Molecules, Volume 29, Issue 2 (January-2 2024) – 273 articles

Thyroid transcription factor 1 (TTF1) is an important cancer-related biomarker for clinical diagnosis, especially for carcinomas of lung and thyroid origin. Herein, a novel label-free electrochemical immunosensor was prepared for TTF1 detection based on nanohybrids of ribbon-like tungsten disulfide-reduced graphene oxide (WS₂-rGO) and gold nanoparticles (AuNPs). The proposed immunosensor employed H₂O₂ as the electrochemical probe because of the excellent peroxidase-like activity of ribbon-like WS2-rGO. The introduction of AuNPs not only enhanced the electrocatalytic activity of the immunosensor, but also provided immobilization sites for binding TTF1 antibodies. The electrochemical signals can be greatly amplified due to their excellent electrochemical performance, which realized the sensitive determination of TTF1 with a wide linear range of 0.025–50 ng mL⁻¹ and a lower detection limit of 0.016 ng mL⁻¹ (S/N = 3). Moreover, the immunosensor exhibited high selectivity, good reproducibility, and robust stability, as well as the ability to detect TTF1 in human serum with satisfactory results. These observed properties of the immunosensor enhance its potential practicability in clinical applications. This method can also be used for the detection of other tumor biomarkers by using the corresponding antigen–antibody complex. Full article

In this paper, the green synthesis of isoeugenol methyl ether (IEME) from eugenol by O-methylation and isomerization is completed using a one-step green process. In the methylation reaction, dimethyl carbonate (DMC) was used as a green chemistry reagent instead of the traditional harmful methylation reagents, in accordance with the current concept of green chemistry. The phase transfer catalyst (PTC) polyethylene glycol 800 (PEG-800) was introduced into the isomerization reaction to break the barrier of difficult contact between solid and liquid phases and drastically reduce the reaction conditions by shortening the reaction time and reducing the alkalinity of the reaction system. The catalytic systems for the one-step green synthesis of IEME were screened, and it was shown that the catalytic system “K₂CO₃ + PEG-800” was the most effective. The effects of reaction temperature, n(DMC):n(eugenol) ratio, n(PEG-800):n(eugenol) ratio, and n(K₂CO₃):n(eugenol) ratio on eugenol conversion, IEME yield, and IEME selectivity were investigated. The results showed that the best reaction was achieved at a reaction temperature of 140 °C, a reaction time of 3 h, a DMC drip rate of 0.09 mL/min, and n(eugenol):n(DMC):n(K₂CO₃):n(PEG-800) = 1:3:0.09:0.08. As a result of the conversion of 93.1% of eugenol to IEME, a yield of 86.1% IEME as well as 91.6% IEME selectivity were obtained. Full article

Lysine-specific demethylase 1 (LSD1/KDM1A) has emerged as a promising therapeutic target for treating various cancers (such as breast cancer, liver cancer, etc.) and other diseases (blood diseases, cardiovascular diseases, etc.), owing to its observed overexpression, thereby presenting significant opportunities in drug development. Since its discovery in 2004, extensive research has been conducted on LSD1 inhibitors, with notable contributions from computational approaches. This review systematically summarizes LSD1 inhibitors investigated through computer-aided drug design (CADD) technologies since 2010, showcasing a diverse range of chemical scaffolds, including phenelzine derivatives, tranylcypromine (abbreviated as TCP or 2-PCPA) derivatives, nitrogen-containing heterocyclic (pyridine, pyrimidine, azole, thieno[3,2-b]pyrrole, indole, quinoline and benzoxazole) derivatives, natural products (including sanguinarine, phenolic compounds and resveratrol derivatives, flavonoids and other natural products) and others (including thiourea compounds, Fenoldopam and Raloxifene, (4-cyanophenyl)glycine derivatives, propargylamine and benzohydrazide derivatives and inhibitors discovered through AI techniques). Computational techniques, such as virtual screening, molecular docking and 3D-QSAR models, have played a pivotal role in elucidating the interactions between these inhibitors and LSD1. Moreover, the integration of cutting-edge technologies such as artificial intelligence holds promise in facilitating the discovery of novel LSD1 inhibitors. The comprehensive insights presented in this review aim to provide valuable information for advancing further research on LSD1 inhibitors. Full article

Ultralong nanowires with ultrahigh aspect ratios exhibit high flexibility, and they are promising for applications in various fields. Herein, a cadmium oleate precursor hydrothermal method is developed for the synthesis of ultralong nanowires of cadmium phosphate hydroxide. In this method, water-soluble cadmium salt is used as the cadmium source, water-soluble phosphate is used as the phosphorus source, and sodium oleate is adopted as a reactant to form cadmium oleate precursor and as a structure-directing agent. By using this method, ultralong nanowires of cadmium phosphate hydroxide are successfully synthesized using CdCl₂, sodium oleate, and NaH₂PO₄ as reactants in an aqueous solution by hydrothermal treatment at 180 °C for 24 h. In addition, a new type of flexible fire-resistant inorganic paper with good electrical insulation performance is fabricated using ultralong nanowires of cadmium phosphate hydroxide. As an example of the extended application of this synthetic method, ultralong nanowires of cadmium phosphate hydroxide can be converted to ultralong CdS nanowires through a convenient sulfidation reaction. In this way, ultralong CdS nanowires are successfully synthesized by simple sulfidation of ultralong nanowires of cadmium phosphate hydroxide under mild conditions. The as-prepared ultralong nanowires of cadmium phosphate hydroxide are promising for applications as the precursors and templates for synthesizing other inorganic ultralong nanowires and have wide applications in various fields. Full article

Monoamine oxidase and xanthine oxidase inhibitors represent useful multi-target drugs for the prevention, attenuation, and treatment of oxidative damage and neurodegenerative disorders. Chimeric molecules, constituted by naturally derived compounds linked to drugs, represent lead compounds to be explored for the discovery of new synthetic drugs acting as enzyme inhibitors. We have previously reported that seven hydroxytyrosol-donepezil hybrid compounds play a protective role in an in vitro neuronal cell model of Alzheimer’s disease. In this work, we analyzed the effects exerted by the hybrid compounds on the activity of monoamine oxidase A (MAO-A) and B (MAO-B), as well as on xanthine oxidase (XO), enzymes involved in both neurodegenerative disorders and oxidative stress. The results pointed to the identification, among the compounds tested, of selective inhibitors between the two classes of enzymes. While the 4-hydroxy-3-methoxyphenethyl 1-benzylpiperidine-4-carboxylate- (HT3) and the 4-hydroxyphenethyl 1-benzylpiperidine-4-carboxylate- donepezil derivatives (HT4) represented the best inhibitors of MAO-A, with a scarce effect on MAO-B, they were almost ineffective on XO. On the other hand, the 4,5-dihydroxy-2-nitrophenethyl 1-benzylpiperidine-4-carboxylate donepezil derivative (HT2), the least efficient MAO inhibitor, acted like the best XO inhibitor. Therefore, the differential enzymatic targets identified among the hybrid compounds synthesized enhance the possible applications of these polyphenol-donepezil hybrids in neurodegenerative disorders and oxidative stress. Full article

Novel CO₂- and H₃PO₄-modified biochars were successfully synthesized from raw honeycomb biomass. They were characterized via several instrumental techniques. The optimal Pt(II) and Pt(IV) adsorption onto the studied biochars was reached for the initial pH of 1.5 and a contact time of 5 min (Pt(II)) and 24–48 h (Pt(IV)). The highest static adsorption capacities for Pt(II) and Pt(IV) were obtained for the H₃PO₄-modified biochar: 47 mg g⁻¹ and 35 mg g⁻¹, respectively. The Freundlich model described the Pt(II) adsorption isotherms onto both materials and the Pt(IV) adsorption isotherm onto the CO₂-activated material, and the Langmuir model was the best fitted to the Pt(IV) adsorption isotherm onto the H₃PO₄-activated biochar. The best medium for the quantitative desorption of the Pt form from the H₃PO₄-modified biochar was 1 mol L⁻¹ thiourea in 1 mol L⁻¹ HCl. The adsorption mechanism of both the studied ions onto the synthesized H₃PO₄-modified biochar was complex and should be further investigated. The H₃PO₄-modified biochar was successfully applied for the first time for Pt(IV) removal from a spent automotive catalyst leaching solution. Full article

Among breast cancer subtypes, triple-negative breast cancer stands out as the most aggressive, with patients facing a 40% mortality rate within the initial five years. The limited treatment options and unfavourable prognosis for triple-negative patients necessitate the development of novel therapeutic strategies. Photodynamic therapy (PDT) is an alternative treatment that can effectively target triple-negative neoplastic cells such as MDA-MB-231. In this in vitro study, we conducted a comparative analysis of the PDT killing rate of unbound Rose Bengal (RB) in solution versus RB-encapsulated chitosan nanoparticles to determine the most effective approach for inducing cytotoxicity at low laser powers (90 mW, 50 mW, 25 mW and 10 mW) and RB concentrations (50 µg/mL, 25 µg/mL, 10 µg/mL and 5 µg/mL). Intracellular singlet oxygen production and cell uptake were also determined for both treatment modalities. Dark toxicity was also assessed for normal breast cells. Despite the low laser power and concentration of nanoparticles (10 mW and 5 µg/mL), MDA-MB-231 cells experienced a substantial reduction in viability (8 ± 1%) compared to those treated with RB solution (38 ± 10%). RB nanoparticles demonstrated higher singlet oxygen production and greater uptake by cancer cells than RB solutions. Moreover, RB nanoparticles display strong cytocompatibility with normal breast cells (MCF-10A). The low activation threshold may be a crucial advantage for specifically targeting malignant cells in deep tissues. Full article

LR004 is a novel chimeric (human/mouse) monoclonal antibody developed for the treatment of advanced colorectal carcinoma with detectable epidermal growth factor receptor (EGFR) expression. We aimed to investigate the preclinical pharmacokinetics (PK) and in vivo biodistribution of LR004. The PK profiles of LR004 were initially established in rhesus monkeys. Subsequently, ¹²⁵I radionuclide-labeled LR004 was developed and the biodistribution, autoradiography, and NanoSPECT/CT of ¹²⁵I-LR004 in xenograft mice bearing A431 tumors were examined. The PK data revealed a prolonged half-life and nonlinear PK characteristics of LR004 within the dose range of 6–54 mg/kg. The radiochemical purity of ¹²⁵I-LR004 was approximately 98.54%, and iodination of LR004 did not affect its specific binding activity to the EGFR antigen. In a classical biodistribution study, ¹²⁵I-LR004 exhibited higher uptake in highly perfused organs than in poorly perfused organs. Prolonged retention properties of ¹²⁵I-LR004 in tumors were observed at 4 and 10 days. Autoradiography and NanoSPECT/CT confirmed the sustained retention of ¹²⁵I-LR004 at the tumor site in xenograft mice. These findings demonstrated the adequate tumor targeting capabilities of ¹²⁵I-LR004 in EGFR-positive tumors, which may improve dosing strategies and future drug development. Full article

Chemical kinetic studies of the β-scission reaction class of hydroperoxyl alkyl hydroperoxyl radicals (•P(OOH)₂) from normal-alkyl cyclohexanes are carried out systematically through high-level ab initio calculations. Geometry optimizations and frequency calculations for all species involved in the reactions are performed at the B3LYP/CBSB7 level of theory. Electronic single-point energy calculations are calculated at the CBS-QB3 level of theory. Rate constants for the reactions of β-scission, in the temperature range of 500–1500 K and the pressure range of 0.01–100 atm, are calculated using transition state theory (TST) and Rice-Ramsberger-Kassel-Marcus/Master-Equation (RRKM/ME) theory taking asymmetric Eckart tunneling corrections and the one-dimensional hindered rotor approximation into consideration. The rate rules are obtained by averaging the rate constants of the representative reactions of this class. These rate rules can greatly assist in constructing more accurate low-temperature combustion mechanisms for normal-alkyl cyclohexanes. Full article

Saturated aqueous salt solutions have diverse applications in food production, mineral processing, pharmaceuticals, and environmental monitoring. However, the random and disordered arrangement of ions in these solutions poses limitations across different fields. In this study, we employ magnetic fields to regulate the disordered arrangement by a comprehensive methodology combining contact angle measurement, Raman spectroscopy, X-ray diffraction, and molecular dynamics simulations on saturated KCl solutions. Our findings reveal that weak magnetic fields impede the formation of K-Cl contact pairs and disrupt hydrogen bond networks, particularly DDAA and free OH types. However, they facilitate the interaction between water molecules and ions, leading to an increase in the number of K-O and Cl-H contact pairs, along with an expansion in ion hydration radius. These changes affect macroscopic properties, including the interaction with solid substrates and potential solubility increases. Our experimental and simulation results mutually validate each other, contributing to a theoretical framework for studying magnetic field–material interactions. Full article

The chemistry of conjugated nitrodienes is becoming increasingly popular. These molecules are successfully applied in cycloaddition to synthesize six-membered rings in Diels-Alder reactions. Nitrodienes can be also applied to obtain bis-compounds in [3+2] cycloaddition. Moreover, the presence of a nitro group in the structure provides a possibility of further modification of the products. The simplest symmetrical representative of conjugated nitrodienes is (1E,3E)-1,4-dinitro-1,3-butadiene. Although the first mentions of the compound date back to the early 1950s, the compound has not yet been examined thoroughly enough. Therefore, in this article, a comprehensive study of (1E,3E)-1,4-dinitro-1,3-butadiene has been described. For this purpose, an experimental study including the synthesis process as well as an evaluation of the spectral characteristics has been conducted. So as to better understand the properties of this compound, a computational study of reactivity indices based on MEDT and also an assessment of pharmacokinetics and biological activity according to ADME and PASS methodologies have been made. On this basis, some future application trends of (1E,3E)-1,4-dinitro-1,3-butadiene have been proposed. Full article

DAPB, a new molecule including danshensu, borneol, and a mother nucleus of ACEI (Angiotensin-converting enzyme inhibitors), is being developed as an antihypertensive candidate compound. A rapid, accurate, and sensitive ultra-performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) method was established and validated for the determination of DAPB in rat plasma. Chromatographic separation was performed on an Agilent SB-C18 column after protein precipitation by acetonitrile with a mobile phase consisting of acetonitrile and deionized water with 0.02% formic acid and 5 mM NH₄F (v/v) at a flow rate of 0.2 mL/min. Quantification was performed using electrospray positive ionization mass spectrometry in the multiple reaction monitoring (MRM) mode. The method was linear over the range of 2–1000 ng/mL. The intra- and inter-day precision was within 12%, with accuracies less than 7%. Stability was within the acceptable limits under various storage and processing conditions. No apparent matrix effect was detected. The validated method was applied to the pre-clinical pharmacokinetic study of DAPB after oral administration of 30 mg/kg and intravenous administration of 6 mg/kg in rats. Full article

Sinomenine, an isoquinoline alkaloid extracted from the roots and stems of Sinomenium acutum, has been extensively studied for its derivatives as bioactive agents. This review concentrates on the research advancements in the biological activities and action mechanisms of sinomenine-related compounds until November 2023. The findings indicate a broad spectrum of pharmacological effects, including antitumor, anti-inflammation, neuroprotection, and immunosuppressive properties. These compounds are notably effective against breast, lung, liver, and prostate cancers, exhibiting IC₅₀ values of approximately 121.4 nM against PC-3 and DU-145 cells, primarily through the PI3K/Akt/mTOR, NF-κB, MAPK, and JAK/STAT signaling pathways. Additionally, they manifest anti-inflammatory and analgesic effects predominantly via the NF-κB, MAPK, and Nrf2 signaling pathways. Utilized in treating rheumatic arthritis, these alkaloids also play a significant role in cardiovascular and cerebrovascular protection, as well as organ protection through the NF-κB, Nrf2, MAPK, and PI3K/Akt/mTOR signaling pathways. This review concludes with perspectives and insights on this topic, highlighting the potential of sinomenine-related compounds in clinical applications and the development of medications derived from natural products. Full article

Most hydrophobes easily diffuse into yeast cells, where they experience reduced evaporation and protection from oxidation, thus allowing inherently biocompatible encapsulation processes. Despite a long-standing industrial interest, the effect of parameters such as how is yeast pre-treated (extraction with ethanol, plasmolysis with hypertonic NaCl, depletion to cell walls), the polarity of the hydrophobes and the process conditions are still not fully understood. Here, we have developed thorough analytical protocols to assess how the effects of the above on S. cerevisiae’s morphology, permeability, and encapsulation efficiency, using three differently polar hydrophobes (linalool, 1,6-dihydrocarvone, limonene) and three separate processes (hydrophobes as pure ‘oils’, water dispersions, or acetone solutions). The harsher the pre-treatment (depleted > plasmolyzed/extracted > untreated cells), the easier the diffusion into yeast became, and the lower both encapsulation efficiency and protection from evaporation, possibly due to denaturation/removal of lipid-associated (membrane) proteins. More hydrophobic terpenes performed worst in encapsulation as pure ‘oils’ or in water dispersion, but much less of a difference existed in acetone. This indicates the specific advantage of solvents/dispersants for ‘difficult’ compounds, which was confirmed by principal component analysis; furthering this concept, we have used combinations of hydrophobes (e.g., linalool and α-tocopherol), with one acting as solvent/enhancer for the other. Our results thus indicate advantages in using untreated yeast and—if necessary—processes based on solvents/secondary hydrophobes. Full article

Silicosis is a complex occupational disease without recognized effective treatment. Celastrol, a natural product, has shown antioxidant, anti-inflammatory, and anti-fibrotic activities, but the narrow therapeutic window and high toxicity severely limit its clinical application. Through structural optimization, we have identified a highly efficient and low-toxicity celastrol derivative, CEL-07. In this study, we systematically investigated the therapeutic potential and underlying mechanisms of CEL-07 in silicosis fibrosis. By constructing a silicosis mouse model and analyzing with HE, Masson, Sirius Red, and immunohistochemical staining, CEL-07 significantly prevented the progress of inflammation and fibrosis, and it effectively improved the lung respiratory function of silicosis mice. Additionally, CEL-07 markedly suppressed the expression of inflammatory factors (IL-6, IL-1α, TNF-α, and TNF-β) and fibrotic factors (α-SMA, collagen I, and collagen III), and promoted apoptosis of fibroblasts by increasing ROS accumulation. Moreover, bioinformatics analysis combined with experimental validation revealed that CEL-07 inhibited the pathways associated with inflammation (PI3K-AKT and JAK2-STAT3) and the expression of apoptosis-related proteins. Overall, these results suggest that CEL-07 may serve as a potential candidate for the treatment of silicosis. Full article

Proton Exchange Membrane Water Electrolysis (PEMWE) under acidic conditions outperforms alkaline water electrolysis in terms of less resistance loss, higher current density, and higher produced hydrogen purity, which make it more economical in long-term applications. However, the efficiency of PEMWE is severely limited by the slow kinetics of anodic oxygen evolution reaction (OER), poor catalyst stability, and high cost. Therefore, researchers in the past decade have made great efforts to explore cheap, efficient, and stable electrode materials. Among them, the RuO₂ electrocatalyst has been proved to be a major promising alternative to Ir-based catalysts and the most promising OER catalyst owing to its excellent electrocatalytic activity and high pH adaptability. In this review, we elaborate two reaction mechanisms of OER (lattice oxygen mechanism and adsorbate evolution mechanism), comprehensively summarize and discuss the recently reported RuO₂-based OER electrocatalysts under acidic conditions, and propose many advanced modification strategies to further improve the activity and stability of RuO₂-based electrocatalytic OER. Finally, we provide suggestions for overcoming the challenges faced by RuO₂ electrocatalysts in practical applications and make prospects for future research. This review provides perspectives and guidance for the rational design of highly active and stable acidic OER electrocatalysts based on PEMWE. Full article

Nitrogen and sulfur co-doped graphene-like carbon nanosheets (CNSs) with a two-dimensional structure are prepared by using methylene blue as a carbon source and expanded vermiculite as a template. After static negative pressure adsorption, high-temperature calcination, and etching in a vacuum oven, they are embedded in the limited space of the vermiculite template. The addition of an appropriate number of mixed elements can improve the performance of a battery. Via scanning electron microscopy, it is found that the prepared nitrogen–sulfur-co-doped carbon nanosheets exhibit a thin yarn shape. The XPS results show that there are four elements of C, N, O, and S in the carbon materials (CNS-600, CNS-700, CNS-800, CNS-900) prepared at different temperatures, and the N atom content shows a gradually decreasing trend. It is mainly doped into a graphene-like network in four ways (graphite nitrogen, pyridine nitrogen, pyrrole nitrogen, and pyridine nitrogen oxide), while the S element shows an increasing trend, mainly in the form of thiophene S and sulfur, which is covalently linked to oxygen. The results show that CNS-700 has a discharge-specific capacity of 460 mAh/g at a current density of 0.1 A/g, and it can still maintain a specific capacity of 200 mAh/g at a current density of 2 A/g. The assembled lithium-ion capacitor has excellent energy density and power density, with a maximum power density of 20,000 W/kg. Full article

The specific and sensitive detection of 17β-estradiol (E2) is critical for diagnosing and treating numerous diseases, and aptamers have emerged as promising recognition probes for developing detection platforms. However, traditional long-sequence E2 aptamers have demonstrated limited clinical performance due to redundant structures that can affect their stability and recognition ability. There is thus an urgent need to further optimize the structure of the aptamer to build an effective detection platform for E2. In this work, we have designed a novel short aptamer that retains the key binding structure of traditional aptamers to E2 while eliminating the redundant structures. The proposed aptamer was evaluated for its binding properties using microscale thermophoresis, a gold nanoparticle-based colorimetric method, and electrochemical assays. Our results demonstrate that the proposed aptamer has excellent specific recognition ability for E2 and a high affinity with a dissociation constant of 92 nM. Moreover, the aptamer shows great potential as a recognition probe for constructing a highly specific and sensitive clinical estradiol detection platform. The aptamer-based electrochemical sensor enabled the detection of E2 with a linear range between 5 pg mL^–1 and 10 ng mL^–1 (R² = 0.973), and the detection capability of a definite low concentration level was 5 pg mL^–1 (S/N = 3). Overall, this novel aptamer holds great promise as a valuable tool for future studies on the role of E2 in various physiological and pathological processes and for developing sensitive and specific diagnostic assays for E2 detection in clinical applications. Full article

The tanning industry generates effluents with high chromium content, which require treatment prior to discharge into the sewage system. This article explores the use of magnetic magnetite nanoparticles (MNPs) to remove Cr(VI) from aqueous solutions, such as tanning effluents. The MNPs were synthesized by coprecipitation reaction using the Olea europaea extract as a reducing agent. Subsequently, they were characterized by dynamic light scattering spectroscopy (DLS), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). MNPs with irregular morphology and diameters ranging from 73.28 to 162.90 nm were obtained. Cr(VI) removal was performed using jar test methodology, and its efficiency was evaluated in the laboratory for different initial Cr(VI) (mg/L) concentration and nanoparticle (g/L) concentration. A kinetic study was developed and indicated that the equilibrium adsorption mechanism corresponds to a pseudo-second-order model. Furthermore, the isotherm analysis revealed that chromium adsorption best fits the Langmuir isotherm. Finally, Cr(VI) removal rates from 85% to 100% were achieved in tanning and retanning effluents. Full article

Bacteriotherapy is emerging as a strategic and effective approach to treat infections by providing putatively harmless bacteria (i.e., probiotics) as antagonists to pathogens. Proper delivery of probiotics or their metabolites (i.e., post-biotics) can facilitate their availing of biomaterial encapsulation via innovative manufacturing technologies. This review paper aims to provide the most recent biomaterial-assisted strategies proposed to treat infections or dysbiosis using bacteriotherapy. We revised the encapsulation processes across multiscale biomaterial approaches, which could be ideal for targeting different tissues and suit diverse therapeutic opportunities. Hydrogels, and specifically polysaccharides, are the focus of this review, as they have been reported to better sustain the vitality of the live cells incorporated. Specifically, the approaches used for fabricating hydrogel-based devices with increasing dimensionality (D)—namely, 0D (i.e., particles), 1D (i.e., fibers), 2D (i.e., fiber meshes), and 3D (i.e., scaffolds)—endowed with probiotics, were detailed by describing their advantages and challenges, along with a future overlook in the field. Electrospinning, electrospray, and 3D bioprinting were investigated as new biofabrication methods for probiotic encapsulation within multidimensional matrices. Finally, examples of biomaterial-based systems for cell and possibly post-biotic release were reported. Full article

In this work, three series of micro-sized heterometallic europium-containing terephthalate MOFs, (Eu_1-xLn_x)₂bdc₃·nH₂O (Ln = La, Gd, Lu), are synthesized via an ultrasound-assisted method in an aqueous medium. La³⁺ and Gd³⁺-doped terephthalates are isostructural to Eu₂bdc₃·4H₂O. Lu³⁺-doped compounds are isostructural to Eu₂bdc₃·4H₂O with Lu contents lower than 95 at.%. The compounds that are isostructural to Lu₂bdc₃·2.5H₂O are formed at higher Lu³⁺ concentrations for the (Eu_1-xLu_x)₂bdc₃·nH₂O series. All materials consist of micrometer-sized particles. The particle shape is determined by the crystalline phase. All the synthesized samples demonstrate an “antenna” effect: a bright-red emission corresponding to the ⁵D₀-⁷F_J transitions of Eu³⁺ ions is observed upon 310 nm excitation into the singlet electronic excited state of terephthalate ions. The fine structure of the emission spectra is determined by the crystalline phase due to the different local symmetries of the Eu³⁺ ions in the different kinds of crystalline structures. The photoluminescence quantum yield and ⁵D₀ excited state lifetime of Eu³⁺ are equal to 11 ± 2% and 0.44 ± 0.01 ms, respectively, for the Ln₂bdc₃·4H₂O structures. For the (Eu_1-xLu_x)₂bdc₃·2.5H₂O compounds, significant increases in the photoluminescence quantum yield and ⁵D₀ excited state lifetime of Eu³⁺ are observed, reaching 23% and 1.62 ms, respectively. Full article

It has been found that the development of some cancers can be attributed to obesity, which is associated with the excessive intake of lipids. Cancer cells undergo metabolic reprogramming, shifting from utilizing glucose to fatty acids (FAs) for energy. CD36, a lipid transporter, is highly expressed in certain kinds of cancer cells. High expressions of CD36 in tumor cells triggers FA uptake and lipid accumulation, promoting rapid tumor growth and initiating metastasis. Meanwhile, immune cells in the tumor microenvironment overexpress CD36 and undergo metabolic reprogramming. CD36-mediated FA uptake leads to lipid accumulation and has immunosuppressive effects. This paper reviews the types of FAs associated with cancer, high expressions of CD36 that promote cancer development and progression, effects of CD36 on different immune cells in the tumor microenvironment, and the current status of CD36 as a therapeutic target for the treatment of tumors with high CD36 expression. Full article

A swarf of aluminum alloy with high corrosion resistance and ductility was successfully converted into fine hydro reactive powders via ball milling with silver powder and either lithium chloride or gallium. The latter substances significantly intensified particle size reduction, while silver formed ‘cathodic’ sites (Ag, Ag₂Al), promoting Al corrosion in aqueous saline solutions with hydrogen generation. The diffraction patterns, microphotographs, and elemental analysis results demonstrated partial aluminum oxidation in the samples and their contamination with tungsten carbide from milling balls. Those factors were responsible for obtaining lower hydrogen yields than expected. For AlCl₃ solution at 60 °C, Al–LiCl–Ag, Al–LiCl, Al–Ga–Ag, and Al–Ga composites delivered (84.6 ± 0.2), (86.8 ± 1.4), (80.2 ± 0.5), and (76.7 ± 0.7)% of the expected hydrogen, respectively. Modification with Ag promoted Al oxidation, thus providing higher hydrogen evolution rates. The samples with Ag were tested in a CaCl₂ solution as well, for which the reaction proceeded much more slowly. At a higher temperature (80 °C) after 3 h of experiment, the corresponding hydrogen yields for Al–LiCl–Ag and Al–Ga–Ag powders were (46.7 ± 2.1) and (31.8 ± 1.9)%. The tested Ag-modified composite powders were considered promising for hydrogen generation and had the potential for further improvement to deliver higher hydrogen yields. Full article

Astaxanthin (AST)-encapsulated nanoparticles were fabricated using glycol chitosan (Chito) through electrostatic interaction (abbreviated as ChitoAST) to solve the aqueous solubility of astaxanthin and improve its biological activity. AST was dissolved in organic solvents and then mixed with chitosan solution, followed by a dialysis procedure. All formulations of ChitoAST nanoparticles showed small diameters (less than 400 nm) with monomodal distributions. Analysis with Fourier transform infrared (FT-IR) spectroscopy confirmed the specific peaks of AST and Chito. Furthermore, ChitoAST nanoparticles were formed through electrostatic interactions between Chito and AST. In addition, ChitoAST nanoparticles showed superior antioxidant activity, as good as AST itself; the half maximal radical scavenging concentrations (RC₅₀) of AST and ChitoAST nanoparticles were 11.8 and 29.3 µg/mL, respectively. In vitro, AST and ChitoAST nanoparticles at 10 and 20 µg/mL properly inhibited the production of intracellular reactive oxygen species (ROSs), nitric oxide (NO), and inducible nitric oxide synthase (iNOS). ChitoAST nanoparticles had no significant cytotoxicity against RAW264.7 cells or B16F10 melanoma cells, whereas AST and ChitoAST nanoparticles inhibited the growth of cancer cells. Furthermore, AST itself and ChitoAST nanoparticles (20 µg/mL) efficiently inhibited the migration of cancer cells in a wound healing assay. An in vivo study using mice and a pulmonary metastasis model showed that ChitoAST nanoparticles were efficiently delivered to a lung with B16F10 cell metastasis; i.e., fluorescence intensity in the lung was significantly higher than in other organs. We suggest that ChitoAST nanoparticles are promising candidates for antioxidative and anticancer therapies of B16F10 cells. Full article

(1) Background: Hexachlorobenzene (HCB) is a persistent organic pollutant that is possibly carcinogenic to humans. It is still found in the environment, humans and animals, and in foods, including milk and dairy products; (2) Methods: The influence of the probiotic cultures Lacticaseibacillus rhamnosus LCR and Lactiplantibacillus plantarum subsp. plantarum LP on the possibility of effecting the biodegradation of HCB in dairy products fermented from mare milk was investigated, taking into account the product storage time (maximum 21 days). HCB content was determined using the GC/MS method; (3) Results: A strong negative Pearson correlation (p < 0.05) was found between HCB concentration and the refrigeration storage time of the fermented beverages. The highest HCB reduction was observed in milk fermented with both Lacticaseibacillus rhamnosus LCR and Lactiplantibacillus plantarum subsp. plantarum LP (78.77%), while the lowest was noted when only Lactiplantibacillus plantarum subsp. plantarum LP was used (73.79%); (4) Conclusions: This pilot study confirmed that probiotics commonly used to give products health-promoting properties can also contribute to reducing the content of undesirable substances, and the bacterial cultures used might provide an alternative method for reducing HCB residues in fermented drinks. Full article

In the present work, several coumarin-3-carboxamides with different azacrown ether moieties were designed and tested as potential luminescent sensors for metal ions. The derivative containing a 1-aza-15-crown-5 as a metal chelating group was found to yield the strongest response for Ca²⁺ and Pb²⁺, exhibiting an eight- and nine-fold emission increase, respectively, while other cations induced no changes in the optical properties of the chemosensor molecule. Job’s plots revealed a 1:1 binding stoichiometry, with association constants of 4.8 × 10⁴ and 8.7 × 10⁴ M^–1, and limits of detection of 1.21 and 8.04 µM, for Ca²⁺ and Pb²⁺, respectively. Computational studies suggest the existence of a PET quenching mechanism, which is inhibited after complexation with each of these two metals. Proton NMR experiments and X-ray crystallography suggest a contribution from the carbonyl groups in the coumarin-3-carboxamide fluorophore in the coordination sphere of the metal ion. Full article

Cannabinoid metabolites have been reported to be more potent than their parent compounds. Among them, ajulemic acid (AJA) is a side-chain analog of Δ⁹-THC-11-oic acid, which would be a good template structure for the discovery of more potent analogues. Herein, we optimized the key allylic oxidation step to introduce the C-11 hydroxy group with a high yield. A series of compounds was prepared with this condition applied including HU-210, 11-nor-Δ⁸-tetrahydrocannabinol (THC)-carboxylic acid and Δ⁹-THC-carboxylic acid. Full article

Extra virgin olive oil (EVOO) is a valuable product and is highly appreciated by consumers for its great nutritional value. However, to date, there has been a lack of uniform systems capable of ranking the nutritional value of EVOO based on its chemical composition in terms of macro- and micronutrients (including phenolic compounds and tocopherols). The aim of this study was to propose a scoring algorithm to rank the nutritional value of EVOO samples, considering their chemical composition in macro- and micronutrients and their sensitivity to oxidation phenomena. Data from more than 1000 EVOO samples were used to assess the variability of the data, considering the selected negative parameters (free acidity, peroxide value, spectrophotometric indices) and positive components (composition in tocopherols via HPLC-DAD, phenolic compounds via HPLC-DAD, and fatty acids via GC-MS) so as to ensure the universal validity of the scoring algorithm. The dataset included samples from the main producing countries worldwide, in addition to Australia, across several production years; data were selected to represent different production realities. A mathematical model was set up for each chemical component, resulting in six variable values. By combining these values with a dimensionless constant value, the algorithm for computing the nutritional value score (NVS) was defined. It allows the nutritional value of an oil to be ranked on a scale of 0 to 100 based on its chemical composition. The algorithm was then successfully tested using chemical data from about 300 EVOO samples obtained from laboratories from different Italian regions. The proposed NVS is a simple and objective tool for scoring the nutritional value of an EVOO, easy to understand for both producers and consumers. Full article

A series of reported Pt(II) carbene complexes possibly have the ability to serve as the new generation of blue emitters in luminescent devices because of their narrow emission spectra, high photoluminescence quantum yields (PLQYs), and rigid molecular skeleton. However, the combination of all carbene ligands with different multidentate structures will affect the overall planarity and horizontal dipole ratio to varying degrees, but the specific extent of this effect has not previously been analyzed in detail. In this work, density functional computation is used to study a class of platinum tetracarbene bidentate complexes with similar absorption and emission band characteristics, which is the main reason for the remarkable difference in quantum efficiency due to subtle differences in electronic states caused by different ligands. From the calculation results, the major reason, which results in significantly decrease in quantum efficiency for [Pt(cyim)₂]²⁺, is that [Pt(cyim)₂]²⁺ can reach the non-radiative deactivation metal-centered d-d excited state through an easier pathway compared with [Pt(meim)₂]²⁺. The result, based on changes in the dihedral angle between ligands, can achieve the goal of improving and designing materials by adjusting the degree of the dihedral angle. (meim: bis(1,1′-dimethyl-3,3′-methylene-diimidazoline-2,2′-diylidene); cyim: bis(1,1′-dicyclohexyl-3,3′-methylene-diimidazoline-2,2′-diylidene). Full article

In this study, a systematic investigation of MoS₂ nanostructure growth on a SiO₂ substrate was conducted using a two-stage process. Initially, a thin layer of Mo was grown through sputtering, followed by a sulfurization process employing the CVD technique. This two-stage process enables the control of diverse nanostructure formations of both MoS₂ and MoO₃ on SiO₂ substrates, as well as the formation of bulk-like grain structures. Subsequently, the addition of reduced graphene oxide (rGO) was examined, resulting in MoS₂/rGO(n), where graphene is uniformly deposited on the surface, exposing a higher number of active sites at the edges and consequently enhancing electroactivity in the HER. The influence of the synthesis time on the treated MoS₂ and also MoS₂/rGO(n) samples is evident in their excellent electrocatalytic performance with a low overpotential. Full article