of dissolved trace elements (DTEs: Al, As, B, Ba, Cd, Co, Cr, Cs, Cu, Fe, Li, Mn, Mo, Ni, Pb, Rb, Sb, U, and Zn) affecting water chemistry in the upper Nakdong River (UNR) catchment and determine the hydrological processes associated with the inflow from anthropogenic sources. Hierarchical cluster analysis (HCA) and principal component analysis (PCA) were employed to estimate main sources affecting water chemistry and its spatiotemporal variability in the four tributaries and main channel of the UNR. Water samples were classified into four groups based on their chemistry. The spatiotemporal variations of DTEs were driven by the presence of anthropogenic sources (including smelters, AMD, mining-related sources), while running toward downstream. The correlations among PCA (and HCA), Zn as smelter impact, and deuterium excess (d-excess = δ 2 H - 8 × δ 18 O) indicated that smelters had a strong influence on water chemistry in the main channel after passing through the smelter. In the dry season, d-excess < ~12 ‰ was observed with increasing Zn levels and factor score for PC2, especially samples influenced by DTEs from smelter, indicating that groundwater affected by the smelters recharged mainly by summer rainwater impacted the spatiotemporal variability of DTEs. This multivariate study suggests that the spatiotemporal variation in DTEs is associated with the complex contributions of natural and anthropogenic sources to water chemistry, which are strongly influenced by hydrological processes and seasonality., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationship that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Background: This study evaluated the effect of nano-silica (NS) incorporation with resin infiltrant on water sorption and solubility of resin infiltrant, mineral density of demineralized enamel, and resin tags penetration., Methods: NS (Sigma-Aldrich, St Louis, Missouri, USA) was added into the resin infiltrant (ICON, DMG, Hamburg, Germany) at two concentrations by weight. The tested groups were: ICON (control), ICON + 0.2, and ICON + 0.5 (n = 10 per group). Water sorption and solubility were assessed using mass variation after 60 days water storage. Mineral density and surface topography were assessed using micro-Computed Tomography scans. Resin tags penetration was measured using a scanning electron microscope. Data were analyzed using one-way Analysis of Variance and Tukey's post-hoc tests (P < .05)., Results: ICON revealed the highest water sorption, solubility mean values (28.90, 7.61) followed by ICON + 0.2 (14.80, 4.82) and ICON + 0.5 (12.32, 0.81) respectively, and vice versa for resin tags penetration. Mineral density of demineralized enamel significantly increased after treatment with ICON + 0.2 and ICON + 0.5., Conclusion: Incorporation of NS to resin infiltrant decreased its water sorption and solubility along with enhancing the mineral density of the demineralized enamel and the penetration of resin tags., Competing Interests: Declarations. Ethics approval and consent to participate: All procedures performed in this study, were carried out in accordance with relevant guidelines and regulations of Helsinki Declarations. The collected premolars were extracted for therapeutic reasons unrelated to the study were collected, with prior informed consent from healthy individuals who were seeking dental care at The Oral and Maxillofacial Surgery Department Clinic, Faculty of Dentistry, Mansoura University. The patients were voluntary donating the extracted teeth to The Faculty for utilizing in research purpose. All the experimental protocols were approved by the Dental Research Ethics Committee of the Faculty of Dentistry, Mansoura University with reference number (A0202024CD). Consent for publication: Not applicable. Competing interests: The authors declare no competing interests., (© 2024. The Author(s).)

Thermoplastic properties in cellulosic materials can be achieved by opening the glucose rings in cellulose and introducing new functional groups. Using molecular dynamics, we simulated amorphous cellulose and eight modified versions under dry and moist conditions. Modifications included ring openings and functionalization with hydroxy, aldehyde, hydroxylamine, and carboxyl groups. These modifications were analyzed for density, glass transition temperature, thermal expansivity, hydrogen bond features, changes in energy term contributions during deformation, diffusivity, free volume, and tensile properties. All ring-opened systems exhibited higher molecular mobility, which, consequently, improved thermoplasticity (processability) compared to that of the unmodified amorphous cellulose. Dialcohol cellulose and hydroxylamine-functionalized cellulose were identified as particularly interesting due to their combination of high molecular mobility at processing temperatures (425 K) and high stiffness and strength at room temperature (300 K). Water and smaller side groups improved processability, indicating that both steric effects and electrostatics have a key role in determining the processability of polymers.

Rational drug design focuses on the explanation and prediction of complex formation between therapeutic targets and small-molecule ligands. As a third and often overlooked interacting partner, water molecules play a critical role in the thermodynamics of protein-ligand binding, impacting both the entropy and enthalpy components of the binding free energy and by extension, on-target affinity and bioactivity. The community has realized the importance of binding site waters, as evidenced by the number of computational tools to predict the structure and thermodynamics of their networks. However, quantitative experimental characterization of relevant protein-ligand-water systems, and consequently the validation of these modeling methods, remains challenging. Here, we investigated the impact of solvent exchange from light (H 2 O) to heavy water (D 2 O) to provide complete thermodynamic profiling of these ternary systems. Utilizing the solvent isotope effects, we gain a deeper understanding of the energetic contributions of various components. Specifically, we conducted isothermal titration calorimetry experiments on trypsin with a series of p -substituted benzamidines, as well as carbonic anhydrase II (CAII) with a series of aromatic sulfonamides. Significant differences in binding enthalpies found between light vs heavy water indicate a substantial role of the binding site water network in protein-ligand binding. Next, we challenged two conceptually distinct modeling methods, the grid-based WaterFLAP and the molecular dynamics-based MobyWat, by predicting and scoring relevant water networks. The predicted water positions accurately reproduce those in available high-resolution X-ray and neutron diffraction structures of the relevant protein-ligand complexes. Estimated energetic contributions of the identified water networks were corroborated by the experimental thermodynamics data. Besides providing a direct validation for the predictive power of these methods, our findings confirmed the importance of considering binding site water networks in computational ligand design.

Cellulose nanocrystals (CNC) have been significantly developed as a building block material for the design of novel functional materials in many fields such as biomedicine, nanotechnology, and materials science due to their excellent optical properties, biocompatibility, and sustainability. Improving the redispersibility of CNC in the sustainable processing of nanocellulose has been a challenge because intense hydrogen bond interaction leads to irreversible aggregation, making CNC difficult to redisperse and increasing the cost of storage and transportation of CNC. Hydroxypropyl cellulose (HPC) is an important hydroxy propylated cellulose ether. As a water-soluble cellulose derivative, HPC has a polyhydroxy structure similar to that of CNC, which leads to good compatibility and high affinity between HPC and CNC. In this work, HPC of different molecular weights was comixed with CNC of different contents, which was then dried using different methods, and the dried samples were redispersed in water. The addition of HPC improved the redispersibility of the CNC. Finally, the redispersed suspension was also redried to form a film, which was found to retain its structure color. These results provide an important avenue for the redispersion of dried CNC and for the development of functional materials from redispersed CNC.

Medical adhesives have been used under surgical conditions. However, it is always a big challenge to maintain long-term adhesion in a water environment. Besides, it usually takes a long time to complete the adhesion, and the operation might be complicated. In this study, tannic acid and gelatin solution under acidic conditions were mixed, flocculated, lyophilized, and crushed; thus, a powdered medical adhesive (POWDER) was prepared with long-lasting adhesion in a water environment, convenience, and low price. Tannic acid bound gelatin and maintained adhesive force primarily through hydrogen bonding and reacted with amino sulfhydryl and other amino acid residues after oxidation into aldehyde, exhibiting excellent underwater adhesion. Oxidized dextran (ODex) powder rich in an aldehyde group was introduced to provide covalent binding in the adhesive. In vitro and in vivo studies showed that POWDER could quickly adhere to various tissues in the water environment. In vitro skin adhesion experiments demonstrated that it could achieve effective adhesion in a water environment for up to 60 days. Its blood compatibility, low cytotoxicity, and biodegradability were also verified. The POWDER developed in this study is of great significance for patients who need rapid wound treatments.

Surface protection is essential when using wood as a construction material. However, the industry lacks sustainable alternatives to replace the presently dominant fossil-based synthetic water-resistant coatings. Here, we show a fully bio-based wood surface protection system using components sourced from birch bark and spruce bark, inspired by the natural barrier function of bark in trees. The coating formulation contains suberinic acids and spruce bark polyphenols, resulting in a waterborne suspension that is safe and easy to apply to wood. The polyphenols play a dual role in the formulation as they stabilize the water-insoluble suberinic acids and serve as nanofillers in the thermally cured coating, enabling the adjustment of the mechanical properties of the resulting coating. When applied to spruce wood, the coating formulation with 10% polyphenol and 90% suberinic acids achieved a water absorption value of 100 g m -2 after 72 hours of water exposure, demonstrating superior performance compared to an alkyd emulsion coating. We conclude that instead of combusting tree bark, it can serve as a valuable resource for wood protection, closing the circle in the wood processing industry.

We performed multiscale simulations of analyte sorption and diffusion in hierarchical porosity models of monolithic silica columns for reversed-phase liquid chromatography to investigate how the mean mesopore size of the chromatographic bed and the analyte-specific interaction with the chromatographic interface influence the analyte diffusivity at various length scales. The reproduced experimental conditions comprised the retention of six analyte compounds of low to moderate solute polarity on a silica-based, endcapped, C 18 stationary phase with water‒acetonitrile and water-methanol mobile phases whose elution strength was varied via the volumetric solvent ratio. Detailed information about the analyte-specific interfacial dynamics received from molecular dynamics simulations was incorporated through appropriate linker schemes into Brownian dynamics diffusion simulations in three hierarchical porosity models received from physical reconstructions of silica monoliths with a mean macropore size of 1.23 µm and mean mesopore sizes of 12.3, 21.3, or 25.7 nm. The mean mesopore size was found to have a similar influence on the effective mesopore diffusivity as the analyte polarity and the mobile-phase elution strength, which together determine the analyte residence time on a column. A smaller mesopore size attenuated the increase of the effective mesopore diffusivity with increasing mobile-phase elution strength significantly. The effective bed diffusivity was limited by the analyte residence time rather than by morphological details of the mesopore space. The stronger an analyte was retained by the chromatographic interface inside the mesopores, the slower became the mass transfer between the pore space hierarchies and the lower was the effective bed diffusivity. The B-terms of the plate height equation were finally generated with the bed diffusivities and phase-based retention factors derived from the hierarchical porosity models using additional information about the stationary-phase limit obtained from the analysis of analyte-bonded phase contacts. The B-terms highlight analyte- and mobile phase-specific behavior relevant to isocratic and gradient elution conditions in chromatographic practice. In particular, U-shaped B-term curves are observed due to the dominating contribution of the retention factor and the bed diffusivity to the B-term at low and high elution strength of the mobile phase, 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.)

Proteins are vital biological macromolecules that execute biological functions and form the core of synthetic biological systems. The history of de novo protein has evolved from initial successes in subordinate structural design to more intricate protein creation, challenging the complexities of natural proteins. Recent strides in protein design have leveraged computational methods to craft proteins for functions beyond their natural capabilities. Molecular dynamics (MD) simulations have emerged as a crucial tool for comprehending the structural and dynamic properties of de novo -designed proteins. In this study, we examined the pivotal role of MD simulations in elucidating the sampling methods, force field, water models, stability, and dynamics of de novo- designed proteins, highlighting their potential applications in diverse fields. The synergy between computational modeling and experimental validation continued to play a crucial role in the creation of novel proteins tailored for specific functions and applications.

Accurate monitoring of glucose levels is essential in the field of diabetes detection and prevention to ensure appropriate treatment planning. Conventional blood glucose monitoring methods, although widely used, are intrusive and frequently result in discomfort. This study investigates the use of Raman spectroscopy as a non-invasive method for estimating glucose concentrations. Our proposition entails employing machine learning models to categorize glucose levels by utilizing Raman spectrum data. The collection consists of deionized water samples containing glucose with defined amounts, guaranteeing great purity and little interference. We assess the efficacy of three machine learning models in categorizing glucose levels which including Extra Trees, Random Forest, and Support Vector Machine (SVM). In addition, we employ data pre-processing techniques such as fluorescence background removal and hotspot series extraction to improve the performance of the model. The primary results demonstrate that the utilization of these pre-processing techniques greatly enhances the accuracy of classification. Among these techniques, the Extra Trees model achieves the highest accuracy, reaching 95%. This study showcases the viability of employing machine learning techniques to forecast glucose levels based on Raman spectroscopy data. Additionally, it emphasizes the significance of data pre-processing in enhancing the accuracy of the model's results., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Quang 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.)

Using the self-consistent reaction field (SCRF) method, the nitrogen isotopic reduction partition function ratio (RPFR), a fundamental physical quantity for theoretical consideration of equilibrium isotope effects, was evaluated by density functional theory (DFT) for 20 proteinogenic and two related amino acids under physiological conditions at pH 7.4. At this pH value, all amino acids were of the zwitterion-type form with α-NH 3 + and α-COO - groups, regardless of the net charge of -1 (monoanion), 0 (zwitterion), or +1 (monocation). The largest RPFR value by far was for proline (Pro). This is due to the fact that the nitrogen atom of Pro has two C-N bonds and two N-H bonds, whereas the α-nitrogen atoms of other amino acids form one C-N bond and three N-H bonds. There was a clear correlation between the RPFR value of α-nitrogen and the distance of the N-H covalent bond of the hydrogen atom involved in the formation of the intramolecular hydrogen bond (HB); the stronger the intramolecular HB, the lower the RPFR value of α-nitrogen. It was suggested that equilibrium isotope effects were partially responsible for the nitrogen isotope fractionation in the enzymatic glutamic acid/aspartic acid transamination and in ammonia assimilation during the formation of glutamine from glutamic acid.

V 4S , a new structural indicator for water specially designed to be suitable for hydration and nanoconfined contexts, has been recently introduced and preliminarily applied for water in contact with self-assembled monolayers and graphene-like systems. This index enabled an accurate detection of defective high local density water molecules (called HDA-like given their structural resemblance with the high-density amorphous ice, HDA). In the present work, we shall apply this new metric to characterize protein hydration water with particular interest in protein binding sites. As a first result, we shall find that protein hydration water has a higher concentration of HDA-like molecular arrangements compared to the bulk. Significantly, we shall show that the concentration of HDA-like molecules sharply decreases beyond the first hydration layer. Finally, we shall also reveal a highly nonuniform spatial distribution of the V 4S values for the first hydration shell on the protein surface, where the higher hydrophobicity inherent to the ligand binding site will be evident from an enrichment in HDA-like molecules as compared to the population exhibited by the global protein surface.

A novel dicyanoisophorone-based colorimetric fluorescent probe 3 has been prepared for recognizing peroxynitrite in aqueous conditions. A large bathochromic shift of the absorption band is observed upon titration with ONOO - , inducing a clearly visible solution color change from yellow to pale pink, which makes "naked-eye" detection possible. Moreover, probe 3 can react instantly with ONOO - and is accompanied by a significant fluorescence enhancement at 621 nm while the detection limit is as low as 37 nM. Most importantly, probe 3 exhibits high selectivity and sensitivity towards ONOO - in the presence of other competitive ions in aqueous solution. Probe 3 has also been successfully applied in living MCF-7 cells, and the results suggest that probe 3 could be applied as a potential candidate for the detection of ONOO - .

This study investigates the application of near-infrared spectroscopy (NIR) for assessing drought resistance in seeds, aiming to offer a rapid and efficient method suitable for large-scale primary screening. NIR spectroscopy is utilized to analyze four key factors (water, sugars, amino acids content, and genes) associated with maize seed drought responses. Signature NIR bands indicative of drought resistance-related molecules are identified using the Competitive Adaptive Reweighted Sampling (CARS) technique. Furthermore, an Improved Discrete Bayesian Optimization Support Vector Machine (ID-BOA-SVM) classification model is developed to address issues related to sparse features in traditional Bayesian Optimization Support Vector Machines (BOA-SVM). To enhance classification performance, a stacking model integrating Random Forest (RF), ID-BOA-SVM, Logistic Regression (LR), and Gradient Boosted Decision Trees (GBDT) classifiers is constructed, ensuring robustness and minimizing overfitting risks. The model achieves satisfactory recognition accuracy (94.28% accuracy, 94% precision, 94.61% recall, and 94.23% F1-score) even under conditions of substantial interference and dataset variability. This research demonstrates that NIR spectroscopy-derived data can support genetic and physiological studies of drought-resistant seed varieties, facilitating a deeper understanding of drought resistance mechanisms and optimizing breeding strategies.

A rapid and reliable evaluation of the aqueous solubility of small molecules is a hot topic for the scientific community and represents a field of particular interest in drug discovery. In fact, aqueous solubility significantly impacts various aspects that collectively influence a drug's overall pharmacokinetics, including absorption, distribution and metabolism. For this reason, in silico approaches that provide fast and cost-effective solubility predictions, can serve as invaluable tools in the early stages of drug development. Although additional molecular features should be considered, accurate solubility predictions can help medicinal chemists rationally planning the synthesis of compounds more likely to exhibit desirable pharmacokinetic properties and in selecting the most promising candidates for further biological testing (e.g., cellular assays) from an initial pool of hit compounds with detected preliminary bioactivity. In this context, we herein report the development and evaluation of WaSPred, our AI-based water solubility predictor for small molecules. WaSPred not only showed high reliability in water solubility predictions performed on structurally heterogeneous compounds, belonging to multiple external datasets, but also demonstrated superior performance compared to a set of other commonly used water solubility predictors, thus confirming its state-of the-art robustness and its usefulness as an in silico approach for water solubility evaluations.., 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.)

Tire wear particles (TWPs) are considered as an emerging threat to soil fauna. However, how TWP toxicity to soil fauna responds to the stress of soil moisture and temperature remains unclear. We assessed the toxicity of environmentally relevant TWPs to the soil model species Enchytraeus crypticus under three soil moisture and two temperature gradients. Typical thermoplastic polypropylene (PP) was selected for comparison. Results showed that compared with PP, TWPs exerted stronger toxicity, including decreasing the worm growth, survival and reproduction rates, disturbing the soil and worm gut microbiota, and leaching more diverse and higher contents of additives. Stress of soil moisture and temperature exacerbated TWP toxicity mainly through affecting the leaching and transformation of additives. Fourteen mediated additives significantly contributed to the shift of the gut microbiota under soil moisture and temperature stress, among which 1,3-diphenylguanidine, N,N'-bis(methylphenyl)-1,4-benzenediamine quinone, N-tert-butyl-2-benzothiazolesulfenamide, and 2-aminobenzothiazole were identified as the main drivers. In addition, this study provided the first clear evidence that increased soil moisture and temperature promoted the transformation of additives in the soil. Our study revealed the non-negligible aggravated toxicity of TWPs to soil fauna under stress of soil moisture and temperature, providing novel insights into the environmental behavior of additives., 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.)

Positron Emission Tomography (PET) is used in oncology for tumor diagnosis, commonly relying on fluorine-18 ( 18 F) emission detection. The conventional method of 18 F incorporation on to probes by covalent bonding is harsh for sensitive biomolecules, which are nonetheless compounds of choice for the development of targeted probes. This study explores gallium- 18 F (Ga 18 F) coordination, a milder alternative method occurring in aqueous media at the final stage of radiosyntheses. Pyclen-based chelating agents were proposed to capture (GaF) species at room temperature and pH≥5 making the radiofluorination process compatible with heat- and acid-sensitive biomolecules. Highly promising results were obtained with the PC2A-based chelating agent LH 2 derived from the new bifunctional PC2A-OAE-NCS compound. The solid-state structure of GaF(L) was elucidated by X-ray diffraction and revealed an unconventional heptacoordination of Ga(III). A high radiochemical conversion (RCC) of 86 % was achieved at room temperature, in water at pH 5 within 20 minutes. Stability studies showed the robustness of the GaF(L) complex in aqueous media for at least one day and at least one hour for the radiolabeled analog Ga 18 F(L). These findings demonstrated that PC2A-based compounds are chelating agents of choice for (Ga 18 F) species, suggesting a real technological breakthrough for PET imaging and precision medicine., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

In the pharmaceutical industry, filtration is traditionally carried out in batch mode. However, with the spread of continuous technologies, there is an increasing demand for robust continuous filtration strategies suitable for processing suspensions produced in continuous crystallizers. Accordingly, this study aimed to investigate a lab-scale horizontal conveyor belt filtration approach for pharmaceutical separation purposes for the first time. The newly developed continuous horizontal belt filter (CHBF) was tested under different systems (microcrystalline cellulose (MCC)/water, lactose/ethanol and acetylsalicylic acid (ASA)/water) and diverse conditions. Filtration was robust using a well-defined unimodal particle size distribution MCC in water system, where the residual moisture content varied within narrow limits of 45-52% independently from the process conditions. Besides, the residual moisture content highly depended on the applied solvent and particle size. It could be reduced to below 2% by processing the suspensions of either a volatile solvent (lactose in ethanol) or an aqueous slurry of a large particle size ASA. Finally, the CHBF was connected to a mixed suspension mixed product removal (MSMPR) or a plug flow crystallizer (PFC). The residual moisture content of the CHBF-filtered ASA product and operation characteristics (onset of steady-state) were evaluated in both continuous crystallizer-filter systems. The MSMPR-CHBF system operated with a longer startup period. The size of the in situ-produced crystals was of a similar order magnitude in both systems, resulting in a similar residual moisture content (around 20%). Overall, the tested continuous filter was robust, did not modify the crystal morphology in the examined experimental range, and could be effectively integrated with continuous crystallizers., 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.)

Plasma-activated water (PAW) is a novel antimicrobial agent with negligible toxicity and environmental burden, holding promise as an alternative to chemical disinfectants and antibiotics. In practice, liquid disinfectants are often soaked with cotton materials before further use. Rich in reducing functional groups on the surface, cotton will inevitably react with PAW, leading to the deterioration of PAW's functions. To resolve this issue, this work proposes a new concept of "secondary activation" for retaining and enhancing PAW's bioactivity, i.e., pre-treating cotton with air plasma before soaking PAW. For the first time, we find that the PAW absorbed by raw cotton completely loses its bactericidal effect, while plasma-treated cotton (PTC) restores the disinfection capacity and prolongs its effective duration. This restoration is attributed to the absorption of plasma-generated reactive species by cotton with oxidizing and nitrifying modifications on the fiber surface. Consequently, the concentrations of aqueous species in PAW increase rather than decrease after absorption by PTC. In addition, the PTC after 28-day storage can still enable PAW to achieve a bacterial reduction of ∼3 logs. This work identifies and addresses a crucial limitation in the disinfection application of PAW and elucidates the mechanism underlying PTC production and secondary activation of PAW., 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.)

Idiopathic pulmonary fibrosis (IPF) is a progressive respiratory disease with no known cause. It is characterized by widespread inflammation and structural abnormalities in the alveoli of the lungs, ultimately leading to the development of pulmonary fibrosis. Triptolide (TP), an epoxy-diterpene lactone compound known for its potent anti-inflammatory and antifibrotic effects, was limited clinical use due to poor water solubility and side effects. Two soluble TP prodrugs (PG490-88 and Minnelide) have entered clinical research. However, their activities are based on enzyme metabolism, which is influenced by species-specific differences. In this study, we present water-soluble TP derivatives synthesized by introducing ethylenediamine carbamate groups (TP-DEAs) at the 14-hydroxy position. The introduced groups were found to spontaneously convert into the parent drug through enzyme-independent metabolic conversion. The water solubility and stability of the compounds were examined in vitro. Notably, TP-DEA2 exhibited high water solubility (30.8 mg/mL), exceeding TP solubility by more than 1181-fold. In vitro, TP-DEA2 converted to TP autonomously without the involvement of enzymes. In addition, TP-DEA2 can inhibit the expression of a disintegrin and metalloproteinase 10 (ADAM 10) induced by TGF-β1 and reduce the secretion of a-SMA in fibroblasts. In vivo, TP-DEA2 transformed into TP, effectively inhibiting fibrosis in the bleomycin group without observed toxicity. Importantly, positive outcomes when administering TP-DEA2 at a later stage post-bleomycin exposure suggest its potential role in treating IPF., 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 Masson SAS. All rights reserved.)

Recent studies have indicated that soil contamination with microplastics (MPs) can negatively affect agricultural productivity, although these effects vary greatly depending on the context. Furthermore, the mechanisms behind these effects remain largely unknown. In this study, we examined the impact of two concentrations of polypropylene (PP) fibers in the soil (0.4 % and 0.8 % w/w) on soybean growth, nitrogen uptake, biological nitrogen fixation (BNF), and water use efficiency by growing plants in two soil types, with and without arbuscular mycorrhizal fungi (AMF). PP contamination consistently reduced vegetative growth (-12 %, on average compared to the control), with the severity of this effect varying significantly by soil type (more pronounced in Alfisol than in Vertisol). The extent of BNF progressively reduced with the increase in PP contamination level in both soils (on average, -17.1 % in PP0.4 and -27.5 % in PP0.8 compared to the control), which poses clear agro-environmental concerns. Water use efficiency was also reduced due to PP contamination but only in the Alfisol (-9 %, on average). Mycorrhizal symbiosis did not seem to help plants manage the stress caused by PP contamination, although it did lessen the negative impact on BNF. These findings are the first to demonstrate the effect of PP on BNF in soybean plants, underscoring the need to develop strategies to reduce PP pollution in the soil and to mitigate the impact of PP on the functionality and sustainability of agroecosystems., 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.)

Natural product evodiamine (Evo) and its synthetic derivatives represent an attractive dual Topo 1/2 inhibitors with broad-spectrum antitumor efficacy. However, the clinical applications of these compounds have been impeded by their poor aqueous solubility. Herein, a series of water-soluble 10-substituted-N(14)-phenylevodiamine derivatives were designed and synthesized. The most potent compound 45 featuring a quaternary ammonium salt fragment achieved robust aqueous solubility and nanomolar potency against a panel of human hepatoma cell lines Huh7, HepG2, SK-Hep-1, SMMC-7721, and SMMC-7721/DOX (doxorubicin-resistant cell). Further studies revealed that 45 could inhibit Topo 1 and Topo 2, induce apoptosis, arrest the cell cycle at the G2/M stage and inhibit the migration and invasion. Compound 45 exhibited potent antitumor activity (TGI = 51.1 %, 10 mg/kg) in the Huh7 xenograft model with acceptable safety profile. In addition, a 21-day long-term dose toxicity study confirmed that the maximum tolerated dose of compound 45 was 20 mg/kg. Overall, this study presented a promising Evo-derived candidate for the treatment of hepatocellular carcinoma., 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 Masson SAS. All rights reserved.)

Nitrobenzothiazinones (BTZs) represent a novel type of antitubercular agents targeting DprE1. Two clinical candidates BTZ043 and PBTZ169, as well as many other BTZs showed potent anti-TB activity, but they are all highly lipophilic and their poor aqueous solubility is still a serious issue need to be addressed. Here, we designed and synthesized a series of new BTZ derivatives, wherein a hydrophilic COOH or NH 2 group is directly attached to the oxime moiety of TZY-5-84 discovered in our lab, through various linkers. Two compounds 1a and 3 were first reported to possess excellent activity against MTB H 37 Rv and MDR-MTB strains (MIC: <0.029-0.095 μM), low toxicity and acceptable oral PK profiles, as well as significantly improved water solubility (1200 and > 2000 μg/mL, respectively), suggesting they may serve as promising hydrophilic BTZs for further antitubercular drug discovery., 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 Masson SAS. All rights reserved.)

Ethnopharmacological Relevance: Rheum palmatum (RP) is a widely used traditional herb, which possesses antioxidant properties, inhibits ROS production and reduces fever., Aim of the Study: The aim of this study was to examine the antioxidative properties of the water extract of RP on oxidative-stressed mice., Materials & Methods: Forty mice were administered with DL-homocysteine (DL-Hcy) to induce oxidative stress and were divided into four groups: 1) CK: NaCl and water; 2) DL-Hcy: DL-Hcy and water; 3) DL-Hcy+50RP: DL-Hcy with 50 mg kg -1 body weight (BW) d -1 RP; and 4) DL-Hcy+150RP: DL-Hcy with 150 mg kg -1 BW d -1 RP. Rhein (0.3 mg g -1 dry matter) was the main active ingredient in RP., Results: When compared with Dl-Hcy mice, the mice with supplementary RP mitigated oxidative stress by reducing the liver concentrations of superoxide dismutase (SOD) by 27% and glutathione peroxidase (GSH-Px) by 32%, and the reactive oxygen species (ROS) in the kidney and spleen. These responses were more pronounced in DL-Hcy+150RP than DL-Hcy+50RP mice. RP also exhibited therapeutic effects on liver steatosis, chronic kidney nephritis and intestinal villus width shortening caused by oxidative stress, and concomitantly decreased the serum glucose concentration (RP vs. DL-HCY, 2.3 vs. 4.1 mmol L -1 )., Conclusion: It was concluded that RP possesses antioxidant and therapeutic properties that can mitigate lesions on organs and prevent diabetes in oxidative-stressed mice. This study highlights the potential of RP as a medicinal supplement for animals in the 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 Elsevier B.V. All rights reserved.)

Calcium ions (Ca 2+ ) are key players in intracellular signaling as second messengers and play a pivotal role in various physiological processes. In this study, near-infrared water-soluble AgInS 2 quantum dots (AIS QDs) for Ca 2+ detection were synthesized by a one-step hydrothermal method. The fluorescence quantum yield (PL QY) of the quantum dots was as high as 23.99 %. With low cytotoxicity and good fluorescence properties, as well as short reaction time, the ternary AIS QDs have excellent synthesis efficiency and quantum yield, which are advantageous for Ca 2+ detection and bioimaging applications. The fluorescence quenching of the quantum dots showed a clear linear relationship with calcium ion concentration in the range of 0-250 μM (detection limit: 0.65 μM). Confocal imaging experiments demonstrate the excellent biofluorescence imaging capability of AIS QDs. By tuning the Ag/In molar ratio, AIS QDs can achieve fluorescence emission in the near-infrared wavelength band (620-700 nm), and the near-infrared fluorescence imaging has deeper tissue penetration, less tissue absorption and photodamage, and lower interference of spontaneous fluorescence, which further expands the potential of QDs for bioimaging 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 B.V. All rights reserved.)

Ethnopharmacological Relevance: Ischemia-reperfusion (IR) injury can result in acute renal failure. Oxidative stress is a major factor in IR-induced cell death in the kidneys. According to traditional Chinese medicine, earthworms (Pheretima aspergillum) can be used to treat various kidney diseases., Aim of the Study: The present study was designed to understand the protective effects of the water extract of earthworms (WEE) against oxidative stress on the kidneys and the crucial molecular events associated with its nephroprotective activity., Materials and Methods: Cytotoxicity caused by H 2 O 2 in HEK293, HK2, and primary mouse renal tubular epithelial cells (TECs) was used to investigate the effect of WEE on oxidative stress-induced renal injury in vitro. IR-induced kidney injury was established using rats as an in vivo model. The WEE-mediated protection of the kidneys against oxidative stress was compared with that of glutathione, a common antioxidant used as a positive control., Results: In HEK293 cells, HK2 cells, and primary mouse TECs, WEE relieved H 2 O 2 -induced mitochondrial damage, apoptosis, and ferroptosis. In kidney cells, WEE increased the expression of Sirt1, boosted LKB1 and AMPK phosphorylation, and upregulated nuclear Nrf2. Suppression of Sirt1 and LKB1 knock down abrogated WEE-induced protection against H 2 O 2 . WEE ameliorated IR-induced kidney injury and intrarenal inflammation in rats. In rat kidneys, WEE mitigated mitochondrial damage and suppressed IR-induced apoptosis and ferroptosis. Mechanistically, WEE increased Sirt1 expression, enhanced the phosphorylation of LKB1 and AMPK, and increased intranuclear Nrf2 levels in IR kidneys. IR treatment resulted in considerable increase in renal MDA levels and a prominent decrease in antioxidative enzyme activity. These lesions were significantly alleviated by WEE., Conclusions: WEE mitigated H 2 O 2 -induced cytotoxicity in kidney cells in vitro and improved IR-induced kidney damage in rats. Mechanistically, WEE potentiated the Sirt1/Nrf2 axis and relieved mitochondrial damage in the kidney cells. These events inhibited the apoptosis and ferroptosis induced by oxidative stress. Our findings support the potential application of WEE for the clinical treatment of kidney diseases caused by intrarenal oxidative stress., Competing Interests: Declaration of Competing interest Authors have no conflict of interest to declare., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Two novel fluorescent probes for Cu 2+ detection have been developed based on thiazoline-quinoline conjugates bearing a 4-ethynyl-N,N-dimethylaniline unit (QT1 and QT2). QT2 exhibits instantaneous fluorescence quenching of Cu 2+ with an emissive change from bright orange to arctic blue under UV light irradiation (365 nm). The plots of I 0 /I against Cu 2+ concentrations show a good linear relationship that ranges from 0 to 50 µM with a coefficient of determination (R 2 ) = 0.9906 and a limit of detection (LOD) of 76 nM, which is considered low (4.84 ppb). A 1:1 complexation between QT2 and Cu 2+ was confirmed by UV-Vis titration, ESI-MS, and SC-XRD. The QT2·Cu 2+ complex was dissociated by the addition of EDTA. The fluorescence quenching mechanism involves the ligand-to-metal charge transfer (LMCT) of a paramagnetic Cu 2+ complex. The QT2 probe on a paper-based strip was used to determine the amount of Cu 2+ in water and food samples (shiitake mushrooms and oysters)., 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.)

Iron ion (Fe 3+ ) detection is crucial for human health since it plays a crucial role in many physiological activities. In this work, a novel Schiff-base functionalized cyanine derivative (CyPy) was synthesized, which was successfully assembled on the surface of upconversion nanoparticles (UCNPs) through an amphiphilic polymer encapsulation method. In the as-designed nanoprobe, CyPy, a recognizer of Fe 3+ , is served as energy donor and β-NaYF 4 :Yb,Er upconversion nanoparticles are adopted as energy acceptor. As a result, a 93-fold enhancement of upconversion luminescence is achieved. The efficient energy transfer from CyPy to β-NaYF 4 :Yb,Er endows the nanoprobe a high sensitivity for Fe 3+ in water with a low detection limit of 0.21 μM. Moreover, the nanoprobe has been successfully applied for Fe 3+ determination in human serum and tap water samples with recovery ranges of 95 %-105 % and 97 %-106 %, respectively. Moreover, their relative standard deviations are all below 3.72 %. This work provides a sensitive and efficient methodology for Fe 3+ detection in clinical and environmental testing., 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.)

Packaged coconut water offers various options, from pure to those with added sugars and other additives. While the purity of coconut water is esteemed for its health benefits, its popularity also exposes it to potential adulteration and misrepresentation. To address this concern, our study combines Fourier transform infrared spectroscopy (FTIR) and machine learning techniques to detect potential adulterants in coconut water through classification models. The dataset comprises infrared spectra from coconut water samples spiked with 15 different types of potential sugar substitutes, including: sugars, artificial sweeteners, and sugar alcohols. The interaction of infrared light with molecular bonds generates unique molecular fingerprints, forming the basis of our analysis. Departing from previous research predominantly reliant on linear-based chemometrics for adulterant detection, our study explored linear, non-linear, and combined feature extraction models. By developing an interactive application utilizing principal component analysis (PCA) and t-distributed stochastic neighbor embedding (t-SNE), non-targeted sugar adulterant detection was streamlined through enhanced visualization and pattern recognition. Targeted analysis using ensemble learning random forest (RF) and deep learning 1-dimensional convolutional neural network (1D CNN) achieved higher classification accuracies (95% and 96%, respectively) compared to sparse partial least squares discriminant analysis (sPLS-DA) at 77% and support vector machine (SVM) at 88% on the same dataset. The CNN's demonstrated classification accuracy is complemented by exceptional efficiency through its ability to train and test on raw data., 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.)

Large household water storage containers are among the most productive habitats for Aedes aegypti (Linnaeus, 1762), the primary mosquito vector for dengue and other arboviral pathogens. Increasing concerns for insecticide resistance and larvicide safety are limiting the successful treatment of large household water storage containers, which are among the most productive habitats for Aedes juveniles. The recent development of species-specific RNAi-based yeast larvicides could help overcome these problems, particularly if shelf stable ready-to-use formulations with significant residual activity in water can be developed. Here we examine the hypothesis that development of a shelf-stable controlled-release RNAi yeast formulation can facilitate lasting control of A. aegypti juveniles in large water storage containers. In this study, a dried inactivated yeast was incorporated into a biodegradable matrix containing a mixture of polylactic acid, a preservative, and UV protectants. The formulation was prepared using food-grade level components to prevent toxicity to humans or other organisms. Both floating and sinking versions of the tablets were prepared for treatment of various sized water containers, including household water storage tank-sized containers. The tablets passed accelerated storage tests of shelf life stability and demonstrated up to six months residual activity in water. The yeast performed well in both small and large containers, including water barrels containing 20-1000 larvae each, and in outdoor barrel trials. Future studies will include the evaluation of the yeast larvicide in larger operational field trials that will further assess the potential for incorporating this new technology into integrated mosquito control programs worldwide., Competing Interests: Competing interests: The funders of this work did not play a role in the design of this study, in the collection, analyses, or interpretation of data, in the writing of the manuscript, nor in the decision to publish the results of this investigation. The opinions, interpretations, conclusions and recommendations are those of the manuscript’s authors and are not necessarily endorsed by the U.S. Army Medical Research Acquisition Activity. In the conduction of research utilizing recombinant DNA, the investigator adhered to NIH Guidelines for research involving recombinant DNA molecules. Although MDS and DWS are inventors on U.S. patent No: 62/361,704, European Application No. 17828458.4, which was filed by Indiana University, this did not affect their interpretations of the data presented in this manuscript and does not impact their adherence to journal policies on sharing data and materials. The research findings presented herein are not related to any products or services currently provided by any third parties. Although MDS is serving as a guest editor for the Vector Control for Neglected Diseases Collection, she had no involvement with the review of this manuscript at Scientific Reports. The other authors declare that they have no competing interests., (© 2024. The Author(s).)

While hydrogel-based flexible sensors find extensive applications in fields such as medicine and robotics, their performance can be hindered by the rapid evaporation of water, leading to diminished sensitivity and mechanical durability. Despite the exploration of some effective solutions, such as introducing organic solvents, electrolytes, and elastomer composites, these approaches still suffer from problems including diminished conductivity, interface misalignment, and insufficient protection under dynamic conditions. Inspired by cell membrane structures, we developed an adaptive lipid-integrated bilayer coating (ALIBC) to enhance water retention in hydrogel-based sensors. Lipid layers and long-chain amphiphilic molecules are used as compact coating and anchoring agents on the hydrogel surface, mimicking the roles of lipids and membrane proteins in cell membranes, while spare lipids from aggregates within hydrogels can migrate to the surface to combat dehydration under deformation. This lipid-integrated bilayer coating prevents the water evaporation of hydrogels at both static and dynamic states without affecting the inherent flexibility, conductivity, and no cytotoxicity. Hydrogel-based sensors with ALIBC exhibited significantly enhanced performance in conditions of body temperature, extensive deformation, and long-term dynamic sensing. This work presents a general approach for precisely controlling the water-retaining capacity of hydrogels and hydrogel-based sensors without compromising their intrinsic physical properties., Competing Interests: Competing interests: The authors declare that they have no competing interests., (© 2024. The Author(s).)