Molecules

16 pages, 5955 KiB

Open AccessArticle

High-Temperature Layered Modification of Mn₂In₂Se₅

by Ivan V. Chernoukhov, Anton D. Pyreu, Andrey N. Azarevich, Alexander N. Samarin, Alexey V. Bogach, Konstantin O. Znamenkov, Andrei V. Shevelkov and Valeriy Yu. Verchenko

Molecules 2025, 30(9), 1904; https://doi.org/10.3390/molecules30091904 (registering DOI) - 24 Apr 2025

Abstract

Layered chalcogenides are interesting from the point of view of the formation of two-dimensional magnetic systems for relevant applications in spintronics. High-spin Mn²⁺ or Fe³⁺ cations with five unpaired electrons are promising in the search for compounds with interesting magnetic properties. [...] Read more.

Layered chalcogenides are interesting from the point of view of the formation of two-dimensional magnetic systems for relevant applications in spintronics. High-spin Mn²⁺ or Fe³⁺ cations with five unpaired electrons are promising in the search for compounds with interesting magnetic properties. In this study, a new layered modification of the Mn₂In₂Se₅ compound from the A₂B₂X₅ family (“225”) was synthesized and investigated. A phase transition to the polymorph with primitive trigonal lattice was recorded at a temperature of 711 °C, which was confirmed by simultaneous thermal analysis, X-ray powder diffraction at elevated temperatures, and sample annealing and quenching. The stability of Mn₂In₂Se₅ in air at high temperatures was investigated by thermal gravimetric analysis and powder X-ray diffraction. The new polymorph of Mn₂In₂Se₅ crystallizes in the Mg₂Al₂Se₅ structure type, as revealed by the Rietveld refinement against powder X-ray diffraction data. The crystal structure can be viewed as a close-packing of Se anions, in which indium and manganese cations are enclosed inside tetrahedral and octahedral voids, respectively, according to the A_MnB_InCB_InC_MnA… sequence. Magnetization measurements reveal an antiferromagnetic-like transition at a temperature of 6.3 K. The same magnetic properties are reported in the literature for the low-temperature R-centered trigonal polymorph. An approximation by the modified Curie–Weiss law yields a significant ratio of |θ|/T_N = 28, which indicates strong magnetic frustration. Full article

(This article belongs to the Section Materials Chemistry)

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13 pages, 3593 KiB

Open AccessArticle

Influence of Metal Composition and Support Material on Carbon Yield and Quality in the Direct Decomposition of Methane

by Uidam Jun, Bon-Jun Ku, Yeji Gwon, Dong-Hyun Kim, Mansu Kim, I-Jeong Jeon, Hongjin Lee, Jae-Oh Shim and Kyubock Lee

Molecules 2025, 30(9), 1903; https://doi.org/10.3390/molecules30091903 - 24 Apr 2025

Abstract

A series of catalysts were synthesized via a combination of evaporation-induced self-assembly and spray pyrolysis; they were then applied to the direct decomposition of methane. Among them, Ni-Cu/MgO catalysts exhibited the smallest Ni particle size (~9 nm), attributed to the Cu-induced suppression of [...] Read more.

A series of catalysts were synthesized via a combination of evaporation-induced self-assembly and spray pyrolysis; they were then applied to the direct decomposition of methane. Among them, Ni-Cu/MgO catalysts exhibited the smallest Ni particle size (~9 nm), attributed to the Cu-induced suppression of Ni crystal growth during synthesis. These catalysts achieved the highest carbon yield, primarily due to the enhanced dispersion and nanoscale size of Ni particles. The interaction between methane and the catalysts, as well as the structural and electrical properties of the resulting carbon nanotubes, such as crystallinity and conductivity, were investigated with respect to the support material (MgO vs. Al₂O₃) and metal composition (Ni vs. Ni-Cu). The findings provide valuable insights for designing advanced catalyst systems for the efficient conversion of methane into high-value carbon-based materials. Full article

(This article belongs to the Special Issue Research on Heterogeneous Catalysis—2nd Edition)

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20 pages, 2135 KiB

Open AccessArticle

Green Synthesis and Characterization of Fe-Ti Mixed Nanoparticles for Enhanced Lead Removal from Aqueous Solutions

by Shamika P. W. R. Hewage and Harshica Fernando

Molecules 2025, 30(9), 1902; https://doi.org/10.3390/molecules30091902 - 24 Apr 2025

Abstract

Heavy metal contamination in water resources presents a significant environmental and public health challenge, with lead being particularly concerning due to its toxicity and persistence. This study reports the green synthesis of Fe-Ti mixed oxide nanoparticles (NPs) using dextrose as a green source [...] Read more.

Heavy metal contamination in water resources presents a significant environmental and public health challenge, with lead being particularly concerning due to its toxicity and persistence. This study reports the green synthesis of Fe-Ti mixed oxide nanoparticles (NPs) using dextrose as a green source and investigates their effectiveness in lead removal from aqueous solutions. The synthesized NPs were characterized using XRD, FTIR, XPS, SEM-EDS, and BET analysis, revealing an amorphous structure with a high surface area (292.89 m² g⁻¹) and mesoporous characteristics. XPS analysis confirmed the presence of mixed Fe³⁺/Fe²⁺ valence states in a Ti⁴⁺-rich framework, creating diverse binding sites for lead adsorption. The material exhibited optimal lead removal at pH 5, with adsorption following pseudo-second-order kinetics (R² > 0.99) and a Langmuir isotherm model (R² > 0.98). Maximum adsorption capacity reached 25.10 mg g⁻¹ at 40 °C, showing endothermic behavior. The low point of zero charge (PZC, 0.22) and surface hydroxyl groups enabled efficient lead binding possibly through multiple mechanisms. Dose optimization studies established 6 g L⁻¹ as the optimal adsorbent concentration. The synergistic combination of iron’s affinity for heavy metals and titanium’s structural stability, coupled with environmentally friendly synthesis, resulted in a promising material for sustainable water treatment applications. Full article

(This article belongs to the Special Issue Advances in Homogeneous/Heterogeneous Photocatalysis to the Degradation of Pollutants in Water)

20 pages, 2160 KiB

Open AccessArticle

Conformational Locking of the Geometry in Photoluminescent Cyclometalated N^C^N Ni(II) Complexes

by Maryam Niazi, Iván Maisuls, Lukas A. Mai, Sascha A. Schäfer, Alex Oster, Lukas S. Diaz, Dirk M. Guldi, Nikos L. Doltsinis, Cristian A. Strassert and Axel Klein

Molecules 2025, 30(9), 1901; https://doi.org/10.3390/molecules30091901 - 24 Apr 2025

Abstract

In our research aimed at replacing precious transition metals like platinum with abundant base metals such as nickel for efficient triplet emitters, we synthesized and studied Ni(II) complexes [Ni(L^NHR)Cl]. These complexes containing the N^C^N cyclometalating dipyridyl-phenide ligand, equipped with pending H-bonding [...] Read more.

In our research aimed at replacing precious transition metals like platinum with abundant base metals such as nickel for efficient triplet emitters, we synthesized and studied Ni(II) complexes [Ni(L^NHR)Cl]. These complexes containing the N^C^N cyclometalating dipyridyl-phenide ligand, equipped with pending H-bonding amine groups (NH(C₆H₅) (L^NHPh) and NH(C₆H₅CH₂), ClL^NHBn). Molecular structures determined from experimental X-ray diffractometry and density functional theory (DFT) calculations in the ground state showed marked deviation of the Cl⁻ coligand (ancillary ligand) from the ideal planar coordination, with τ₄ values of 0.35 and 0.33, respectively, along with hydrogen bonding interactions of the ligand NH function with the Cl⁻ coligand. The complexes exhibit long-wavelength absorption bands at approximately 425 nm in solution, with the experimental spectra being accurately reproduced through time-dependent density functional theory (TD-DFT) calculations. Vibrationally structured emission profiles and steady-state photoluminescence quantum yields of 30% for [Ni(L^NHPh)Cl] and 40% for [Ni(L^NHBn)Cl] (along with dual excited state lifetimes in the ns and in the ms range) were found in frozen 2-methyl-tetrahydrofuran (2MeTHF) glassy matrices at 77 K. Furthermore, within a poly(methyl methacrylate) matrix, the complexes showed emission bands centered at around 550 nm within a temperature range from 6 K to 300 K with lifetimes similar to 77 K. Based on TD-DFT potential scans along the metal–ligand (Ni–N) coordinate, we found that in a rigid environment that restricts the geometry to the Franck-Condon region, either the triplet T₅ or the singlet S₄ state could contribute to the photoluminescence. Full article

(This article belongs to the Special Issue 30th Anniversary of Molecules—Recent Advances in Inorganic Chemistry)

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20 pages, 1442 KiB

Open AccessArticle

Liquid Chromatography-Tandem Mass Spectrometry Method Development and Validation for the Determination of a New Mitochondrial Antioxidant in Mouse Liver and Cerebellum, Employing Advanced Chemometrics

by Anthi Panara, Dimitra Biliraki, Markus Nussbaumer, Michaela D. Filiou, Nikolaos S. Thomaidis, Ioannis K. Kostakis and Evagelos Gikas

Molecules 2025, 30(9), 1900; https://doi.org/10.3390/molecules30091900 - 24 Apr 2025

Abstract

Anxiety and stress-related disorders affect all ages in all geographical areas. As high anxiety and chronic stress result in the modulation of mitochondrial pathways, intensive research is being carried out on pharmaceutical interventions that alleviate pertinent symptomatology. Therefore, innovative approaches being currently pursued [...] Read more.

Anxiety and stress-related disorders affect all ages in all geographical areas. As high anxiety and chronic stress result in the modulation of mitochondrial pathways, intensive research is being carried out on pharmaceutical interventions that alleviate pertinent symptomatology. Therefore, innovative approaches being currently pursued include substances that target mitochondria bearing an antioxidant moiety. In this study, a newly synthesized antioxidant consisting of triphenylphosphine (TPP), a six-carbon alkyl spacer, and hydroxytyrosol (HT) was administered orally to mice via drinking water. Cerebellum and liver samples were collected and analyzed using ultra-high-performance liquid chromatography-tandem triple quadrupole mass spectrometry (UHPLC-MS/MS) to assess the levels of TPP-HT in the respective tissues to evaluate in vivo administration efficacy. Sample preparation included extraction with appropriate solvents and a preconcentration step to achieve the required sensitivity. Both methods were validated in terms of selectivity, linearity, accuracy, and limits of detection and quantification. Αdditionally, a workflow for evaluating and statistically summarizing multiple fortified calibration curves was devised. TPP-HT penetrates the blood–brain barrier (BBB), with a level of 11.5 ng g⁻¹ quantified in the cerebellum, whereas a level of 4.8 ng g⁻¹ was detected in the liver, highlighting the plausibility of orally administering TPP-HT to achieve mitochondrial targeting. Full article

(This article belongs to the Special Issue The 30th Anniversary of Molecules—Recent Advances in Chemical Biology)

24 pages, 1233 KiB

Open AccessReview

CD44 Variant Expression in Follicular Cell-Derived Thyroid Cancers: Implications for Overcoming Multidrug Resistance

by Benny Mosoane, Michelle McCabe, Brandon S. Jackson and Zodwa Dlamini

Molecules 2025, 30(9), 1899; https://doi.org/10.3390/molecules30091899 - 24 Apr 2025

Abstract

Thyroid cancer (TC) is a significant global health issue that exhibits notable heterogeneity in incidence and outcomes. In low-resource settings such as Africa, delayed diagnosis and limited healthcare access exacerbate mortality rates. Among follicular cell-derived thyroid cancers—including papillary (PTC), follicular (FTC), anaplastic (ATC), [...] Read more.

Thyroid cancer (TC) is a significant global health issue that exhibits notable heterogeneity in incidence and outcomes. In low-resource settings such as Africa, delayed diagnosis and limited healthcare access exacerbate mortality rates. Among follicular cell-derived thyroid cancers—including papillary (PTC), follicular (FTC), anaplastic (ATC), and poorly differentiated (PDTC) subtypes—the role of CD44 variants has emerged as a critical factor influencing tumor progression and multidrug resistance (MDR). CD44, a transmembrane glycoprotein, and its splice variants (CD44v) mediate cell adhesion, migration, and survival, contributing to cancer stem cell (CSC) maintenance and therapy resistance. Differential expression patterns of CD44 isoforms across TC subtypes have shown diagnostic, prognostic, and therapeutic implications. Specifically, CD44v6 expression in PTC has been correlated with metastasis and aggressive tumor behavior, while in FTC, its expression aids in distinguishing malignant from benign lesions. Furthermore, CD44 contributes to MDR through enhanced drug efflux via ABC transporters, apoptosis evasion, and CSC maintenance via the Wnt/β-catenin and PI3K/Akt pathways. Targeted therapies against CD44 such as monoclonal antibodies, hyaluronic acid-based nanocarriers, and gene-editing technologies hold promise in overcoming MDR. However, despite the mounting evidence supporting CD44-targeted strategies in various cancers, research on this therapeutic potential in TC remains limited. This review synthesizes existing knowledge on CD44 variant expression in follicular cell-derived thyroid cancers and highlights potential therapeutic strategies to mitigate MDR, particularly in high-burden regions, thereby improving patient outcomes and survival. Full article

(This article belongs to the Special Issue New Therapeutic Tools against MDR Tumors: Discovery, Synthesis and Evaluation of Bioactive Compounds)

17 pages, 3911 KiB

Open AccessArticle

Wood-Based Micro-Biochars in a Cement Mixture

by Minkyeong Pyo, Jongsun Kim, Seungwook Seok, Chan Ho Park and Wonchang Choi

Molecules 2025, 30(9), 1898; https://doi.org/10.3390/molecules30091898 - 24 Apr 2025

Abstract

Immediate action is required to achieve carbon neutrality within the cement industry. The integration of biochar into cement as a component of reinforced concrete has potential to mitigate carbon emissions in the construction sector by enabling carbon sequestration. In pursuit of eco-friendly practices [...] Read more.

Immediate action is required to achieve carbon neutrality within the cement industry. The integration of biochar into cement as a component of reinforced concrete has potential to mitigate carbon emissions in the construction sector by enabling carbon sequestration. In pursuit of eco-friendly practices and improved physical properties of cement composites, this study investigated the properties of wood-based, micron-sized biochar as a non-carbonate raw material, including its chemical composition, morphology, and wettability. The characterization of lignocellulosic micro-biochar and its mechanical impact on cement composites was a focus of this study. Cement was partially replaced with varying weight percentages of micro-biochar (1, 3, and 5 wt%), and the effects were evaluated through compressive strength tests after 7 and 28 d. The results demonstrated that the micro-biochar could sustain strength even when substituted for cement. Notably, after 28 d, the compressive strength of the sample with only cement was 29.6 MPa, while the sample with 3 wt% biochar substitution showed 30.9 MPa, indicating a 4.4% increase. This research contributes to sustainable construction practices by offering a green solution for reducing carbon emissions in the industry. Full article

(This article belongs to the Special Issue Carbon-Based Materials for Sustainable Chemistry: 2nd Edition)

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37 pages, 8170 KiB

Open AccessArticle

Drug Repurposing to Inhibit Oncostatin M in Crohn’s Disease

by Faranak Bahramimehr, Axel Guthart, Stefanie Kurz, Yuanping Hai, Mona Dawood, Rümeysa Yücer, Nasim Shahhamzehei, Ralf Weiskirchen, Wilfried Roth, Wolfgang Stremmel, Gerhard Bringmann and Thomas Efferth

Molecules 2025, 30(9), 1897; https://doi.org/10.3390/molecules30091897 - 24 Apr 2025

Abstract

Crohn’s disease is an inflammatory bowel disease (IBD) that currently lacks satisfactory treatment options. Therefore, new targets for new drugs are urgently needed to combat this disease. In the present study, we investigated the transcriptomics-based mRNA expression of intestinal biopsies from patients with [...] Read more.

Crohn’s disease is an inflammatory bowel disease (IBD) that currently lacks satisfactory treatment options. Therefore, new targets for new drugs are urgently needed to combat this disease. In the present study, we investigated the transcriptomics-based mRNA expression of intestinal biopsies from patients with Crohn’s disease. We compared the mRNA expression profiles of the ileum and colon of patients with those of healthy individuals. A total of 72 genes in the ileum and 33 genes in the colon were differentially regulated. Among these, six genes were overexpressed in both tissues, including IL1B, TCL1A, HCAR3, IGHG1, S100AB, and OSM. We further focused on OSM/oncostatin M. To confirm the responsiveness of intestinal tissues from patients with Crohn’s disease to oncostatin M inhibition, we examined the expression of the oncostatin M receptor using immunohistochemistry in patient biopsies as well as in kindlin-1^−/− and kindlin-2^−/− knockout mice, which exhibit an inflammatory bowel disease (IBD) phenotype, and found strong oncostatin M expression in all samples examined. Next, we conducted a drug-repurposing study using the supercomputer MOGON and bioinformatic methods. A total of 13 candidate compounds out of 1577 FDA-approved drugs were identified by PyRx-based virtual drug screening and AutoDock-based molecular docking. Their lowest binding energies (LBEs) ranged from −10.46 (±0.08) to −8.77 (±0.08) kcal/mol, and their predicted inhibition constants (pK_i) ranged from 21.62 (±2.97) to 373.78 (±36.78) nM. Ecamsule has an interesting stereostructure with two C₂-symmetric enantiomers (1S,4R-1′S,4′R and 1R,4S-1′R,4′S) (1a and 1b) and one meso diastereomer (1S,4R-1′R,4′S) (1c). These three stereoisomers showed strong, albeit differing, binding affinities in molecular docking. As examined by nuclear magnetic resonance and polarimetry, the 1S,4R-1′S,4′R isomer was the stereoisomer present in our commercially available preparations used for microscale thermophoresis. Ecamsule (1a) was chosen for in vitro validation using recombinant oncostatin M and microscale thermophoresis. Considerable dissociation constants were obtained for ecamsule after three repetitions with a K_d value of 11.36 ± 2.83 µM. Subsequently, we evaluated, by qRT-PCR, the efficacy of ecamsule (1a) as a potential drug that could prevent oncostatin M activation by inhibiting downstream inflammatory marker genes (IL6, TNFA, and CXCL11). In conclusion, we have identified oncostatin M as a promising new drug target for Crohn’s disease through transcriptomics and ecamsule as a potential new drug candidate for Crohn’s disease through a drug-repurposing approach both in silico and in vitro. Full article

(This article belongs to the Special Issue Bioorganic Chemistry in Europe)

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21 pages, 9966 KiB

Open AccessArticle

Optimization of Zinc and Aluminum Hydroxyquinolines for Applications as Semiconductors in Molecular Electronics

by María Elena Sánchez Vergara, Francisco Iñaki Díaz Morales, Bertha Molina, Edgar Alvarez-Zauco, Lourdes Bazán-Díaz and Roberto Salcedo

Molecules 2025, 30(9), 1896; https://doi.org/10.3390/molecules30091896 - 24 Apr 2025

Abstract

This work explores the dispersed heterojunction of tris-(8-hydroxyquinoline) aluminum (AlQ₃) and 8-hydroxyquinoline zinc (ZnQ₂) with tetracyanoquinodimethane (TCNQ) and 2,6-diaminoanthraquinone (DAAq). Thin films of these organic semiconductors were deposited and analyzed, with their structures calculated with the B3PW91/6-31G** method. The [...] Read more.

This work explores the dispersed heterojunction of tris-(8-hydroxyquinoline) aluminum (AlQ₃) and 8-hydroxyquinoline zinc (ZnQ₂) with tetracyanoquinodimethane (TCNQ) and 2,6-diaminoanthraquinone (DAAq). Thin films of these organic semiconductors were deposited and analyzed, with their structures calculated with the B3PW91/6-31G** method. The optimized structure for AlQ₃-TCNQ, AlQ₃-DAAq, is achieved by means of three hydrogen bonds, whereas for ZnQ₂-DAAq, two hydrogen interactions are predicted. These structures were recalculated including the GD3 dispersion term. A stable ordering was also achieved for AlQ₃-TCNQ-GD3, AlQ₃-DAAq-GD3, and ZnQ₂-DAAq-GD3 with four and two hydrogen contacts for the former and the two latter, respectively. Infrared (IR) and UV-visible spectroscopy confirmed these theoretical predictions, in addition to obtaining the optical band gap for the films. The optical band gap values ranged between 1.62 and 2.97 eV (theoretical) and between 2.46 and 2.87 eV (experimental). Additional optical parameters and electrical behavior were obtained, which indicates the potential of the films to be used as organic semiconductors. All three films showed transmittance above 76%, which also broadens the range of applications in electrodes, transparent transistors, or photovoltaic cells. Devices fabricated using these materials displayed ohmic electrical behavior, with peak current values between 2 × 10⁻³ and 6 × 10⁻³ A. Full article

(This article belongs to the Special Issue Recent Advancements in Semiconductor Materials)

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27 pages, 3118 KiB

Open AccessReview

Implications of Mucin-Type O-Glycosylation in Alzheimer’s Disease

by Nancy Vela Navarro, Gustavo De Nadai Mundim and Maré Cudic

Molecules 2025, 30(9), 1895; https://doi.org/10.3390/molecules30091895 - 24 Apr 2025

Abstract

Alzheimer’s disease (AD) is one of the most common neurodegenerative disorders linked to aging. Major hallmarks of AD pathogenesis include amyloid-β peptide (Aβ) plaques, which are extracellular deposits originating from the processing of the amyloid precursor protein (APP), and neurofibrillary tangles (NFTs), which [...] Read more.

Alzheimer’s disease (AD) is one of the most common neurodegenerative disorders linked to aging. Major hallmarks of AD pathogenesis include amyloid-β peptide (Aβ) plaques, which are extracellular deposits originating from the processing of the amyloid precursor protein (APP), and neurofibrillary tangles (NFTs), which are intracellular aggregates of tau protein. Recent evidence indicates that disruptions in metal homeostasis and impaired immune recognition of these aggregates trigger neuroinflammation, ultimately driving disease progression. Therefore, a more comprehensive approach is needed to understand the underlying causes of the disease. Patients with AD present abnormal glycan profiles, and most known AD-related molecules are either modified with glycans or involved in glycan regulation. A deeper understanding of how O-glycosylation influences the balance between amyloid-beta peptide production and clearance, as well as microglia’s pro- and anti-inflammatory responses, is crucial for deciphering the early pathogenic events of AD. This review aims to provide a comprehensive summary of the extensive research conducted on the role of mucin-type O-glycosylation in the pathogenesis of AD, discussing its role in disease onset and immune recognition. Full article

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16 pages, 970 KiB

Open AccessArticle

Green Analytical Method Using Single-Drop Microextraction Followed by Gas Chromatography for Nitro Compound Detection in Environmental Water and Forensic Rinse Water

by Tamara Pócsová, Senad Okanovič and Svetlana Hrouzková

Molecules 2025, 30(9), 1894; https://doi.org/10.3390/molecules30091894 - 24 Apr 2025

Abstract

The extensive use of nitro compounds in agriculture, industry, armaments, and pharmaceuticals, along with their toxic effects on living organisms, necessitates efficient and environmentally sustainable analytical methods. Traditional extraction techniques often involve practices that are not eco-friendly, such as the use of large [...] Read more.

The extensive use of nitro compounds in agriculture, industry, armaments, and pharmaceuticals, along with their toxic effects on living organisms, necessitates efficient and environmentally sustainable analytical methods. Traditional extraction techniques often involve practices that are not eco-friendly, such as the use of large volumes of solvents, toxic chemicals, and the generation of significant waste; therefore, the single-drop microextraction technique was involved in overcoming these limitations. This study shows an environmentally friendly method for nitro compound analysis focusing on NB (Nitrobenzene), 2-NT (2-Nitrotoluene), 3-NT (3-Nitrotoluene), 4-NT (4-Nitrotoluene), 1,3-DNB (1,3-Dinitrobenzene), 1,2-DNB (1,2-Dinitrobenzene), 2,4-DNT (2,4-Dinitrotoluene), and TNT (Trinitrotoluene). To separate and to detect selected nitro compounds, gas chromatography with an electron capture detector was utilized, which is highly selective for analytes containing nitro groups. To determine optimal experimental conditions, extraction parameters were studied, including the impact of salt addition, temperature, and pH on extraction efficiency. Key performance parameters, such as limit of detection (LOD), limit of quantification (LOQ), repeatability, extraction recoveries, calibration range, and matrix effects, were assessed. The LOD values ranged from 0.01 to 0.09 μg/L in deionized water, 0.01 to 0.06 μg/L in tap water, 0.01 to 0.03 μg/L in seawater, and 0.03 to 0.11 μg/L in model forensic rinse water. The optimized method was successfully applied to the determination of nitro compounds in real environmental water samples and forensic rinse water samples. The environmental sustainability and greenness of the proposed method was evaluated with the AGREE, AGREEprep, and AESA techniques. Full article

(This article belongs to the Special Issue Analytical Methods for Food and Environmental Pollutants: Current and Future Perspectives)

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29 pages, 7203 KiB

Open AccessArticle

New Cu(II), Cu(I) and Ag(I) Complexes of Phenoxy-Ketimine Schiff Base Ligands: Synthesis, Structures and Antibacterial Activity

by Miriam Caviglia, Zhenzhen Li, Carlo Santini, Jo’ Del Gobbo, Cristina Cimarelli, Miao Du, Alessandro Dolmella and Maura Pellei

Molecules 2025, 30(9), 1893; https://doi.org/10.3390/molecules30091893 - 24 Apr 2025

Abstract

Two phenoxy-ketimines ligands, 2-(1-(benzylimino)ethyl)phenol (HL^BSMe) and 2-((benzylimino)(phenyl)methyl)phenol (HL^BSPh), were synthesized and used as supporting ligands of new copper(II), copper(I), and silver(I) complexes. In order to confer different solubility properties to the metal complexes and to stabilize Cu and Ag [...] Read more.

Two phenoxy-ketimines ligands, 2-(1-(benzylimino)ethyl)phenol (HL^BSMe) and 2-((benzylimino)(phenyl)methyl)phenol (HL^BSPh), were synthesized and used as supporting ligands of new copper(II), copper(I), and silver(I) complexes. In order to confer different solubility properties to the metal complexes and to stabilize Cu and Ag in their +1 oxidation state, the lipophilic triphenylphosphine (PPh₃) and the hydrophilic 1,3,5-triaza-7-phosphaadamantane (PTA) were selected as co-ligands in the syntheses of the Cu(I) and Ag(I) complexes. All compounds were characterized by CHN analysis, NMR, FT-IR spectroscopy, and electrospray ionization mass spectrometry (ESI-MS); the molecular structure of the copper(II) complex [Cu(L^BSPh)₂] was also determined by single-crystal X-ray diffraction. Finally, the antibacterial activity of the metal complexes, the Schiff base ligands and phosphane co-ligands, were assessed by determining the minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) against Gram-negative (Escherichia coli) and Gram-positive bacteria (Staphylococcus aureus). Full article

(This article belongs to the Topic Metal Ions in Health and Diseases: Current Progress and Future Challenges)

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20 pages, 6359 KiB

Open AccessArticle

Antioxidant and Anti-Inflammatory Activities of Astilboides tabularis (Hemsl.) Engl. Root Extract

by Nam Ho Yoo, Young Sun Baek, Hee Kyu Kim, Chan Ok Lee and Myong Jo Kim

Molecules 2025, 30(9), 1892; https://doi.org/10.3390/molecules30091892 - 24 Apr 2025

Abstract

Here, we examined the antioxidant and anti-inflammatory activities of the ethyl acetate (EtOAc) fraction of Astilboides tabularis (Hemsl.) Engl. root extracts, initially prepared from a 70% ethanol extraction. This EtOAc fraction exhibited significant scavenging activity against DPPH radicals (IC₅₀: 11.38 ± [...] Read more.

Here, we examined the antioxidant and anti-inflammatory activities of the ethyl acetate (EtOAc) fraction of Astilboides tabularis (Hemsl.) Engl. root extracts, initially prepared from a 70% ethanol extraction. This EtOAc fraction exhibited significant scavenging activity against DPPH radicals (IC₅₀: 11.38 ± 0.48 µg/mL) and ABTS radicals (IC₅₀: 7.46 ± 0.58 µg/mL), and had a high total phenolic content (i.e., 407.02 ± 13.56 mg GAE/g). In addition, the EtOAc fraction demonstrated concentration-dependent protective effects in a RAW264.7 macrophage cell model subjected to oxidative stress. In lipopolysaccharide (LPS)-stimulated RAW264.7 cells, nitric oxide (NO) production and the expression of inflammatory mediators (iNOS, COX-2, TNF-α, IL-1β, IFN-β) were inhibited in a concentration-dependent manner. Western blot and real-time PCR (RT-PCR) analyses revealed that the EtOAc fraction also suppressed inflammatory mediator expression via inhibiting the activation of the NF-κB and MAPK signaling pathways. Finally, LC-QTOF-MS and LC-MS/MS analyses identified gallic acid and bergenin as compounds contributing to observed antioxidant and anti-inflammatory effects. In conclusion, the EtOAc fraction of A. tabularis root extracts exhibited strong anti-oxidant and anti-inflammatory properties, suggesting potential usage for treating various inflammatory diseases. Full article

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33 pages, 3639 KiB

Open AccessReview

“Pepper”: Different Spices, One Name—Analysis of Sensory and Biological Aspects

by Pierina Díaz-Guerrero, Sofia Panzani, Chiara Sanmartin, Chiara Muntoni, Isabella Taglieri and Francesca Venturi

Molecules 2025, 30(9), 1891; https://doi.org/10.3390/molecules30091891 - 24 Apr 2025

Abstract

Spices are a part of modern and ancient cultures due to their recognized culinary and medicinal properties. Pepper is commonly used in many recipes; however, in the field of gastronomy, the term “pepper” usually refers to a group that includes several different spices, [...] Read more.

Spices are a part of modern and ancient cultures due to their recognized culinary and medicinal properties. Pepper is commonly used in many recipes; however, in the field of gastronomy, the term “pepper” usually refers to a group that includes several different spices, such as black pepper (Piper nigrum L.), cubeb pepper (Piper cubeba L.f.), long pepper (Piper longum L.), pink pepper (Schinus terebinthifolius Raddi), allspice (Pimenta dioica L. Merrill), and Japanese pepper (Zanthoxylum piperitum DC.). Despite the extensive study of the chemical characterization and medicinal and culinary properties of “pepper”, sensory analysis (color, aroma profile, odor profile, and chemesthesis) of these spices have not been completed. Therefore, the aim of this review was to identify the strengths, weaknesses, opportunities, and threats within the spice supply chain considering these six “peppers” to analyze their positive and negative aspects. Finally, we selected the most representative molecules and properties of spices referred to as “pepper” to expand the research focus and highlight their key aspects related to health and sensory science for future applications. In this sense, this review provides a new strategic guideline that will help us understand and assess the key internal and external factors of pepper, allowing them to be applied in different sectors with different approaches. Full article

(This article belongs to the Special Issue Nutrition and Sensory Analysis of Food)

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21 pages, 3065 KiB

Open AccessArticle

Reactive Behaviour of Platinum(II) Salts with Ethylenediamine in Sustainable Water/Choline Chloride-Based Deep Eutectic Solvents Mixtures

by Nicola Garofalo, Francesco Messa, Alessandra Barbanente, Francesco Paolo Fanizzi, Antonio Salomone, Nicola Margiotta and Paride Papadia

Molecules 2025, 30(9), 1890; https://doi.org/10.3390/molecules30091890 - 24 Apr 2025

Abstract

Deep eutectic solvents (DESs) are environmentally friendly solvents formed by combining hydrogen bond donors and acceptors, resulting in a eutectic mixture with a lower melting point than the individual components. While there is extensive research on the electrochemical synthesis of platinum nanoparticles in [...] Read more.

Deep eutectic solvents (DESs) are environmentally friendly solvents formed by combining hydrogen bond donors and acceptors, resulting in a eutectic mixture with a lower melting point than the individual components. While there is extensive research on the electrochemical synthesis of platinum nanoparticles in DESs, to the best of our knowledge, there are no studies on the chemical reactivity of platinum(II) complexes in these systems. This study investigates the simple model reaction between K₂PtCl₄ and ethylenediamine (en), exploring the behaviour in DES environment, to optimize the synthesis of simple cisplatin-like platinum compounds with the potential objective of improving the traditional methods, decreasing the number of steps required for obtaining target compounds and reducing chemical waste. The reactions were performed in two hydrophilic DESs: choline chloride:glycerol 1:2 (glyceline, GL) and choline chloride:ethylene glycol 1:2 (ethaline, EG). The experiments, conducted in a 70% (v/v) DES and 30% 1:1 H₂O/D₂O mixture to allow for direct NMR analysis, revealed that en quickly formed [PtCl₂(en)], which further reacted to produce [Pt(en)₂]Cl₂. Reaction products were characterised by 1D (¹H and ¹⁹⁵Pt{¹H}) and 2D ([¹H,¹³C]-HSQC and [¹H,¹⁵N]-HSQC) NMR experiments. The discolouration of solutions, due to the consumption of K₂PtCl₄, and the precipitation of the purple Magnus salt [Pt(en)₂][PtCl₄] occurred over time. The main observed difference between the two solvent mixtures was the slower reactivity in glyceline, due to the much higher viscosity of the solution. Diffusion-ordered spectroscopy (DOSY) indicated lower water mobility in DES mixtures than pure water, with the reaction products closely associated with DES molecules. Full article

(This article belongs to the Special Issue Applications of NMR Spectroscopy to Problem Solving for Inorganic, Organometallic, and Organic Compounds)

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13 pages, 4069 KiB

Open AccessArticle

Bioresorbable High-Strength HA/PLLA Composites for Internal Fracture Fixation

by Jie Liu, Mingtao Sun, Yipeng He, Weixia Yan, Muhuo Yu and Keqing Han

Molecules 2025, 30(9), 1889; https://doi.org/10.3390/molecules30091889 - 23 Apr 2025

Abstract

In modern surgery, the internal fixation plates fabricated from hydroxyapatite/poly(L-lactide) (HA/PLLA) composites encounter clinical limitations in fracture treatment due to their inadequate mechanical properties. In this work, pressure-induced flow (PIF) technique is employed to address this limitation. Under optimal processing conditions (140 °C [...] Read more.

In modern surgery, the internal fixation plates fabricated from hydroxyapatite/poly(L-lactide) (HA/PLLA) composites encounter clinical limitations in fracture treatment due to their inadequate mechanical properties. In this work, pressure-induced flow (PIF) technique is employed to address this limitation. Under optimal processing conditions (140 °C and 250 MPa), the HA/PLLA composites exhibit an impressive flexural strength of 199.2 MPa, which is comparable to that of human cortical bone, the strongest bone tissue in the body. The tensile strength and the notched Izod impact strength are close to 84.2 MPa and 16.7 kJ/m², respectively. Meanwhile, the HA/PLLA composites develop multi-level stacked crystal layers during PIF processing, accompanied by increases in crystallinity (53.1%), crystal orientation (81.6%) and glass transition temperature (78.8 °C). After 2 months of in vitro degradation, the HA/PLLA composites processed by the PIF technique still maintain considerable flexural strength (135.3 MPa). The excellent mechanical properties of HA/PLLA composites processed by PIF technique expand their potential as an internal fixation plate. Full article

(This article belongs to the Special Issue Molecular Scaffolds Design and Biomedical Applications)

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29 pages, 1843 KiB

Open AccessReview

Molecular Links Between Circadian Rhythm Disruption, Melatonin, and Neurodegenerative Diseases: An Updated Review

by Kemal Hüsnü Can Baser, Ismail Celil Haskologlu and Emine Erdag

Molecules 2025, 30(9), 1888; https://doi.org/10.3390/molecules30091888 - 23 Apr 2025

Abstract

Circadian rhythms are molecular oscillations governed by transcriptional–translational feedback loops (TTFLs) operating in nearly all cell types and are fundamental to physiological homeostasis. Key circadian regulators, such as circadian locomotor output cycles kaput (CLOCK), brain and muscle ARNT-like 1 (BMAL1), period [...] Read more.

Circadian rhythms are molecular oscillations governed by transcriptional–translational feedback loops (TTFLs) operating in nearly all cell types and are fundamental to physiological homeostasis. Key circadian regulators, such as circadian locomotor output cycles kaput (CLOCK), brain and muscle ARNT-like 1 (BMAL1), period (PER), and cryptochrome (CRY) gene families, regulate intracellular metabolism, oxidative balance, mitochondrial function, and synaptic plasticity. Circadian disruption is known as a central contributor to the molecular pathophysiology of neurodegenerative disorders. Disease-specific disruptions in clock gene expression and melatoninergic signaling are known as potential early-stage molecular biomarkers. Melatonin, a neurohormone secreted by the pineal gland, modulates clock gene expression, mitochondrial stability, and inflammatory responses. It also regulates epigenetic and metabolic processes through nuclear receptors and metabolic regulators involved in circadian and cellular stress pathways, thereby exerting neuroprotective effects and maintaining neuronal integrity. This review provides recent findings from the past five years, highlighting how circadian dysregulation mediates key molecular and cellular disturbances and the translational potential of circadian-based therapies in neurodegenerative diseases. Full article

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16 pages, 3975 KiB

Open AccessArticle

Perfluoropropionic Acid (CF₃CF₂C(O)OH): Three Conformations and Dimer Formation

by Carlos O. Della Védova, Rosana M. Romano, Hans-Georg Stammler and Norbert W. Mitzel

Molecules 2025, 30(9), 1887; https://doi.org/10.3390/molecules30091887 - 23 Apr 2025

Abstract

Perfluoropropionic acid (CF₃CF₂C(O)OH) has been investigated with a focus on its complex structural properties. As a formal derivative of propanoic acid, the incorporation of fluorine atoms imparts unique structural features, including three distinct monomeric conformations and a dimeric structure. [...] Read more.

Perfluoropropionic acid (CF₃CF₂C(O)OH) has been investigated with a focus on its complex structural properties. As a formal derivative of propanoic acid, the incorporation of fluorine atoms imparts unique structural features, including three distinct monomeric conformations and a dimeric structure. This study presents experimental findings, supported by computational modeling, to explore these characteristics. The analysis includes an FTIR study of the isolated species in an Ar-cryogenic matrix and the low-temperature determination of its crystalline structure using single-crystal X-ray diffraction. Full article

(This article belongs to the Special Issue From Spectroscopic Insights to Structural Wonders: A Theme Issue Dedicated to Professor Jaan Laane)

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15 pages, 1352 KiB

Open AccessArticle

Evaluation of Polycyclic Aromatic Hydrocarbons (PAHs) in Pork Meat Cooked with Two Different Methods

by Chiara Conchione, Silvia Socal, Laura Barp and Sabrina Moret

Molecules 2025, 30(9), 1886; https://doi.org/10.3390/molecules30091886 - 23 Apr 2025

Abstract

During domestic grilling, polycyclic aromatic hydrocarbons (PAHs), which include genotoxic and carcinogenic compounds, can be produced as a result of fat pyrolysis, leakage of cellular juices onto the heat source, and incomplete combustion of fuel. This study aimed to assess the formation of [...] Read more.

During domestic grilling, polycyclic aromatic hydrocarbons (PAHs), which include genotoxic and carcinogenic compounds, can be produced as a result of fat pyrolysis, leakage of cellular juices onto the heat source, and incomplete combustion of fuel. This study aimed to assess the formation of PAHs in pork neck cooked using two different grilling methods (traditional flat grill with beech charcoal and asado grill with beech wood flame) under controlled conditions, with cooking stopping at a core temperature of 72 °C. The impact of marinating and cooking speed (fast or slow) was also evaluated over three cooking sessions. After grilling, the meat samples underwent microwave-assisted extraction, purification through solid-phase extraction (SPE), and analysis using ultra-high-performance liquid chromatography (UHPLC) with spectrofluorometric detection. Statistical analysis was performed using ANOVA (R software, version 4.3.0). None of the samples exceeded the legal limits for benzo[a]pyrene (BaP) and PAH4 (sum of chrysene, benzo[a]anthracene, BaP, and benzo[b]fluoranthene). However, the asado grill showed a significantly higher average PAH contamination (1.21 µg/kg of BaP and 3.92 µg/kg of PAH4) compared with the traditional grill (0.22 µg/kg of BaP and 1.71 µg/kg of PAH4). Marinating and cooking speed did not have a significant impact on PAH levels. Full article

(This article belongs to the Special Issue Molecules in 2025)

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9 pages, 1045 KiB

Open AccessArticle

The Effects of Solvation Enthalpy, Surface Tension, and Conductivity of Common Additives on Positive Electrospray Ionization in Selected Pharmaceuticals

by Pieter Venter

Molecules 2025, 30(9), 1885; https://doi.org/10.3390/molecules30091885 - 23 Apr 2025

Abstract

This study investigates the effects of common additives, which provide distinct proton sources—ammonium (NH₄⁺) and hydronium (H₃O⁺)—along with their corresponding conjugate base species, on signal intensity in positive ionization mode. The findings reveal that signal intensity [...] Read more.

This study investigates the effects of common additives, which provide distinct proton sources—ammonium (NH₄⁺) and hydronium (H₃O⁺)—along with their corresponding conjugate base species, on signal intensity in positive ionization mode. The findings reveal that signal intensity is influenced by factors such as solvation enthalpy, surface tension, and conductivity. At lower additive concentrations (<10 mM), based on fold changes, no clear distinction could be made between formic acid, acetic acid, and their corresponding salts. At higher additive concentrations, NH₄⁺ appears to be a more efficient proton source than H⁺ (H₃O⁺), likely due to its more positive solvation enthalpy, which promotes greater enrichment of NH₄⁺ on the droplet surface, as well as the reduced surface tension of ammonium salts compared to their acid counterparts. Additionally, ammonium hydroxide proves to be the most effective ammonium-based modifier, likely due to its anionic conjugate base, hydroxide, which has a more negative solvation enthalpy compared to acetate and formate. This characteristic is hypothesized to reduce charge neutralization of cations on the droplet surface and/or in the gas phase. Furthermore, ammonium hydroxide exhibits lower conductivity compared to the other ammonium additives, which is believed to enhance signal intensity. Ammonium bicarbonate, the second most effective additive, uniquely prevents metal adduct formation, leading to enhanced [M + H]⁺ ion signals. Full article

(This article belongs to the Section Analytical Chemistry)

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21 pages, 5086 KiB

Open AccessArticle

Insights into the Involvement of TRPA1 Channels in the Neuro-Inflammatory Machinery of Trigeminal Neuralgia

by Chiara Demartini, Rosaria Greco, Anna Maria Zanaboni, Miriam Francavilla, Sara Facchetti, Cristina Nativi and Cristina Tassorelli

Molecules 2025, 30(9), 1884; https://doi.org/10.3390/molecules30091884 - 23 Apr 2025

Abstract

Antagonism of transient receptor potential ankyrin type-1 (TRPA1) channels counteracts the experimentally induced trigeminal neuralgia (TN) pain. TRPA1 channels activated/sensitized by inflammatory stimuli can modulate glial cell activity, a driving force for pathological pain. Additionally, the evidence of a link between TRPA1 and [...] Read more.

Antagonism of transient receptor potential ankyrin type-1 (TRPA1) channels counteracts the experimentally induced trigeminal neuralgia (TN) pain. TRPA1 channels activated/sensitized by inflammatory stimuli can modulate glial cell activity, a driving force for pathological pain. Additionally, the evidence of a link between TRPA1 and the inflammatory-related Toll-like receptors 4 (TLR4) and 7 (TLR7) highlights the potential of the TRPA1-blocking strategy to reduce pain and inflammation in TN. In this study, we aimed to further investigate the putative involvement of TRPA1 channels in the inflammatory pathways following the development of TN. We focused on the possible modulation of glial activity after TRPA1 blockade and the crosstalk of TRPA1 with TLR7 and TLR4. In a rat model of TN, based on chronic constriction injury of the infraorbital nerve, the impact of TRPA1 antagonism through ADM_12 treatment was assessed following the onset of mechanical allodynia (26 days post-surgery). The evaluation of central and peripheral inflammatory mediators (by rt-PCR and ELISA) and immunofluorescence staining of glial expression in the trigeminal nucleus caudalis was investigated using plasma samples and areas related to the trigeminal system (trigeminal ganglion and areas containing the trigeminal nucleus caudalis). Compared to sham-operated rats, the TN-like animals showed significant increases in the number of microglial and astroglial cells in the trigeminal nucleus caudalis, with higher and lower protein plasma levels of pro-inflammatory and anti-inflammatory cytokines, respectively. Additionally, in the trigeminal-related areas, TN-like animals showed significantly higher gene expression levels of TLR4, TLR7, miR-let-7b, and high-mobility group box-1. TRPA1 antagonism reverted all the observed alterations in TN-like rats in the trigeminal-related areas and plasma except microglial cell number in the trigeminal nucleus caudalis. The findings suggest that, in addition to their known involvement in the nociceptive pathway, TRPA1 channels may also play a direct or indirect role in pain-related inflammation, through the activation of TLR4- and TLR7-mediated pathways at the neuronal and glial levels. Full article

(This article belongs to the Special Issue Carriers, Channels, Receptors, and Enzymes: Protein Targets of New Synthetic and Natural Compounds)

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15 pages, 3410 KiB

Open AccessArticle

Comparison of Phosphonium and Sulfoxonium Ylides in Ru(II)-Catalyzed Dehydrogenative Annulations: A Density Functional Theory Study

by Wei Zhou, Lei Zhang, Dan-Yang Liu, Xiaosi Ma, Jie Zhang and Jiajia Kang

Molecules 2025, 30(9), 1883; https://doi.org/10.3390/molecules30091883 - 23 Apr 2025

Abstract

Density functional theory calculations have been performed to explore the detailed mechanism of a ruthenium-catalyzed dehydrogenative annulation between α-carbonyl phosphonium ylide (A) and sulfoxonium ylide (B). The proposed catalytic cycles consist of several elementary steps in succession, namely the [...] Read more.

Density functional theory calculations have been performed to explore the detailed mechanism of a ruthenium-catalyzed dehydrogenative annulation between α-carbonyl phosphonium ylide (A) and sulfoxonium ylide (B). The proposed catalytic cycles consist of several elementary steps in succession, namely the C–H activation of ylide A, the insertion of ylide B, reductive elimination, protodemetallation, and an intramolecular Wittig reaction, in which C–H activation is rate-limiting, with a free energy barrier of 31.7 kcal/mol. As A and B are both capable of being a C–H activation substrate and a carbene precursor, there are potentially four competing pathways including homo-coupling reactions. Further calculations demonstrate that A is more reactive in the C–H activation step than B, while the opposite conclusion is true for the ylide insertion step, which can successfully explain the fact that the solely observed product originated from the use of A as the C–H activation substrate and B as the carbene precursor. Molecular electrostatic potential, charge decomposition, and electron density difference analyses were performed to understand the distinct behaviors of the two ylides and the nature of the key ruthenium–carbene intermediate. Full article

(This article belongs to the Special Issue Molecular Electron Density Theory (MEDT) and Organic Chemistry Reactivity—in Honor of the Great Contributions of Prof. Dr. Luis R. Domingo)

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15 pages, 1171 KiB

Open AccessArticle

An Electron Paramagnetic Resonance Study of the Superoxide-Scavenging and Redox-Modulating Effects of Lecithinized Superoxide Dismutase in the Bloodstream

by Dessislava Lazarova, Plamen Getsov, Rumiana Bakalova, Biliana Nikolova, Severina Semkova, Zhivko Zhelev, Zhiwei Qiao, Tomohiro Ishikawa, Koichiro Fukuda, Kensuke Osada, Milka Mileva, Tohru Mizushima and Ichio Aoki

Molecules 2025, 30(9), 1882; https://doi.org/10.3390/molecules30091882 - 23 Apr 2025

Abstract

Lecithinized superoxide dismutase (PC-SOD) was found to have a significantly improved half-life in the bloodstream and better pharmacological effects compared with unmodified SOD. However, there is no direct evidence that parenterally administered PC-SOD decreases superoxide levels in blood and tissues in vivo. In [...] Read more.

Lecithinized superoxide dismutase (PC-SOD) was found to have a significantly improved half-life in the bloodstream and better pharmacological effects compared with unmodified SOD. However, there is no direct evidence that parenterally administered PC-SOD decreases superoxide levels in blood and tissues in vivo. In the present study, we investigated the ability of PC-SOD versus unmodified SOD as a superoxide scavenger in mice subjected to oxidative stress. Experiments were performed on a lipopolysaccharide (LPS) mouse model of acute inflammation known to be accompanied by the overproduction of superoxide in the blood. The mice were divided into four groups: untreated (healthy; n = 6), LPS-treated (n = 7), LPS/SOD-treated (n = 6), and LPS/PC-SOD-treated (n = 7) mice. SOD and PC-SOD were injected intravenously. Blood samples were collected at four time intervals and analyzed by electron paramagnetic resonance (EPR) spectroscopy using a nitroxide probe, 3-carbamoyl-2,2,5,5-tetramethylpyrrolidine-1-oxyl (CMP). The following effects were observed: (i) In the blood of healthy mice, the EPR signal was significantly lower compared with the control (p < 0.001) and LPS-treated mice (p < 0.01); (ii) in the blood of LPS-treated mice, the EPR signal was identical to that of the control; and (iii) in the blood of LPS/SOD-treated mice collected immediately after enzyme injection, the EPR signal was significantly lower compared with the control (p < 0.01) and LPS-treated mice (p < 0.05). However, the effect disappeared in the samples collected 30 min and 1 h after enzyme injection. (iv) In LPS/PC-SOD-treated mice, the EPR signal was significantly lower compared with the control (p < 0.01) and LPS-treated mice (p < 0.05), even in the blood samples collected within 1 h after enzyme injection. The data indicate that the blood of healthy mice was characterized by a high reducing capacity, while the blood of LPS-treated mice was characterized by a high oxidative capacity. SOD decreased superoxide production immediately after enzyme injection. However, the effect was short-lived and disappeared within 30 min. PC-SOD effectively decreased superoxide production in the bloodstream of LPS-treated mice and restored the redox balance to the control level even two hours after enzyme injection. The effects of PC-SOD were more pronounced and long-lasting compared with those of SOD. The possible reason is the longer half-life of PC-SOD in the bloodstream, its better stability, and its slower clearance from the circulation due to the increased hydrophobicity of the enzyme and its interaction with plasma proteins. The data are discussed in the context of recent clinical trials showing that PC-SOD is a promising pharmaceutical product for adjuvant therapy of a variety of pathologies accompanied by inflammation, redox imbalance, and oxidative stress. Full article

(This article belongs to the Special Issue A New Diagnosis Tool of Cancer by Spectroscopic Analysis-Second Edition)

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24 pages, 2892 KiB

Open AccessArticle

Electrochemical Degradation of Venlafaxine on Platinum Electrodes: Identification of Transformation Products by LC-MS/MS and In Silico Ecotoxicity Assessment

by Angelica R. Zizzamia, Veronica Pasquariello, Filomena Lelario, Carmen Tesoro and Rosanna Ciriello

Molecules 2025, 30(9), 1881; https://doi.org/10.3390/molecules30091881 - 23 Apr 2025

Abstract

Antidepressants are emerging contaminants that have raised global concern due to their abuse. Venlafaxine (VFX), a serotonin and norepinephrine reuptake inhibitor, can cause adverse and potentially toxic effects on aquatic organisms. Electrochemical advanced oxidation processes (EAOPs) are gaining attention as promising degradation techniques [...] Read more.

Antidepressants are emerging contaminants that have raised global concern due to their abuse. Venlafaxine (VFX), a serotonin and norepinephrine reuptake inhibitor, can cause adverse and potentially toxic effects on aquatic organisms. Electrochemical advanced oxidation processes (EAOPs) are gaining attention as promising degradation techniques for a variety of drugs. EAOP methods proposed for VFX degradation mainly utilize boron-doped diamond (BDD) electrodes, characterized by low background current and high oxygen overpotential. However, challenges arise, including delamination from the substrate, difficulties in scaling up, and limited service life. In this study, platinum was employed as an anode for the galvanostatic degradation of VFX, due to its stability and well-established surface cleaning procedure, which ensured high reproducibility. A 0.1 M Na₂SO₄ solution at pH 9 was used as the supporting electrolyte, and a current density of 25 mA/cm² was applied. After 7 h, a degradation efficiency of 94% was achieved for a 25 ppm VFX solution. The hydroxyl and sulfate radicals generated in the electrochemical system were the active species responsible for VFX degradation, which followed a first-order kinetic model with a rate constant of 0.0084 min⁻¹. The main degradation intermediates were identified through LC-MS, including two isomers with a nominal m/z of 276 and three isomers with a nominal m/z of 294. The toxicity of the VFX degradation products was assessed by an in silico prediction model. This evaluation confirmed the sustainability of the developed method. Full article

(This article belongs to the Special Issue Determination, Adsorption and Degradation Mechanisms of Environmental Pollutants)

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16 pages, 713 KiB

Open AccessArticle

The Influence of Integrated and Intensive Grain Production on the Content and Properties of Chemical Components in Rye Grain

by Krzysztof Buksa, Alicja Sułek and Michał Szczypek

Molecules 2025, 30(9), 1880; https://doi.org/10.3390/molecules30091880 - 23 Apr 2025

Abstract

The effect of integrated and intensive grain production technologies on the content and properties of chemical components in rye (Secale cereale L.) grain of new varieties is not known. This study aimed to examine the effect of production technology on the content [...] Read more.

The effect of integrated and intensive grain production technologies on the content and properties of chemical components in rye (Secale cereale L.) grain of new varieties is not known. This study aimed to examine the effect of production technology on the content and properties of chemical components of rye grain. Grain from four Polish rye varieties obtained as a result of integrated and intensive production was examined. In general, the use of intensive technology resulted in receiving a 7.9% higher yield of grain with a 3.7% higher content of starch, characterized by a higher share of amylose and lower molar mass compared to grain cultivated using the integrated method. Moreover, grain from intensive production contained 0.6% more water-soluble arabinoxylan of a high molar mass but a lower content of ferulic acid, compared to grain obtained by the integrated method. Rye grain from intensive production contained 0.4% more protein, 0.3% more soluble dietary fiber, and similar amounts of phytates than grain cultivated using the integrated method. Regardless of the production method, the hybrid varieties KWS Vinetto and KWS Bono had the highest grain yield and grain with a low content of protein, total and soluble dietary fiber, and extractable arabinoxylan of a high molar mass but low content of ferulic acid. Full article

(This article belongs to the Special Issue Bioactive Compounds in Food and Their Applications)

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19 pages, 5653 KiB

Open AccessArticle

Implementation of Machine Learning in Flat Die Extrusion of Polymers

by Nickolas D. Polychronopoulos, Ioannis Sarris and John Vlachopoulos

Molecules 2025, 30(9), 1879; https://doi.org/10.3390/molecules30091879 - 23 Apr 2025

Abstract

Achieving a uniform thickness and defect-free production in the flat die extrusion of polymer sheets and films is a major challenge. Dies are designed for one extrusion scenario, for a polymer grade with specified rheological behavior, and for a given throughput rate. The [...] Read more.

Achieving a uniform thickness and defect-free production in the flat die extrusion of polymer sheets and films is a major challenge. Dies are designed for one extrusion scenario, for a polymer grade with specified rheological behavior, and for a given throughput rate. The extrusion of different polymer grades and at different flow rates requires trial-and-error procedures. This study investigated the application of machine learning (ML) to provide guidance for the extrusion of sheets and films with a reduced thickness, non-uniformities, and without defects. A dataset of 200 cases was generated using computer simulation software for flat die extrusion. The dataset encompassed variations in die geometry by varying the gap under a restrictor, polymer rheological and thermophysical properties, and processing conditions, including throughput rate and temperatures. The dataset was used to train and evaluate the following three powerful machine learning (ML) algorithms: Random Forest (RF), XGBoost, and Support Vector Regression (SVR). The ML models were trained to predict thickness variations, pressure drops, and the lowest wall shear rate (targets). Using the SHapley Additive exPlanations (SHAP) analysis provided valuable insights into the influence of input features, highlighting the critical roles of polymer rheology, throughput rate, and the gap beneath the restrictor in determining targets. This ML-based methodology has the potential to reduce or even eliminate the use of trial and error procedures. Full article

(This article belongs to the Special Issue Synthesis, Characterization and Application of Polymer-Based Materials, 2nd Edition)

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17 pages, 9967 KiB

Open AccessArticle

Colon-Targeted Mucoadhesive PLGA Microspheres Loaded with Ramulus Mori Alkaloids for Enhanced Water-Soluble Drug Delivery in Ulcerative Colitis Treatment

by Mo Wang, Yu Jiang, Zhiyang Chen, Dengbao Jiang, Xuan Jiang, Jun Ye, Hongliang Wang and Yuling Liu

Molecules 2025, 30(9), 1878; https://doi.org/10.3390/molecules30091878 - 23 Apr 2025

Abstract

Ulcerative colitis (UC) is a chronic inflammation disease with severe impact on quality of life, with limited treatment options. Ramulus Mori alkaloids (SZ-A) from Morus alba show promise for UC treatment due to their safety and pharmacological effects, including anti-inflammation and barrier repair. [...] Read more.

Ulcerative colitis (UC) is a chronic inflammation disease with severe impact on quality of life, with limited treatment options. Ramulus Mori alkaloids (SZ-A) from Morus alba show promise for UC treatment due to their safety and pharmacological effects, including anti-inflammation and barrier repair. However, their clinical use has been limited by gastrointestinal flatulence as a side effect due to their pharmacological action as an α-glucosidase inhibitor targeting the small intestine following oral administration. Therefore, constructing a colon-targeted formulation to deliver SZ-A is an advantageous strategy to improve UC therapy. In this study, we used the complex formed by thiolated hyaluronic acid, which has mucosal adhesion and inflammation-targeting properties, and SZ-A as an intermediate carrier and prepared sodium alginate-modified PLGA microspheres (SZ-A@MSs) with the double emulsion method to achieve efficient encapsulation of SZ-A. Specifically, sodium alginate serves as a gastric acid protectant and microbiota-responsive material, enabling the precise and responsive release of microspheres in the colonic region. SZ-A@MSs have a particle size of about 30 µm, a drug loading of about 12.0%, and an encapsulation efficiency of about 31.7% and function through intestinal adhesion to and targeting of inflammatory sites. SZ-A@MSs showed antioxidant and anti-inflammatory abilities in Raw264.7 cells. In vivo imaging results suggest that SZ-A@MSs have good colon site retention and sustained-release effect. Pharmacodynamic results show that SZ-A@MSs display good efficacy, including the ability to inhibit weight loss, inhibit colonic atrophy, and inhibit the secretion of inflammatory factors. In conclusion, SZ-A@MSs have good colon-targeting properties, can improve therapeutic effects, and provide a potential treatment method for UC. Full article

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25 pages, 17345 KiB

Open AccessArticle

The Influence of Osmotic Treatment, Edible Coatings Application, and Reduced Pressure on Microwave–Vacuum-Dried Carrot Properties

by Anna Ignaczak, Łukasz Woźniak, Agata Marzec, Jolanta Kowalska, Małgorzata Chobot and Hanna Kowalska

Molecules 2025, 30(9), 1877; https://doi.org/10.3390/molecules30091877 - 23 Apr 2025

Abstract

The study investigated the effect of osmotic treatment, edible coatings, and reduced pressure on the quality of carrots dried by the microwave–vacuum method (MVD) at 3.5 or 6.5 kPa and microwave power of 250 W. Initial osmotic enrichment (OE) of carrots was carried [...] Read more.

The study investigated the effect of osmotic treatment, edible coatings, and reduced pressure on the quality of carrots dried by the microwave–vacuum method (MVD) at 3.5 or 6.5 kPa and microwave power of 250 W. Initial osmotic enrichment (OE) of carrots was carried out in chokeberry NFC juice, and osmotic dehydration (OD) in chokeberry juice concentrate. Coatings were prepared using sodium alginate or citrus pectin solutions of 1.0 or 1.5%. Osmotic treatment, and then drying pressure, had the greatest effect on increasing the dry matter (DM), total phenolic content (TPC), and color changes, but also on decreasing the water activity (AW) of dried carrot. The highest DM (average 98.7%) and the lowest AW (average 0.25) were obtained in OE carrots and dried at 3.5 kPa. Drying carrots, combined with osmotic treatment and coating, increased TPC by 13-fold, from 225 in fresh to 3229 mg GAE/100 g d.m. in dried carrots. Osmotic treatment did not affect the antioxidant activity of DPPH•, but OD significantly increased ABTS•+ compared to the raw material. Coatings had a smaller effect on color changes and antioxidant activity (DPPH• and ABTS•+) and no significant impact on DM and AW. The color changes of the control and coated samples were an increase in color lightness, redness, yellowness, and saturation (vividness), and those subjected to osmotic treatment showed a decrease in these parameters. The lower AW of dried carrots positively affected higher hardness. All samples were sensory accepted, including color, texture, and smell, especially after OD in chokeberry juice concentrate, while crunchiness was the lowest (five out of nine points). Full article

(This article belongs to the Special Issue Active Ingredients in Functional Foods and Their Impact on Health, 2nd Edition)

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13 pages, 1533 KiB

Open AccessArticle

Surface-Enhanced Raman Spectroscopy on Gold Nanoparticle for Sperm Quality Discrimination

by Yeira P. Lopez-Lora, Nataly J. Galán-Freyle, Natally Vidal-Figueroa, Antony A. Cardozo-Puello, Antonio J. Acosta-Hoyos, Guido Parra-Anaya, Elvin S. Lebrón-Ramírez, Fabián Espitia-Almeida, Samuel P. Hernández-Rivera, Maximiliano Méndez-López, Ornella Fiorillo-Moreno, Karin Rondon-Payare and Leonardo C. Pacheco-Londoño

Molecules 2025, 30(9), 1876; https://doi.org/10.3390/molecules30091876 - 23 Apr 2025

Abstract

Spermatozoa were isolated from the seminal fluid using washing (wash), post-capacitation (POS), and swim-up (SU) techniques, followed by analysis through Surface-Enhanced Raman Spectroscopy (SERS). Density gradient and swim-up methods were applied to 35 semen samples to validate sperm quality. The resulting spectra showed [...] Read more.

Spermatozoa were isolated from the seminal fluid using washing (wash), post-capacitation (POS), and swim-up (SU) techniques, followed by analysis through Surface-Enhanced Raman Spectroscopy (SERS). Density gradient and swim-up methods were applied to 35 semen samples to validate sperm quality. The resulting spectra showed notable variations at 408 cm⁻¹ (S–S stretch attributed to lysozyme) and 728 cm⁻¹ (associated with DNA alterations and methylation). These spectral markers were incorporated into partial least squares discriminant analysis (PLS-DA) models to distinguish among sperm populations prepared by different methods. One PLS-DA model differentiated wash from POS and SU, attaining 86% sensitivity and 91% accuracy. Another model distinguished between POS and SU, achieving 77% sensitivity and 74% accuracy. The combined use of SERS and multivariate analysis offers a promising alternative for assessing sperm quality, supported by motility assessments in 35 validated samples. This approach could enhance both the accuracy and efficiency of reproductive diagnostics. Full article

(This article belongs to the Special Issue Molecular Spectroscopy in Applied Chemistry)

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16 pages, 6102 KiB

Open AccessArticle

Study on the Influence of Sn Concentration on Non-Substitutional Defect Concentration and Sn Surface Segregation in GeSn Alloys

by Zihang Zhou, Jiayi Li, Mengjiang Jia, Hai Wang, Wenqi Huang and Jun Zheng

Molecules 2025, 30(9), 1875; https://doi.org/10.3390/molecules30091875 - 23 Apr 2025

Abstract

GeSn alloys are among the most promising materials for the fabrication of high-efficiency silicon-based light sources. However, due to the tendency of Sn to segregate to the surface during growth, it is challenging to achieve a high Sn concentration while maintaining high-quality GeSn [...] Read more.

GeSn alloys are among the most promising materials for the fabrication of high-efficiency silicon-based light sources. However, due to the tendency of Sn to segregate to the surface during growth, it is challenging to achieve a high Sn concentration while maintaining high-quality GeSn alloys. Both theoretical and experimental studies have confirmed that non-substitutional Sn defects (VSnV) are the primary driving factors in Sn surface segregation. However, there is a discrepancy between existing theoretical and experimental findings regarding the variation in VSnV concentration with total Sn concentration. To clarify this issue, we first prepared GeSn materials with varying Sn concentrations using molecular beam epitaxy (MBE) and subjected them to annealing at different temperatures. Subsequently, we characterized the VSnV concentration and Sn surface segregation. The results indicate that a higher total Sn concentration and temperature lead to an increased VSnV concentration, and the proportion of VSnV relative to the total Sn concentration also increases, which is consistent with existing theoretical research. To explain these phenomena, we employed first-principles calculations based on density functional theory (DFT) to investigate the effect of varying the total Sn concentration on the formation of substitutional Sn (Sn_s) and VSnV in GeSn alloys, while simultaneously studying the migration kinetics of Sn atoms. The results demonstrate that as the total Sn concentration increases, the formation of Sn_s becomes more difficult, while the formation of VSnV becomes easier, and Sn atoms exhibit enhanced migration tendencies. The analysis of binding energies and charge density distribution maps reveals that this is due to the weakening of Ge-Sn bond strength with increasing Sn concentration, whereas the binding strength of VSnV exhibits the opposite trend. These findings demonstrate excellent agreement with experimental observations. This study provides both theoretical and experimental references for GeSn material growth and VSnV defect control through a combined theoretical–experimental approach, offering significant guidance for enhancing device performance. Full article

(This article belongs to the Section Materials Chemistry)

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Molecules, Volume 30, Issue 9 (May-1 2025) – 43 articles

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