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Molecules, Volume 30, Issue 22 (November-2 2025) – 168 articles

Cover Story (view full-size image): Saffron (Crocus sativus L.) is rich in bioactive apocarotenoids with antioxidant, neuroprotective, and anticancer properties. To enhance its therapeutic efficacy, stigmas were extracted and purified via solid-phase extraction to enrich crocin and picrocrocin fractions. These extracts were included in liposomes prepared by the reverse-phase evaporation method, with saturated or unsaturated lipids used to enhance their bioavailability and gastrointestinal absorption by oral administration while protecting them from the harsh gastric environment and to promote their release in the gastrointestinal tract. Results indicate that liposomes show greater encapsulation capacity for hydrophilic apocarotenoids, supporting their use in improving the stability and bioavailability of saffron extracts for nutraceutical and pharmaceutical applications. View this paper
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15 pages, 1894 KB  
Article
Assessment of ADC Higher Order Structure Through 2D NMR Analysis
by Emily M. Grasso, Angela N. Marquard, Zachary Sparta, David Fry and Nareshkumar Jain
Molecules 2025, 30(22), 4490; https://doi.org/10.3390/molecules30224490 - 20 Nov 2025
Viewed by 1036
Abstract
Antibody–drug conjugates (ADCs) represent a growing class of important chemotherapeutic molecules. Our understanding of the physical properties of the antibody, linker, and payload is still quite limited, but a better understanding may lead to superior ADCs. Biomolecular NMR has shown promise in the [...] Read more.
Antibody–drug conjugates (ADCs) represent a growing class of important chemotherapeutic molecules. Our understanding of the physical properties of the antibody, linker, and payload is still quite limited, but a better understanding may lead to superior ADCs. Biomolecular NMR has shown promise in the characterization of antibody higher-order structure, suggesting that the same should be true for ADCs. We applied 2D NMR techniques to trastuzumab alone and to trastuzumab conjugated to MMAE and DXd linker-payloads at drug-antibody ratios (DAR) 2, 4, and 8 to assess the effects of drug conjugation on antibody higher-order structure. Trastuzumab alone generated high-quality NMR spectra under a variety of temperatures and concentrations. Spectra of low DAR species were remarkably similar both to each other and to the free antibody, except for notable new peaks in the spectra from the linker-payloads. Increasing DAR resulted in the disappearance of many well-dispersed peaks; at the highest DAR, both T-MMAE and T-DXd showed a global broadening of signals, although this effect was more extreme in T-MMAE. These spectra demonstrate the promise of biomolecular NMR to provide a direct window into the solution behavior of ADCs. Full article
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24 pages, 8509 KB  
Article
Ganoderma lucidum Glycoprotein Microemulsion: Improved Transdermal Delivery and Protective Efficacy in UV-Induced Cell and Animal Models
by Ye Jin, Xushuang Jia, Dongmei Fan, Xuyan Zhou, Xiao Tan, Da Liu, Ning Cui and Jiawei Wen
Molecules 2025, 30(22), 4489; https://doi.org/10.3390/molecules30224489 - 20 Nov 2025
Viewed by 660
Abstract
Background: Photoaging, induced by chronic ultraviolet (UV) exposure, is a multifactorial skin disorder characterized by oxidative stress, inflammation, and extracellular matrix degradation. Ganoderma lucidum glycoprotein (Gl-Gp) exhibits potent antioxidant activity, but its topical application is limited by poor transdermal permeability. This study aimed [...] Read more.
Background: Photoaging, induced by chronic ultraviolet (UV) exposure, is a multifactorial skin disorder characterized by oxidative stress, inflammation, and extracellular matrix degradation. Ganoderma lucidum glycoprotein (Gl-Gp) exhibits potent antioxidant activity, but its topical application is limited by poor transdermal permeability. This study aimed to develop a microemulsion-based system to enhance Gl-Gp delivery and evaluate its anti-photoaging efficacy. Methods: Gl-Gp was extracted and purified from G. lucidum fruiting bodies and structurally characterized for O-glycosidic linkages and O-GlcNAc modifications. Fourier-transform infrared (FT-IR) spectroscopy further confirmed the polysaccharide–protein complex structure of Gl-Gp. A water-in-oil Gl-Gp microemulsion was prepared and assessed in vitro for antioxidant and cytoprotective effects in HaCaT cells, including reactive oxygen species (ROS) reduction, mitochondrial membrane potential stabilization, and apoptosis inhibition. Transdermal penetration was compared with aqueous Gl-Gp. In vivo efficacy was evaluated in a UV-induced rat model by measuring skin morphology, histology, oxidative stress markers, matrix metalloproteinases, and proinflammatory cytokines. Results: The microemulsion enhanced Gl-Gp stability and transdermal delivery. In vitro, it reduced ROS, preserved mitochondrial function, and decreased apoptosis in HaCaT cells. In rats, topical application attenuated erythema and epidermal hyperplasia, promoted dermal restoration, increased SOD and GSH-Px activities, and decreased MDA, hydroxyproline, MMPs, and inflammatory mediators. Conclusions: The Gl-Gp microemulsion exerts antioxidant, anti-inflammatory, and anti-collagen-degrading effects, representing a promising strategy for transdermal delivery and topical prevention of photoaging. Full article
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18 pages, 501 KB  
Article
Adaptive Serum Biochemistry Responses to Ethanol Administration in a Mouse Model: Implications for Metabolic Regulation Under Analgesia
by Bożena Witek, Krzysztof Wróbel, Grażyna Świderska-Kołacz, Szymon Zmorzyński, Anna Wojciechowska and Joanna Czerwik-Marcinkowska
Molecules 2025, 30(22), 4488; https://doi.org/10.3390/molecules30224488 - 20 Nov 2025
Viewed by 370
Abstract
Analgesia, or reduced pain sensitivity, can result from pharmacological or stress-induced mechanisms, but human studies are limited by complex physiological and psychological variables. This study aimed to evaluate the impact of ethanol consumption on key metabolic markers in two genetically distinct mouse lines [...] Read more.
Analgesia, or reduced pain sensitivity, can result from pharmacological or stress-induced mechanisms, but human studies are limited by complex physiological and psychological variables. This study aimed to evaluate the impact of ethanol consumption on key metabolic markers in two genetically distinct mouse lines selectively bred for pain sensitivity: high analgesia (HA) and low analgesia (LA). Forty-eight male Swiss-Webster mice were randomly assigned to four groups: HA and LA with or without heavy alcohol (ethanol) exposure. Blood serum was analyzed for its lipid profile, enzymatic activity, electrolyte levels and regulatory/energetic compounds. In HA mice, ALAT and AspAT activities and, albumin, creatinine, iron, and potassium levels were elevated, whereas glucose and sodium levels were decreased. LA mice presented increased bilirubin, cholesterol, LDL, HDL, and lipase activity. ChE, LDH, and CK activities differed significantly between the HA and LA groups. Ethanol intake influenced potassium, magnesium, and sodium serum concentrations. Discriminant analysis highlighted distinct biochemical profiles depending on the LA and HA groups. HA mice predominantly exhibit cytolytic liver damage, altered muscle metabolism, and increased iron levels, indicating oxidative stress. HA and LA display distinct adaptive metabolic strategies: protein/muscle and lipid/electrolyte metabolism, respectively. Genetic differences between HA and LA mice determine different metabolic responses to ethanol. Full article
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30 pages, 1332 KB  
Review
In Vivo Behavior of Biomimetic Nanoparticles: Strategies for Clearance Avoidance, Targeting, and Functional Delivery
by Polina Lazareva, Vladimir Chulanov, Dmitry Kostyushev and Maxim Abakumov
Molecules 2025, 30(22), 4487; https://doi.org/10.3390/molecules30224487 - 20 Nov 2025
Viewed by 787
Abstract
Biomimetic cell membrane-coated nanoparticles (BMCNPs) are an attractive drug delivery platform that combines the advantages of an inorganic core with the biological functionality of a natural cell membrane. This hybrid design merges the versatility of engineered nanomaterials with the complexity and specificity of [...] Read more.
Biomimetic cell membrane-coated nanoparticles (BMCNPs) are an attractive drug delivery platform that combines the advantages of an inorganic core with the biological functionality of a natural cell membrane. This hybrid design merges the versatility of engineered nanomaterials with the complexity and specificity of biological systems, enabling prolonged circulation, immune evasion, enhanced tissue targeting, and improved therapeutic efficacy. In this review, we explore the in vivo behavior of BMCNPs, focusing on their interactions with biological barriers, including evasion of mononuclear phagocyte system clearance, biodistribution patterns, and circulation kinetics. We also examine how membrane source and surface properties influence targeting efficiency and delivery outcomes, while highlighting key considerations and emerging strategies to optimize therapeutic performance and translational potential. Full article
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15 pages, 1210 KB  
Article
Theoretical-Experimental Analysis to Elucidate the Mechanism of Action of Novel Anabolic Agents
by Israel Quiroga, Maura Cardenas-Garcia, María Guadalupe Hernández-Linares, Gabriel Guerrero-Luna and Fermín Flores-Manuel
Molecules 2025, 30(22), 4486; https://doi.org/10.3390/molecules30224486 - 20 Nov 2025
Viewed by 468
Abstract
Research into muscle tissue pathologies offers great opportunities for new pharmaceutical agents. Current therapies, including corticosteroids and immunosuppressants, have limited efficacy and significant adverse effects. In this context, steroidal hydrazone compound 4d was investigated for its ability to promote muscle growth and regeneration [...] Read more.
Research into muscle tissue pathologies offers great opportunities for new pharmaceutical agents. Current therapies, including corticosteroids and immunosuppressants, have limited efficacy and significant adverse effects. In this context, steroidal hydrazone compound 4d was investigated for its ability to promote muscle growth and regeneration as a potential anabolic and regenerative modulator. Flow cytometry analysis showed that 4d significantly increases cell populations in S phase, indicating a strong proliferative stimulus in pathways regulated by TNF-α, AKT, MAFbX, and SMAD2/3. Molecular docking studies showed that 4d shares strong interactions with the known MasR agonist (EP-2825), exhibiting a higher predicted binding affinity. Furthermore, 4d demonstrated the ability to interact with ACVR1/2A receptors, mimicking the binding profiles of known antagonists and potentially inhibiting myostatin/SMAD signaling. Taken together, experimental and computational evidence supports a dual-mechanistic model in which 4d promotes muscle proliferation and regeneration by (1) activating the MasR–PI3K/AKT/mTOR axis and (2) inhibiting the ACVR1/2A–SMAD pathway, counteracting the action of myostatin. These findings position compound 4d as a promising therapeutic candidate against muscle wasting disorders, including cancer-related cachexia, by inducing a robust and multifactorial anabolic response. Full article
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23 pages, 1826 KB  
Review
System Design in CO2 Electrolysis: Integrating Value-Added Anode Reactions with Cathodic Reduction
by Yuehui Zhai, Chong Wang and Zheng Chen
Molecules 2025, 30(22), 4485; https://doi.org/10.3390/molecules30224485 - 20 Nov 2025
Viewed by 757
Abstract
Paired electrolysis represents a paradigm shift in overcoming the energy intensity of conventional CO2 electrolysis. By supplanting the oxygen evolution reaction with value-added anodic oxidations, this technology simultaneously slashes energy demands and diversifies output. This review critically synthesizes design principles for pairing [...] Read more.
Paired electrolysis represents a paradigm shift in overcoming the energy intensity of conventional CO2 electrolysis. By supplanting the oxygen evolution reaction with value-added anodic oxidations, this technology simultaneously slashes energy demands and diversifies output. This review critically synthesizes design principles for pairing these anodic reactions with two key cathode pathways, namely CO2 electroreduction and electrocarboxylation, supported by an analysis of pioneering systems from the past three years. We further explore advanced reactor designs for co-production, and the pivotal role of operando characterization and machine learning in unraveling complex mechanisms. We conclude with a perspective on the key challenges and pathways to industrial adoption, aiming to bridge fundamental advances with practical implementation. Full article
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17 pages, 1295 KB  
Article
Physicochemical Profiling, Bioactive Properties, and Spectroscopic Fingerprinting of Cow’s Milk from the Pampas Valley (Tayacaja, Peru): A Chemometric Approach to Geographical Differentiation
by Eudes Villanueva, Harold P. J. Ore-Quiroz, Gino P. Prieto-Rosales, Raquel N. Veliz-Sagarvinaga, Yaser M. Chavez-Solano, Elza Aguirre, Gustavo Puma-Isuiza and Beetthssy Z. Hurtado-Soria
Molecules 2025, 30(22), 4484; https://doi.org/10.3390/molecules30224484 - 20 Nov 2025
Viewed by 594
Abstract
This study aimed to characterize the physicochemical and functional properties of bovine milk from four districts (Acraquia, Ahuaycha, Pampas, and Daniel Hernández) of the Pampas Valley, Tayacaja province, Huancavelica (Peru), and assess its geographical traceability using vibrational spectroscopy and chemometric tools. Milk samples [...] Read more.
This study aimed to characterize the physicochemical and functional properties of bovine milk from four districts (Acraquia, Ahuaycha, Pampas, and Daniel Hernández) of the Pampas Valley, Tayacaja province, Huancavelica (Peru), and assess its geographical traceability using vibrational spectroscopy and chemometric tools. Milk samples were analyzed for composition (fat, protein, lactose, salts), fatty acid profile, total phenolic compounds (TPC), antioxidant capacity (AC), and spectral features using mid-infrared (MIR) and Raman spectroscopy. The results revealed significant compositional differences among localities, particularly in fat, protein, and salt content, with Daniel Hernández milk showing higher nutritional density. The fatty acid profile, although statistically similar across districts, highlighted a favorable nutritional composition dominated by oleic, palmitic, and stearic acids. TPC and AC values were homogeneous among districts, reflecting similar feeding and management practices. Molecular vibration analysis via MIR and Raman spectroscopy allowed for the identification of key biochemical differences, particularly in lipid and carbohydrate regions. SIMCA classification models, based on MIR spectral data, successfully discriminated samples by origin with Inter-Class Distance (ICD) values exceeding 3, confirming statistically significant separation. Discriminating power plots revealed that proteins (amide I), lactose (C–O, C–C), and lipid-associated bands (C=O, CH2) were major contributors to class differentiation. These findings demonstrate the effectiveness of combining spectroscopic and chemometric approaches to trace the geographical origin of milk and provide scientific support for potential quality labeling systems. This methodology contributes to ensuring product authenticity, promoting regional value-added dairy production, and supporting sustainable rural development in high-Andean ecosystems. Full article
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10 pages, 900 KB  
Article
Cytotoxic Cytochalasans from Sponge-Derived Aspergillus sp. SCSIO 41044
by Xiaoyan Pang, Ini Wong, Qinlin Cao, Junfeng Wang, Xuefeng Zhou, Bin Yang, Junjian Wang, Hong Wang and Yonghong Liu
Molecules 2025, 30(22), 4483; https://doi.org/10.3390/molecules30224483 - 20 Nov 2025
Viewed by 335
Abstract
Two new cytochalasans (12), along with eight known ones (310) were isolated from sponge-derived Aspergillus sp. SCSIO 41044. The planar structures of 12 were elucidated through extensive spectroscopic analyses and their absolute configurations [...] Read more.
Two new cytochalasans (12), along with eight known ones (310) were isolated from sponge-derived Aspergillus sp. SCSIO 41044. The planar structures of 12 were elucidated through extensive spectroscopic analyses and their absolute configurations determined by modified Mosher’s methods. Biological evaluation revealed that 5, 7, and 8 showed potent cytotoxicity against small cell lung cancers H446 and H1048, with IC50 values ranging from 0.0441 to 1.61 μM. Full article
(This article belongs to the Section Natural Products Chemistry)
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10 pages, 10521 KB  
Article
Electrically Controlled Structures in Cholesteric Droplets with Planar Anchoring
by Oxana O. Prishchepa, Mikhail N. Krakhalev and Anna P. Gardymova
Molecules 2025, 30(22), 4482; https://doi.org/10.3390/molecules30224482 - 20 Nov 2025
Viewed by 400
Abstract
Structure transformations in cholesteric droplets with planar anchoring induced by an electric field are studied experimentally. The radial spherical structure is formed initially, then it transforms into the quasi-nematic untwisting state under the action of an electric field E=1.75 V/μ [...] Read more.
Structure transformations in cholesteric droplets with planar anchoring induced by an electric field are studied experimentally. The radial spherical structure is formed initially, then it transforms into the quasi-nematic untwisting state under the action of an electric field E=1.75 V/μm. The dependence of structure transformations on the voltage switching-off mode is examined. At the one-step voltage-off mode, the Lyre structure is realized in cholesteric droplets at the relative chiral parameter in the range 4.3N8.5. The axis-symmetric bipolar structure and the low-symmetric planar bipolar structure are obtained at the multi-step voltage-off mode. The possibility of forming such structures and their stability are determined by the type of voltage switching-off mode, the N value, the surface anchoring strength (the value of cholesteric helix pitch), and the presence of the surface point defects. Full article
(This article belongs to the Special Issue Liquid Crystals, 3rd Edition)
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14 pages, 5850 KB  
Article
Ball-Milling-Assisted Coating and Magnetic Properties of Fluorescent Biodegradable Powders for Fingerprint Detection
by Hélio L. Barros, Nuno Martinho, Susana Cardoso and Vasco D. B. Bonifácio
Molecules 2025, 30(22), 4481; https://doi.org/10.3390/molecules30224481 - 20 Nov 2025
Viewed by 377
Abstract
The development of environmentally friendly materials for forensic applications is a growing area of interest. Traditional forensic methods often rely on resource-intensive processes and hazardous materials, and thus a demand for sustainable efficient materials without compromising performance is needed. Fluorescent, regular and magnetic [...] Read more.
The development of environmentally friendly materials for forensic applications is a growing area of interest. Traditional forensic methods often rely on resource-intensive processes and hazardous materials, and thus a demand for sustainable efficient materials without compromising performance is needed. Fluorescent, regular and magnetic powders were prepared through ball-milling-assisted coating using biodegradable matrices such as silica, chitosan, and tri-sodium citrate. The effect of the magnetic core on the optical properties, along with the influence of matrix type on the photophysical and magnetic properties of the powders, was assessed. The results suggest that the polymeric matrix effectively prevented fluorescence quenching, although a reduction in fluorescence intensity was observed when comparing magnetic and non-magnetic powders. For core–shell structures based on chitosan and tri-sodium citrate, the reduction in fluorescence caused by the absorption of the magnetic core (Fe3O4) was less pronounced. Additionally, these structures exhibited better magnetic properties when compared with a silica-based core–shell. All fluorescent powders proved highly efficient in fingerprint detection on various surfaces, yielding similar results to commercially available powders. The produced powders are not only safe and cost-effective but also environmentally friendly, making them an alternative to the current commercial powders used in forensic applications. Full article
(This article belongs to the Topic Molecular and Supramolecular Mechanosynthesis)
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19 pages, 1786 KB  
Article
Citric Acid Extraction Impact on Chemical and Bioavailable Forms of Metals in Soil
by Krzysztof Barbusiński, Beata Karwowska and Ewa Neczaj
Molecules 2025, 30(22), 4480; https://doi.org/10.3390/molecules30224480 - 20 Nov 2025
Cited by 1 | Viewed by 517
Abstract
The presence of heavy metals in soils poses a serious threat due to these harmful elements being transported into the food chain. The aim of the presented research was to evaluate the effect of the extraction of selected heavy metals from soil with [...] Read more.
The presence of heavy metals in soils poses a serious threat due to these harmful elements being transported into the food chain. The aim of the presented research was to evaluate the effect of the extraction of selected heavy metals from soil with a 1 M aqueous solution of citric acid (CA) on the chemical (including mobile) forms of these elements and their bioavailability. A soil sample taken in an industrial area was extracted. Then the total content of selected heavy metals (Pb, Zn, Cu, Cd, Ni), their chemical forms (determined by sequential extraction according to the BCR procedure) and bioavailable forms (determined by one-step extraction with a 1 M HCl) were determined in both types of soil, before and after extraction. The tested soil contained significant amounts of the tested metals, and the amounts can be compared as follows: Pb ≥ Zn > Cu ≥ Cd > Ni. The greatest threat to the environment is associated with the presence of cadmium and lead in the tested soil, the content of which exceeds the limits set for soils in industrial areas. In addition, the level of presence of heavy metals in bioavailable and mobile chemical forms, was considered significant. No clear correlation was observed between the content of the analyzed metals in mobile and bioavailable forms. The tested soil contained significant concentrations of Pb (2141 mg/kg), Zn (2030 mg/kg), Cu (68 mg/kg), Cd (63 mg/kg), and Ni (23 mg/kg), which were reduced to 857, 589, 42, 28, and 14 mg/kg, respectively, after extraction with 1 M CA. The extraction process with a CA solution reduced the content of all metals, and the efficiency of the process can be compared as follows: Zn > Pb > Cd > Ni ≥ Cu, with efficiencies of 71%, 60%, 55%, 41% and 39%, respectively. The extraction process reduced the metal content of all the bioavailable and chemical fractions. The shares of metals in the mobile fractions decreased in favor of the immobilized fractions and ones more stable in the environment. After the process of leaching metals from the soil, a clear tendency towards equalization of the heavy metal content in the mobile and bioavailable fractions was observed. Full article
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14 pages, 1848 KB  
Article
Conformational Evolution of Bicalutamide in Chloroform: A Comprehensive NMR Study
by Konstantin V. Belov and Ilya A. Khodov
Molecules 2025, 30(22), 4479; https://doi.org/10.3390/molecules30224479 - 20 Nov 2025
Viewed by 10804
Abstract
This study presents new findings on the conformational mobility of the nonsteroidal antiandrogen blocker, bicalutamide, in deuterated chloroform. Based on NOE NMR spectral analysis, quantitative information was obtained regarding the distribution of «open» and «closed» conformer groups in four systems: one with a [...] Read more.
This study presents new findings on the conformational mobility of the nonsteroidal antiandrogen blocker, bicalutamide, in deuterated chloroform. Based on NOE NMR spectral analysis, quantitative information was obtained regarding the distribution of «open» and «closed» conformer groups in four systems: one with a solid phase (16.7%/83.3%), one without the solid phase (19.7%/80.3%), and two diluted solutions at different concentrations (16.1%/83.9% and 85.3%/14.7%). It was shown that the preparation of molecules for nucleation and the transition to the «closed» conformation occurs at low concentrations and is maintained as the concentration increases until the solid phase is formed. This behavior of conformational evolution contrasts previous understandings of the solid phase’s influence on molecular conformation in solution. The results obtained will offer deeper insights into the conformational evolution of small molecules during nucleation, using bicalutamide as a model. Full article
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14 pages, 1992 KB  
Article
A Novel and Validated GC-MS/MS Method for the Detection of Four Opioids and Seven Fentanoids in Oral Fluid for Forensic Applications
by Roberta Tittarelli, Davide Filardi, Federico Mineo and Giulio Mannocchi
Molecules 2025, 30(22), 4478; https://doi.org/10.3390/molecules30224478 - 20 Nov 2025
Viewed by 616
Abstract
In recent years, the marked increase in the abuse of fentanyl and its analogues has emphasized the importance of developing highly sensitive and selective analytical methods for their detection in biological matrices. Oral fluid (OF) has emerged as a useful alternative to blood [...] Read more.
In recent years, the marked increase in the abuse of fentanyl and its analogues has emphasized the importance of developing highly sensitive and selective analytical methods for their detection in biological matrices. Oral fluid (OF) has emerged as a useful alternative to blood in forensic toxicology, offering a non-invasive and easily accessible matrix for the identification of a recent drug intake. However, its composition requires rigorous sample preparation and robust analytical techniques. A gas chromatography–tandem mass spectrometry (GC-MS/MS) method was developed and validated for the quantification of four opioids and seven fentanyl analogues. A fast and simple solid-phase extraction (SPE) procedure was optimized, enabling the identification and quantification of all analytes in 11 min. The method was validated according to international guidelines, showing a satisfactory degree of linearity (R2 ≥ 0.993), precision, accuracy, and sensitivity, with limit of detections (LODs) ranging from 0.10 to 0.20 ng/mL. The method was then successfully applied to n = 10 real OF samples collected during traffic stops set up by police forces which tested negative at the screening tests. Two samples tested positive for codeine and morphine, and one was positive for fentanyl and norfentanyl. The small number of samples currently limits the interpretation of the results. However, our study represents a good starting point for further application of this method to a wider population of real samples. Full article
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79 pages, 41051 KB  
Review
The Crystal Chemistry and Topology of Modular Structures. III. 2D and 3D Zeolites Containing Tetrahedral Layers with the Apophyllite-Type Topology
by Sergey M. Aksenov, Nikita V. Chukanov, Ramiza K. Rastsvetaeva, Dmitry Yu. Pushcharovsky, Dina V. Deyneko, Galina O. Kalashnikova, Ivan G. Tananaev and Peter C. Burns
Molecules 2025, 30(22), 4477; https://doi.org/10.3390/molecules30224477 - 20 Nov 2025
Cited by 1 | Viewed by 658
Abstract
Materials of the 2D zeolite class retain local catalytically active sites and the stability of traditional zeolites but with layered structures. Synthetic and naturally occurring single- and multilayer apophyllite-related compounds are prototypes of advanced industrial materials for use in various technologies. Their surface [...] Read more.
Materials of the 2D zeolite class retain local catalytically active sites and the stability of traditional zeolites but with layered structures. Synthetic and naturally occurring single- and multilayer apophyllite-related compounds are prototypes of advanced industrial materials for use in various technologies. Their surface chemistry allows for functionalization, and these layers serve as fundamental building blocks for zeolitic frameworks. The discovery of the first triple-layer silicate, günterblassite, provided a critical link that established a fundamental crystal–chemical relationship between layered and framework structures in a wide range of micro- and mesoporous minerals and synthetic materials. The most prominent topic in the development of 2D zeolites remains the synthesis and structural characterization of these 2D zeolite structures This review offers a comprehensive overview of the current state of 2D and 3D zeolites constructed based on apophyllite-type layers. In accordance with the terms of modular crystal chemistry, we present a straightforward classification scheme based on the topological and symmetrical distinctions of the layers and provide ways for their stacking, creating a valuable basis for understanding the modular assembly of advanced porous materials. Full article
(This article belongs to the Special Issue Advances in Coordination Chemistry, 3rd Edition)
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17 pages, 2115 KB  
Review
Evolution of Model Compounds and Functional Group Compositions for Molecular Dynamics Simulations of Aged Asphalt Binder
by Edgar A. O’Rear, Liangliang Huang and Musharraf Zaman
Molecules 2025, 30(22), 4476; https://doi.org/10.3390/molecules30224476 - 20 Nov 2025
Viewed by 317
Abstract
To apply molecular dynamics (MD) simulations in the study of virgin asphalt binder, researchers have relied on basis sets of representative model structures from the SARA categories of saturated aliphatics (S), naphthenic aromatics (A), polar aromatics or resins (R), and asphaltenes (A). The [...] Read more.
To apply molecular dynamics (MD) simulations in the study of virgin asphalt binder, researchers have relied on basis sets of representative model structures from the SARA categories of saturated aliphatics (S), naphthenic aromatics (A), polar aromatics or resins (R), and asphaltenes (A). The evolution of these model compounds for MD of binder is reviewed with emphasis on addition of oxidized species for simulations of recycled aged binders. The level and type of oxygen functional groups in many MD simulations are not consistent with reported findings. Oxidation of primary, secondary, and tertiary benzylic carbons has been used as a rational approach to generate an extended basis set with functional groups reflecting ageing of virgin binder model compounds. Moieties known to be present in aged binder, though not wholly represented in prior work, include carboxylic acids, ketones, alcohols, anhydrides, and sulfoxides. A specific modified basis set for oxidized asphalt binder is proposed along with a methodology for generating other oxygen-consistent basis sets from virgin binder structures. An example illustrates how selection of compounds from the modified basis set and their amounts can be used to match observed functional group compositions. The objective of this approach is more realistic representation of the molecular interactions between aged asphalt binder structures and those in a waste cooking/motor oil, for example, used to rejuvenate the rheological properties of a binder. Full article
(This article belongs to the Section Physical Chemistry)
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15 pages, 1962 KB  
Article
A Competing Hydrogen Bond Network Offers Access to a New Conformation in 24-Atom Triazine Macrocycles
by K. Harsha Vardan Reddy, Arshad Mehmood, Akop Yepremyan and Eric E. Simanek
Molecules 2025, 30(22), 4475; https://doi.org/10.3390/molecules30224475 - 20 Nov 2025
Viewed by 479
Abstract
For a family of 24-atom triazine macrocycles, a single intramolecular hydrogen bond (IMHB) network leads to a conserved, hinge-like motif in solution. Modifications to the backbone of these macrocycles preserve this motif. Modifications to peripheral sites lead to conformational isomers due to hindered [...] Read more.
For a family of 24-atom triazine macrocycles, a single intramolecular hydrogen bond (IMHB) network leads to a conserved, hinge-like motif in solution. Modifications to the backbone of these macrocycles preserve this motif. Modifications to peripheral sites lead to conformational isomers due to hindered bond rotation while conserving the hinge motif. Here, a competitive IMHB network is introduced by the addition of a hydrogen bond donor on the periphery. Cyclization remains quantitative, but multiple conformers result. Three conformers are derived from the hinge motif. Three others are attributed to a new motif that utilizes the new IMHB network. Crystallographic analysis confirms this hypothesis and establishes that this new motif differs significantly from the original with respect to overall shape and disposition of groups. Variable temperature 1H NMR spectroscopy is used to partially assign the spectra because conformers adopting the hinge motif undergo dynamic motion on the NMR timescale, while the new motif appears static. QTAIM analysis corroborates the hydrogen bond designations in the new conformer and categorizes these interactions as moderate and strong. Full article
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21 pages, 1851 KB  
Article
Development and Validation of an HPLC-DAD Method for the Quantitative Determination of Benzoyl Peroxide, Curcumin, Rosmarinic Acid, Resveratrol and Salicylic Acid in a Face Mask—In Vitro/Ex Vivo Permeability Study
by Sofia Almpani, Maria Mitsiou, Paraskevi Kyriaki Monou and Catherine K. Markopoulou
Molecules 2025, 30(22), 4474; https://doi.org/10.3390/molecules30224474 - 19 Nov 2025
Viewed by 889
Abstract
Acne is a common skin condition that causes pimples, redness and inflammation. Benzoyl peroxide (BENZ), salicylic acid (SAL), curcumin (CUR), rosmarinic acid (ROS) and resveratrol (RESV) exhibit antimicrobial, anti-inflammatory and antioxidant properties and are recommended for its treatment. These five active pharmaceutical ingredients [...] Read more.
Acne is a common skin condition that causes pimples, redness and inflammation. Benzoyl peroxide (BENZ), salicylic acid (SAL), curcumin (CUR), rosmarinic acid (ROS) and resveratrol (RESV) exhibit antimicrobial, anti-inflammatory and antioxidant properties and are recommended for its treatment. These five active pharmaceutical ingredients (APIs) were incorporated into a green clay, honey and gelatin face mask and determined by an HPLC-DAD (diode array) method. For the chromatographic separation of the analytes, a gradient mobile phase with two solvents mixtures: A, comprising H2O with 0.1% TFA-ACN with 0.1% TFA, 85:15 v/v, and B, comprising 100% ACN with 0.1% TFA, and a C18 column (250 × 4.6 mm, 5 μm), at 40 °C (diluent: MeOH-ACN 0.1% TFA 2:1 v/v), were selected. The method was validated according to the ICH guidelines for pharmaceutical products (R2 > 0.999, %RSD < 1.2, % Recovery > 98.2, LODμg/mL: ROS = 0.267, RES = 0.047, SAL = 0.636, CUR = 0.296 and BENZ = 0.083). For the processing of mask samples and the quantitative extraction of the analytes, the “D-optima mixture” experimental design methodology was applied (% Recovery 95.4–102.1%, %RSD < 2.4). Finally, the permeability rate (Papp) of the mask ingredients through the skin was studied using Franz vertical diffusion cells, in a cellulose membrane (in vitro), in rat tissue and in human skin (ex vivo). To ensure the reliability of the results, APIs’ stability rate under the given experimental conditions was studied. In addition, a second method for sample processing in Franz cells was developed and validated (% Recovery > 90.6–106.9, %RSD < 5.2). Based on the results obtained, both the effectiveness of the new face mask formulation and the suitability of the membranes were evaluated. Full article
(This article belongs to the Special Issue Recent Advances in Chromatography for Pharmaceutical Analysis)
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11 pages, 1428 KB  
Article
Design of a Novel Class of N-Heterocyclic Carbene Cycloplatinated Complexes Containing Pyrene Chromophores
by Zeping Zhang, Yaping Cheng, Geoffrey Gontard, Tim Riesebeck, Sandy Fornal, Thomas Strassner and Hani Amouri
Molecules 2025, 30(22), 4473; https://doi.org/10.3390/molecules30224473 - 19 Nov 2025
Viewed by 386
Abstract
Cycloplatinated complexes incorporating pyrene chromophores of the formulae (C^C*)Pt(acac) (3, 4), (C^C* = Pyrenyl-NHC, acac = acetylacetonate) were prepared and fully characterized. For comparison, two regioisomeric complexes were prepared following synthetic procedures developed by us. One isomer has the Pt(II) [...] Read more.
Cycloplatinated complexes incorporating pyrene chromophores of the formulae (C^C*)Pt(acac) (3, 4), (C^C* = Pyrenyl-NHC, acac = acetylacetonate) were prepared and fully characterized. For comparison, two regioisomeric complexes were prepared following synthetic procedures developed by us. One isomer has the Pt(II) center attached to the 2-position of the pyrene chromophore, while the other regioisomer has the metal center attached at the 1-position of the organic chromophore. The molecular structures of 3 and 4 were ascertained by X-ray diffraction, and they prove the identity of the targeted compounds. Both complexes are emissive at room temperature in the red part of the spectrum in poly(methyl methacrylate) (PMMA), as well as at 77 K in 2-methyltetrahydrofuran (2-MeTHF). The regioisomer containing the Pt(II) at the 1-position shows enhanced emissive properties compared to the other regioisomer. Full article
(This article belongs to the Special Issue Inorganic Chemistry in Europe 2025)
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15 pages, 2211 KB  
Article
Structural and Spectroscopic Study of Benzoperimidines Derived from 1-Aminoanthraquinone and Their Application to Bioimaging
by Elena Kirilova, Armands Maļeckis, Muza Kirjušina, Ligita Mežaraupe, Ilze Rubeniņa, Aija Brakovska, Veronika Pavlova, Sanita Kecko, Inta Umbraško, Vladimir Kiyan, Lyudmila Lider, Aleksandrs Pučkins and Sergey Belyakov
Molecules 2025, 30(22), 4472; https://doi.org/10.3390/molecules30224472 - 19 Nov 2025
Viewed by 352
Abstract
In this research, we studied the synthesis and characterization of a novel amidine derivative of benzoperimidine derived from 1-aminoanthraquinone, focusing on its emission properties and potential applications in confocal laser scanning microscopy. The synthesized compound exhibited pronounced solvatochromic behavior in various solvents. Spectroscopic [...] Read more.
In this research, we studied the synthesis and characterization of a novel amidine derivative of benzoperimidine derived from 1-aminoanthraquinone, focusing on its emission properties and potential applications in confocal laser scanning microscopy. The synthesized compound exhibited pronounced solvatochromic behavior in various solvents. Spectroscopic analysis, including 1H-, 13C-, and mass spectrometry, confirmed the chemical structure. The structure of three compounds was also determined using X-ray diffraction analysis; this study revealed the structural features of these substances in the solid state. The compound’s antimicrobial activity was evaluated using the agar diffusion method with the bacterium Bacillus subtilis subsp. Spizizenii. Furthermore, the study introduces a dye designed for imaging of the parasitic flatworm Opisthorchis felineus, demonstrating its potential in visualizing biological specimens. Full article
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39 pages, 2305 KB  
Review
Green and Emerging Microextraction Strategies for Bioanalytical Determination of Hormones: Trends, Challenges, and Applications
by David Vicente-Zurdo, Sonia Morante-Zarcero and Isabel Sierra
Molecules 2025, 30(22), 4471; https://doi.org/10.3390/molecules30224471 - 19 Nov 2025
Viewed by 469
Abstract
Accurate and sensitive determination of hormones in biological matrices is essential for clinical diagnostics, therapeutic monitoring, and endocrine research. However, hormone determination presents significant challenges due to their typically low concentrations, complex sample matrices, and structural diversity. In recent years, microextraction techniques have [...] Read more.
Accurate and sensitive determination of hormones in biological matrices is essential for clinical diagnostics, therapeutic monitoring, and endocrine research. However, hormone determination presents significant challenges due to their typically low concentrations, complex sample matrices, and structural diversity. In recent years, microextraction techniques have emerged as strategic tools in bioanalytical chemistry, offering advantages in terms of miniaturization, enhanced selectivity, and compatibility with the principles of green analytical chemistry (GAC). This review provides a comprehensive overview of green and emerging microextraction approaches for the determination of steroidal, thyroid, peptide, and other hormones in biological samples. Key techniques such as solid-phase microextraction (SPME) and dispersive liquid–liquid microextraction (DLLME), followed by high-performance liquid chromatography (HPLC) coupled to diode array detectors (DADs) or mass spectrometry (MS), are critically discussed. Special emphasis is placed on the use of environmentally friendly solvents, such as deep eutectic solvents (DESs), supramolecular solvents (SUPRASs), and advanced sorbents including molecularly imprinted polymers (MIPs) and nanostructured magnetic phases. Applications across various bioanalytical matrices (urine, plasma, serum, saliva, tissues…) are examined in terms of sensitivity, selectivity, and validation parameters. Finally, current challenges, method development gaps, and future directions are highlighted to support the continued advancement of sustainable hormone determination in complex biological systems. Full article
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30 pages, 5792 KB  
Article
Comprehensive Chemical Composition Evaluation of Ziziphus jujuba var. spinosa Germplasm Resources and Selection of Elite Cultivars for Seed, Pulp, and Leaf Utilization
by Xiaochen Song, Yongqing Zhang and Longfei Zhang
Molecules 2025, 30(22), 4470; https://doi.org/10.3390/molecules30224470 - 19 Nov 2025
Viewed by 527
Abstract
Background: Ziziphus jujuba Mill. var. spinosa (Bunge) Hu ex H. F. Chow. (ZS) is a valuable plant with diverse economic applications, as all its organs contain bioactive secondary metabolites. The seeds, known as Suanzaoren in traditional Chinese medicine, are utilized as both [...] Read more.
Background: Ziziphus jujuba Mill. var. spinosa (Bunge) Hu ex H. F. Chow. (ZS) is a valuable plant with diverse economic applications, as all its organs contain bioactive secondary metabolites. The seeds, known as Suanzaoren in traditional Chinese medicine, are utilized as both a medicinal and edible resource, while the fruit pulp and leaves serve as significant raw materials in the food industry. Increasing market demand for Suanzaoren has led to expanded cultivation, though current production practices emphasize seed utilization, resulting in the underutilization of pulp and leaf tissues. In agricultural systems, developing elite varieties is an effective strategy for enhancing crop yield and quality. Breeding initiatives should establish specific objectives aligned with particular end uses, such as seed, pulp, or leaf production. Germplasm serves as the foundational material for breeding programs, so its selection must correspond to intended applications. Evaluating existing germplasm resources based on chemical composition profiles will provide a basis for developing improved ZS varieties. Objective: This study aimed to systematically compare the characteristic chemical composition in the seeds, pulp, and leaves of ZS. By quantifying key chemical components—such as flavonoid glycosides and saponins in seeds, organic acids and phenolic compounds in pulp, and flavonol glycosides and phenolic acids in leaves—we evaluated the quality of ZS germplasm resources. The resulting compositional profiles provide a concrete basis for selecting and breeding elite cultivars tailored to specific end uses, including seed, pulp, or leaf production. Methods: Chemical characterization was performed using ultra-high-performance liquid chromatography coupled with hybrid quadrupole-orbitrap mass spectrometry (UPLC-Q-Exactive Orbitrap MS/MS). Quantitative analysis of chemical composition was conducted using high-performance liquid chromatography with evaporative light scattering detection (HPLC-ELSD). Multivariate statistical analyses—including principal component analysis (PCA), orthogonal partial least squares discriminant analysis (OPLS-DA), and entropy-weighted technique for order preference by similarity to an ideal solution (entropy-weighted TOPSIS)(EWT)—were employed for comprehensive data evaluation. Results: A comprehensive phytochemical analysis of Ziziphi spinosae (ZS) was conducted, identifying 144 distinct compounds across the seeds, pulp, and leaves. Of these, 114 were found in the seeds, 84 in the leaves, and 79 in the pulp. The seeds were particularly rich in flavonoid glycosides, such as spinosin and 6‴-feruloylspinosin, as well as saponins like jujuboside A and B. The pulp was dominated by organic acids, including citric acid, and phenolic compounds, while the leaves were abundant in flavonol glycosides, including rutin, and phenolic acids such as isochlorogenic acid B. Based on the chemical composition profiles, the ZS germplasms were evaluated for specific applications. ZS24, ZS22, and ZS3 were identified as the most suitable for seed production, ZS3, ZS6, and ZS9 for pulp utilization, and ZS20, ZS3, and ZS18 for leaf-based applications. With respect to the integrated utilization of multiple plant parts (roots, stems, and leaves), ZS6, ZS3, and ZS24 demonstrated the highest potential. Conclusions: The identification of superior germplasm resources provides strategic direction for the breeding of elite ZS cultivars. These findings will enable the comprehensive utilization of ZS plant resources and support the high-quality development of related industries. Full article
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21 pages, 14246 KB  
Article
Sol–Gel Synthesis of NiO-Fe2O3-SiO2/Al2O3 Catalysts with Statistical and AI-Based Analysis of Experimental Results
by Aleksandr A. Buzaev, Valerya A. Tkachuk, Konstantin S. Ushenin, Daria N. Staritsyna, Sofya V. Gandybina, Alexandra M. Zakharkiva, Darina K. Ivanova, Ekaterina S. Lyutova, Mariya P. Shcherbakova-Sandu, Irina A. Kurzina and Lyudmila P. Borilo
Molecules 2025, 30(22), 4469; https://doi.org/10.3390/molecules30224469 - 19 Nov 2025
Viewed by 435
Abstract
The development of efficient and cost-effective catalysts is crucial for modern catalytic processes, especially in oxidation reactions. In this study, a sol–gel method was successfully adapted for the synthesis of NiO-Fe2O3-SiO2/Al2O3 catalysts. The optimized [...] Read more.
The development of efficient and cost-effective catalysts is crucial for modern catalytic processes, especially in oxidation reactions. In this study, a sol–gel method was successfully adapted for the synthesis of NiO-Fe2O3-SiO2/Al2O3 catalysts. The optimized sol–gel process incorporates precise heat treatment control, enabling the production of catalysts with a particle size of 44 nm and a specific surface area of 134.79 m2/g. Extensive characterization revealed several significant advantages: a decrease in the heat treatment temperature to 400 °C, maintaining high material dispersion, and eliminating expensive modifiers. Critical synthesis parameters were identified: the Ni/Fe ratio and the heating rate of the heat treatment. Catalytic activity was demonstrated in a model reaction of decane oxidation. Experimental results were confirmed by statistical analysis, and large language models further assisted in the mechanistic interpretation of the results. Full article
(This article belongs to the Section Materials Chemistry)
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23 pages, 3499 KB  
Article
Study on the Isolated Asphaltene Thermal Cracking from an Unconventional Oil Using Diverse Estimating Arrhenius Parameter Approaches
by Guillermo Félix, Alexis Tirado, Mikhail A. Varfolomeev, Eder Lugo-Medina, Carlos A. Soto-Robles and Jorge Ancheyta
Molecules 2025, 30(22), 4468; https://doi.org/10.3390/molecules30224468 - 19 Nov 2025
Viewed by 349
Abstract
The lack of complex schemes and proper kinetic studies for asphaltenes pyrolysis is a significant problem for understanding the reaction mechanisms. Therefore, this study evaluates various parameter estimation approaches (focusing on reaction rate coefficients and Arrhenius parameters), objective functions (sum of squared errors [...] Read more.
The lack of complex schemes and proper kinetic studies for asphaltenes pyrolysis is a significant problem for understanding the reaction mechanisms. Therefore, this study evaluates various parameter estimation approaches (focusing on reaction rate coefficients and Arrhenius parameters), objective functions (sum of squared errors and average absolute errors), and reaction schemes (4-lump and 6-lump) for kinetic modeling of asphaltene pyrolysis. The reaction schemes include asphaltenes, maltenes, gases, and coke, as well as the fractionation of maltenes into polar aromatics, naphthene aromatics, and saturates. Both networks showed adequate accuracy, but the 6-lump model improves yield predictions. Using Method 1 (optimizing reaction rate coefficients) and the sum of square errors as the objective function yields the best accuracy. The analyses confirm that temperature influences selectivity: lower temperatures (below 390 °C) favor the generation of maltenes and gases, while higher temperatures (above 390 °C) promote coke formation. Extended high-temperature exposure leads to secondary cracking of maltenes. Furthermore, the key transformations include the cleavage of aliphatic chains, the aromatization of saturated aromatics, and the polyaddition of free radicals. Full article
(This article belongs to the Special Issue Chemistry Applied to Enhanced Oil Recovery)
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25 pages, 2776 KB  
Article
Effective Antioxidants as Plausible Ligands in Chromium(III) Supplementation: How Complexation Modulates Catechol-Based Polyphenols
by Hanna Lewandowska, Zhe Chen, Krystian Marszałek, Włodzimierz Lewandowski and Renata Świsłocka
Molecules 2025, 30(22), 4467; https://doi.org/10.3390/molecules30224467 - 19 Nov 2025
Viewed by 450
Abstract
This study examines the impact of metal coordination on the antioxidant and pro-oxidant properties of 3,4-dihydroxybenzoic acid (3,4-DHBA) and caffeic acid (CA). Their Na(I), K(I) salts and Cr(III) complexes were evaluated in vitro using radical scavenging assays (ABTS, DPPH, hydroxyl, and superoxide), ferric- [...] Read more.
This study examines the impact of metal coordination on the antioxidant and pro-oxidant properties of 3,4-dihydroxybenzoic acid (3,4-DHBA) and caffeic acid (CA). Their Na(I), K(I) salts and Cr(III) complexes were evaluated in vitro using radical scavenging assays (ABTS, DPPH, hydroxyl, and superoxide), ferric- and cupric-reducing power, and inhibition of linoleic acid peroxidation. Alkali metal coordination generally decreased radical scavenging activity, though K complexes and Cr–3,4-DHBA improved lipid peroxidation inhibition. Cr(III) chelation produced ligand-dependent effects: it markedly increased the reducing power of CA while reducing that of 3,4-DHBA and uniquely promoted pro-oxidant behavior in CA under superoxide conditions. These outcomes reflect how chromium chelation alters electronic distribution and charge transfer, enhancing reducing power in single-electron transfer assays while enabling redox cycling in radical scavenging systems, underscoring its dual and ligand-dependent biological significance. Full article
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18 pages, 5188 KB  
Article
On the Role of MoSe2 in Promoting Persulfate Activation by Fe-Based Catalysts: Dual Redox Cycles and Performance and Mechanism of Efficient Phenol Degradation in Water
by Yirong Ren, Hao Zhao, Zerui Lu and Zuoyan Chen
Molecules 2025, 30(22), 4466; https://doi.org/10.3390/molecules30224466 - 19 Nov 2025
Viewed by 398
Abstract
The recalcitrance and biological toxicity of phenolic pollutants pose a serious threat to the safety of aquatic environments, and developing efficient and stable catalytic degradation technologies is a key research focus in the current environmental field. In this study, a composite material (MSN) [...] Read more.
The recalcitrance and biological toxicity of phenolic pollutants pose a serious threat to the safety of aquatic environments, and developing efficient and stable catalytic degradation technologies is a key research focus in the current environmental field. In this study, a composite material (MSN) of NH2-MIL-101(Fe) modified by MoSe2 nanosheets was constructed via a one-step composite strategy, aiming to address the bottlenecks of low Fe3+/Fe2+ cycling efficiency and iron ion leaching in traditional Fe-based MOFs when activating peroxymonosulfate (PMS). Characterization results showed that MoSe2 nanosheets were uniformly dispersed on the surface of NH2-MIL-101(Fe), and strong electronic interactions existed between them, which significantly optimized the electronic environment of active sites. MSN-3 exhibited excellent performance in activating PMS for phenol degradation: the degradation rate reached 90% within 30 min, with a k = 0.073 min−1, which was much higher than that of other systems. It also showed good structural stability and cyclic regeneration ability. Mechanistic studies confirmed that the core active species in the MSN-3/PMS system are 1O2, •SO4 and •OH. The two-dimensional layered structure of MoSe2 can serve as an efficient electron transport bridge to promote Fe3+/Fe2+ cycling; amino modification further optimizes the electron density of Fe active centers. The two synergistically construct a dual redox cycle of Fe3+/Fe2+ and Mo4+/Mo6+, significantly enhancing PMS activation efficiency and 1O2 production. This study provides a new strategy for designing Fe-MOFs-based PMS activation catalysts and also offers technical support for the practical treatment of recalcitrant organic pollutants in water. Full article
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30 pages, 6871 KB  
Article
Robust All-Solid-State Batteries with Sodium Ion Electrolyte, Aluminum and Additive Manufacturing Inconel 625 Electrodes
by Manuela C. Baptista, Antonio B. Vale, Jose M. Costa and Maria Helena Braga
Molecules 2025, 30(22), 4465; https://doi.org/10.3390/molecules30224465 - 19 Nov 2025
Viewed by 764
Abstract
This study investigates all-solid-state batteries employing multifunctional metallic current collectors/electrodes that remain electrochemically inert toward an alkali-based Na ion solid electrolyte. Inconel 625 was evaluated as the positive current collector in combination with aluminum as the negative electrode and the ferroelectric electrolyte Na2.99Ba0.005OCl. [...] Read more.
This study investigates all-solid-state batteries employing multifunctional metallic current collectors/electrodes that remain electrochemically inert toward an alkali-based Na ion solid electrolyte. Inconel 625 was evaluated as the positive current collector in combination with aluminum as the negative electrode and the ferroelectric electrolyte Na2.99Ba0.005OCl. The inertness of both electrodes enabled the construction of a robust device architecture that behaved as a true battery, exhibiting a two-phase equilibrium discharge plateau at ~1.1 V despite the absence of traditional Faradaic reactions. After a one-month rest period, the cell was sequentially discharged through external resistors and retained full functionality for one year. Cyclic voltammetry confirmed a stable electrochemical response over repeated cycling. The final long-term discharge under a 9.47 kΩ load produced a steady ~0.92 V plateau and delivered a total capacity of 35 mAh (~2.3 mAh·cm−2). Post-mortem analyses revealed excellent chemical and mechanical stability of Inconel 625 after extended operation, while aluminum showed superficial surface degradation attributed to residual moisture, with X-ray diffraction indicating the formation of aluminum hydroxide. Scanning Kelvin probe measurements guided electrode selection and provided insight into interfacial energetics, whereas scanning electron microscopy confirmed interface integrity. Complementary density functional theory simulations optimized the crystalline bulk and surfaces of Inconel, demonstrating interfacial stability at the atomic scale. Overall, this work elucidates the fundamental driving forces underlying traditional battery operation by studying a “capacity-less” system, highlighting the central role of interfacial electrostatics in sustaining battery-like discharge behavior in the absence of redox-active electrodes. Full article
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18 pages, 3358 KB  
Article
Green Synthesis of Silica Nanoparticles from Sugarcane Bagasse Ash for Stable Pickering Oil-in-Water Emulsions
by Daniel Jaramillo-Vélez, Mariana Ochoa-Castaño, Andrea Flórez-Caro, Luis David Botero, Esteban Ureña-Benavides, Raúl Adolfo Valencia-Cardona, Jorge Andrés Velásquez-Cock and Catalina Gómez-Hoyos
Molecules 2025, 30(22), 4464; https://doi.org/10.3390/molecules30224464 - 19 Nov 2025
Viewed by 595
Abstract
The present study explores novel alternatives for the exploitation of sugarcane bagasse ash by obtaining and modifying SiO2 nanoparticles through a green synthesis method. The hydrophilic nature of the nanoparticles was modified using oleic acid. The nanoparticles were characterized using FTIR, FESEM, [...] Read more.
The present study explores novel alternatives for the exploitation of sugarcane bagasse ash by obtaining and modifying SiO2 nanoparticles through a green synthesis method. The hydrophilic nature of the nanoparticles was modified using oleic acid. The nanoparticles were characterized using FTIR, FESEM, and DLS, and their performance in the stabilization of Pickering emulsions was also studied. FESEM micrographs of the nanoparticles revealed an irregular and agglomerated structure. EDS confirmed that their main components are oxygen and silicon, and ATR-FTIR spectra demonstrated that oleic acid effectively modified the nanoparticles. Subsequently, O/W Pickering emulsions were fabricated by combining rotor–stator homogenization and probe ultra-sonication, using dodecane and liquid paraffin as model oil phases and SiO2 NPs as stabilizers. Static light scattering measurements showed that the emulsions exhibited polydispersity, while photographic monitoring confirmed that their physical stability was affected by the concentrations of oleic acid and nanoparticles: concentrations of up to 20.0 wt% and 1.0 wt%, respectively, produced emulsions that remained stable for 7 to 15 days. This study identifies the behavior and challenges associated with novel pathways for the valorization of sugarcane bagasse ash. The stabilization of Pickering emulsions using the obtained SiO2 NPs highlights their potential in pharmaceutical, cosmetic, and food applications. Full article
(This article belongs to the Special Issue Bioactive Compounds in Plants: Extraction and Application)
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16 pages, 2043 KB  
Article
Paramagnetic Agents for SE DNP: Synthesis and ESR Characterization of New Lipophilic Derivatives of Finland Trityl
by Victor M. Tormyshev, Danil A. Kuznetsov, Arthur E. Raizvikh, Olga Yu. Rogozhnikova, Tatiana I. Troitskaya and Elena G. Bagryanskaya
Molecules 2025, 30(22), 4463; https://doi.org/10.3390/molecules30224463 - 19 Nov 2025
Viewed by 369
Abstract
Triarylmethyl radicals (TAMs) have recently emerged as highly effective polarizing agents in dynamic nuclear polarization (DNP) under viscous conditions, enabling substantial hyperpolarization via the solid-effect (SE) DNP mechanism even at room temperature. A comparable, though less pronounced, enhancement was observed for BDPA radicals [...] Read more.
Triarylmethyl radicals (TAMs) have recently emerged as highly effective polarizing agents in dynamic nuclear polarization (DNP) under viscous conditions, enabling substantial hyperpolarization via the solid-effect (SE) DNP mechanism even at room temperature. A comparable, though less pronounced, enhancement was observed for BDPA radicals embedded in phosphocholine-based lipid bilayers. Given the increasing interest in elucidating the structure and dynamics of biopolymers and their high-molecular-weight assemblies—such as cell membranes—this study focuses on the design, synthesis, and characterization of paramagnetic agents tailored for DNP-based structural biology. To this end, we synthesized a series of TAM derivatives functionalized with lipophilic substituents and characterized their magnetic resonance properties, including isotropic hyperfine interaction (HFI) constants on carbon nuclei and electron spin relaxation times (T1 and Tm) at low temperatures (80 K). Echo-detected EPR spectra and electron spin echo envelope modulations (ESEEM) were recorded for novel TAM incorporated into liposomes composed of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). These low-temperature measurements revealed that the radicals are localized either at the liposome surface or within the lipid bilayer, ensuring optimal accessibility to water molecules. Crucially, the presence of a single cholesterol moiety provides strong noncovalent anchoring within the hydrophobic core of the bilayer. Guided by these findings, we identify an amphiphilic TAM bearing a single cholesterol group and polar carboxyl functionalities as a highly promising candidate for DNP applications in membrane biology, combining efficient polarization transfer, bilayer integration, and aqueous accessibility. Full article
(This article belongs to the Section Physical Chemistry)
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11 pages, 1145 KB  
Article
Co(II)-Catalyzed Picolinamide-Directed C(sp3)-S Bond Formation with N-(phenylsulfanyl)succinimides
by Jinjing Qin, Shaodong Zhou, Jinwen Luo, Guodong Wang and Kai Wang
Molecules 2025, 30(22), 4462; https://doi.org/10.3390/molecules30224462 - 19 Nov 2025
Viewed by 380
Abstract
Herein, we disclose a novel and efficient cobalt-catalyzed cross-coupling strategy for picolinamide-directed direct C(sp3)-H bond formation with N-(phenylsulfanyl)succinimides. This method enables the direct construction of C(sp3)–S bonds under mild conditions and exhibits excellent functional group tolerance along with [...] Read more.
Herein, we disclose a novel and efficient cobalt-catalyzed cross-coupling strategy for picolinamide-directed direct C(sp3)-H bond formation with N-(phenylsulfanyl)succinimides. This method enables the direct construction of C(sp3)–S bonds under mild conditions and exhibits excellent functional group tolerance along with a broad substrate scope. Notably, the catalytic system achieves oxidative C–H functionalization without relying on costly or environmentally detrimental oxidants, offering a more sustainable and practical alternative for C–S bond formation. Full article
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17 pages, 1370 KB  
Review
Microplastic Formation and Surface Crack Patterns: A Method for Waste Plastic Identification
by Hisayuki Nakatani and Anh Thi Ngoc Dao
Molecules 2025, 30(22), 4461; https://doi.org/10.3390/molecules30224461 - 19 Nov 2025
Viewed by 518
Abstract
Accumulation of plastic debris in marine environments has become a critical global issue, with microplastics (MPs) posing persistent ecological risks. This review synthesizes current knowledge on the formation mechanisms of MPs from polyolefins such as polypropylene (PP) and polyethylene (PE), emphasizing the influence [...] Read more.
Accumulation of plastic debris in marine environments has become a critical global issue, with microplastics (MPs) posing persistent ecological risks. This review synthesizes current knowledge on the formation mechanisms of MPs from polyolefins such as polypropylene (PP) and polyethylene (PE), emphasizing the influence of marine conditions on degradation pathways. Autoxidation is identified as the dominant mechanism; however, salinity and chloride ions significantly retard radical formation, altering photodegradation kinetics and crack propagation. These effects lead to distinctive surface morphologies—such as rectangular and trapezoidal crack patterns in PP—which can serve as reliable indicators for polymer identification. This review further explores the role of polymer chain orientation and spherulite structures in crack development and discusses how these features can be leveraged for cost-effective sorting and recycling strategies. Finally, emerging approaches using AI-based image recognition for automated identification of weathered plastics are highlighted as promising tools to enhance resource recovery and mitigate marine plastic pollution. Full article
(This article belongs to the Special Issue 10th Anniversary of Green Chemistry Section)
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