Molecules

18 pages, 3610 KiB

Open AccessArticle

Evaluation of the Toxicity Potential of the Metabolites of Di-Isononyl Phthalate and of Their Interactions with Members of Family 1 of Sulfotransferases—A Computational Study

by Silvana Ceauranu, Alecu Ciorsac, Vasile Ostafe and Adriana Isvoran

Molecules 2023, 28(18), 6748; https://doi.org/10.3390/molecules28186748 - 21 Sep 2023

Cited by 3 | Viewed by 1663

Abstract

Di-isononyl phthalates are chemicals that are widely used as plasticizers. Humans are extensively exposed to these compounds by dietary intake, through inhalation and skin absorption. Sulfotransferases (SULTs) are enzymes responsible for the detoxification and elimination of numerous endogenous and exogenous molecules from the [...] Read more.

Di-isononyl phthalates are chemicals that are widely used as plasticizers. Humans are extensively exposed to these compounds by dietary intake, through inhalation and skin absorption. Sulfotransferases (SULTs) are enzymes responsible for the detoxification and elimination of numerous endogenous and exogenous molecules from the body. Consequently, SULTs are involved in regulating the biological activity of various hormones and neurotransmitters. The present study considers a computational approach to predict the toxicological potential of the metabolites of di-isononyl phthalate. Furthermore, molecular docking was considered to evaluate the inhibitory potential of these metabolites against the members of family 1 of SULTs. The metabolites of di-isononyl phthalate reveal a potency to cause liver damage and to inhibit receptors activated by peroxisome proliferators. These metabolites are also usually able to inhibit the activity of the members of family 1 of SULTs, except for SULT1A3 and SULT1B1. The outcomes of this study are important for an enhanced understanding of the risk of human exposure to di-isononyl phthalates. Full article

(This article belongs to the Special Issue Advances in Molecular Modeling in Chemistry)

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11 pages, 2753 KiB

Open AccessArticle

Poly Caprolactam Supported Hexaethylene Glycolic Imidazolium Ionic Liquid as a Heterogeneous Promoter for Nucleophilic Fluorination

by Mudumala Veeranarayana Reddy, Keun Heok Park and Dong Wook Kim

Molecules 2023, 28(18), 6747; https://doi.org/10.3390/molecules28186747 - 21 Sep 2023

Viewed by 1102

Abstract

Hexaethylene glycolic vinyl imidazolium (hexaEGVIM) was supported on N-vinyl caprolactam via covalent bonds through simple copolymerization to form poly caprolactam-supported hexaethylene glycol-substituted imidazolium salts (PCLS-hexaEGIM). The resulting heterogeneous PCLS-hexaEGIM promoter was active, selective, and stable for aliphatic nucleophilic substitution reactions using alkali [...] Read more.

Hexaethylene glycolic vinyl imidazolium (hexaEGVIM) was supported on N-vinyl caprolactam via covalent bonds through simple copolymerization to form poly caprolactam-supported hexaethylene glycol-substituted imidazolium salts (PCLS-hexaEGIM). The resulting heterogeneous PCLS-hexaEGIM promoter was active, selective, and stable for aliphatic nucleophilic substitution reactions using alkali metal salts. The alkali metal salts dramatically enhanced the reactivity of this heterogeneous catalyst with easily isolable higher product yields, reducing the formation of by-products. Therefore, nucleophilic fluorination and other substitution reactions can act as highly efficient catalysts in various sulfonyloxyalkanes and haloalkanes with regard to their corresponding fluorinated products. Full article

(This article belongs to the Special Issue Advances in Modern Fluorine Chemistry)

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19 pages, 4519 KiB

Open AccessArticle

Aquatic Peptide: The Potential Anti-Cancer and Anti-Microbial Activity of GE18 Derived from Pathogenic Fungus Aphanomyces invadans

by Manikandan Velayutham, P. Snega Priya, Purabi Sarkar, Raghul Murugan, Bader O. Almutairi, Selvaraj Arokiyaraj, Zulhisyam Abdul Kari, Guillermo Tellez-Isaias, Ajay Guru and Jesu Arockiaraj

Molecules 2023, 28(18), 6746; https://doi.org/10.3390/molecules28186746 - 21 Sep 2023

Cited by 2 | Viewed by 2193

Abstract

Small molecules as well as peptide-based therapeutic approaches have attracted global interest due to their lower or no toxicity in nature, and their potential in addressing several health complications including immune diseases, cardiovascular diseases, metabolic disorders, osteoporosis and cancer. This study proposed a [...] Read more.

Small molecules as well as peptide-based therapeutic approaches have attracted global interest due to their lower or no toxicity in nature, and their potential in addressing several health complications including immune diseases, cardiovascular diseases, metabolic disorders, osteoporosis and cancer. This study proposed a peptide, GE18 of subtilisin-like peptidase from the virulence factor of aquatic pathogenic fungus Aphanomyces invadans, which elicits anti-cancer and anti-microbial activities. To understand the potential GE18 peptide-induced biological effects, an in silico analysis, in vitro (L6 cells) and in vivo toxicity assays (using zebrafish embryo), in vitro anti-cancer assays and anti-microbial assays were performed. The outcomes of the in silico analyses demonstrated that the GE18 peptide has potent anti-cancer and anti-microbial activities. GE18 is non-toxic to in vitro non-cancerous cells and in vivo zebrafish larvae. However, the peptide showed significant anti-cancer properties against MCF-7 cells with an IC50 value of 35.34 µM, at 24 h. Besides the anti-proliferative effect on cancer cells, the peptide exposure does promote the ROS concentration, mitochondrial membrane potential and the subsequent upregulation of anti-cancer genes. On the other hand, GE18 elicits significant anti-microbial activity against P. aeruginosa, wherein GE18 significantly inhibits bacterial biofilm formation. Since the peptide has positively charged amino acid residues, it targets the cell membrane, as is evident in the FESEM analysis. Based on these outcomes, it is possible that the GE18 peptide is a significant anti-cancer and anti-microbial molecule. Full article

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19 pages, 1832 KiB

Open AccessReview

Advances in Biosynthesis of Non-Canonical Amino Acids (ncAAs) and the Methods of ncAAs Incorporation into Proteins

by Liang Chen, Xiulan Xin, Yuning Zhang, Shunyao Li, Xiaoman Zhao, Song Li and Zhaochu Xu

Molecules 2023, 28(18), 6745; https://doi.org/10.3390/molecules28186745 - 21 Sep 2023

Cited by 7 | Viewed by 3537

Abstract

The functional pool of canonical amino acids (cAAs) has been enriched through the emergence of non-canonical amino acids (ncAAs). NcAAs play a crucial role in the production of various pharmaceuticals. The biosynthesis of ncAAs has emerged as an alternative to traditional chemical synthesis [...] Read more.

The functional pool of canonical amino acids (cAAs) has been enriched through the emergence of non-canonical amino acids (ncAAs). NcAAs play a crucial role in the production of various pharmaceuticals. The biosynthesis of ncAAs has emerged as an alternative to traditional chemical synthesis due to its environmental friendliness and high efficiency. The breakthrough genetic code expansion (GCE) technique developed in recent years has allowed the incorporation of ncAAs into target proteins, giving them special functions and biological activities. The biosynthesis of ncAAs and their incorporation into target proteins within a single microbe has become an enticing application of such molecules. Based on that, in this study, we first review the biosynthesis methods for ncAAs and analyze the difficulties related to biosynthesis. We then summarize the GCE methods and analyze their advantages and disadvantages. Further, we review the application progress of ncAAs and anticipate the challenges and future development directions of ncAAs. Full article

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13 pages, 2037 KiB

Open AccessArticle

Comparison of the Chemical Composition and Antioxidant Properties of Propolis from Urban Apiaries

by Katarzyna Pobiega, Anna M. Kot, Jarosław L. Przybył, Alicja Synowiec and Małgorzata Gniewosz

Molecules 2023, 28(18), 6744; https://doi.org/10.3390/molecules28186744 - 21 Sep 2023

Cited by 4 | Viewed by 1331

Abstract

Bee products from urban apiaries are increasingly used. They are mainly used to promote local apiaries and cities in which they are located. The aim of the study was to compare the chemical composition and antioxidant activity of propolis from 6 Polish apiaries [...] Read more.

Bee products from urban apiaries are increasingly used. They are mainly used to promote local apiaries and cities in which they are located. The aim of the study was to compare the chemical composition and antioxidant activity of propolis from 6 Polish apiaries located in cities (Legionowo, Torun, Cracow, Warsaw, Katowice, Lodz). The chemical composition was analyzed using liquid chromatography (HPLC-DAD) and the analysis of antioxidant activity by scavenging free radicals (ABTS and DPPH) and FRAP. The obtained results showed the presence of 24 phenolic compounds in propolis extracts. The tested samples showed differentiation in terms of the content of individual chemical components, however, cinnamic acid and its derivatives were dominant. High antioxidant activity of the tested extracts was demonstrated (ABTS was in the range of 16.80–51.53 mg Te/mL, DPPH was in the range of 7.54–22.13 mg Te/mL, while FRAP reduction was in the range of 10.93–29.55 mg Te/mL). The obtained results compared with literature data on propolis from agricultural areas allow to conclude that propolis samples from both Poland types of areas are similar and can be classified as poplar propolis. Full article

(This article belongs to the Special Issue Biological Activity of Phenolics and Polyphenols in Nature Products)

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13 pages, 2247 KiB

Open AccessArticle

Preparation of Herbal Extracts for Intestinal Immune Modulation Activity Based on In Vitro Screening and In Vivo Evaluation of Zingiber officinale Rosc. Extracts

by Su Ji Min, Sung Jin Kim, Jun Yeon Park, Chang-Seob Seo and You-Kyong Choi

Molecules 2023, 28(18), 6743; https://doi.org/10.3390/molecules28186743 - 21 Sep 2023

Cited by 3 | Viewed by 1422

Abstract

Ten traditional herbal extracts effective against diarrhea, infectious diseases, and bacterial activity were selected and analyzed for Peyer’s patch cell-mediated intestinal immunomodulatory activity in vitro and in vivo. Among the 10 herbal extracts, Zingiber officinale Rosc. (ZO) extract induced the highest secretion [...] Read more.

Ten traditional herbal extracts effective against diarrhea, infectious diseases, and bacterial activity were selected and analyzed for Peyer’s patch cell-mediated intestinal immunomodulatory activity in vitro and in vivo. Among the 10 herbal extracts, Zingiber officinale Rosc. (ZO) extract induced the highest secretion of immunoglobulin A (IgA) and granulocyte macrophage colony-stimulating factor (GM-CSF) in the cells of Peyer’s patches. Furthermore, animal experiments showed that IA production was enhanced with the oral administration of ZO extract (100 mg/kg and 300 mg/kg) for 10 days. In addition, 6-, 8-, 10-gingerol, and 6-, 8-, 10-shogaol, the six major index compounds of ZO extract, were analyzed using HPLC. Our study findings confirm the intestinal immunomodulatory activity of ZO extract and lay a strong foundation for future analytical studies aimed at determining the active components of ZO extracts. Full article

(This article belongs to the Special Issue Antimicrobial and Immunomodulatory Activities of Natural Products)

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22 pages, 11949 KiB

Open AccessArticle

Potential of Natural Phenolic Compounds as Antimicrobial Agents against Multidrug-Resistant Staphylococcus aureus in Chicken Meat

by Alaa Eldin M. A. Morshdy, Karima M. E. Abdallah, Heba E. Abdallah, Fahad D. Algahtani, Mohamed Tharwat Elabbasy, Suleman Atique, Khursheed Ahmad, Mohammad A. A. Al-Najjar, Hossam M. Abdallah and Abdallah Fikry A. Mahmoud

Molecules 2023, 28(18), 6742; https://doi.org/10.3390/molecules28186742 - 21 Sep 2023

Cited by 4 | Viewed by 2059

Abstract

Staphylococcus aureus is one of the most widespread foodborne bacteria that cause high morbidity, mortality, and economic loss, primarily if foodborne diseases are caused by pathogenic and multidrug-resistant (MDR) strains. This study aimed to determine the prevalence of S. aureus in chicken meat [...] Read more.

Staphylococcus aureus is one of the most widespread foodborne bacteria that cause high morbidity, mortality, and economic loss, primarily if foodborne diseases are caused by pathogenic and multidrug-resistant (MDR) strains. This study aimed to determine the prevalence of S. aureus in chicken meat in Egyptian markets. Thus, this study might be the first to assess the efficiency of different natural phenolic compounds as novel antibacterial agents against MDR S. aureus pathogens isolated from raw chicken meat in the Egyptian market. The incidence and quantification of pathogenic S. aureus were detected in retail raw chicken meat parts (breast, thigh, fillet, and giblets). In total, 73 out of 80 (91.3%) of the chicken meat parts were contaminated, with S. aureus as the only species isolated. Of the 192 identified S. aureus isolates, 143 were coagulase-positive S. aureus and 117 isolates were MDR (81.8%, 117/143). Twenty-two antibiotic resistance profile patterns were detected. One strain was randomly selected from each pattern to further analyze virulence and resistance genes. Extracted DNA was assessed for the presence of antibiotic-resistance genes, i.e., vancomycin-resistance (vanA), aminoglycosides-resistance (aacA–aphD), apramycin-resistance (apmA), and methicillin-resistance (mecA), penicillin-resistance (blaZ), and virulence genes staphylococcal enterotoxins (sea and seb), Panton–Valentine leucocidin (pvl), clumping factor A (clfA), and toxic shock syndrome toxin (tst). Clustering analyses revealed that six S. aureus strains harbored the most virulence and resistance genes. The activity of hydroquinone was significantly higher than thymol, carvacrol, eugenol, and protocatechuic acid. Therefore, phenolic compounds, particularly hydroquinone, could potentially alternate with conventional antibiotics against the pathogenic MDR S. aureus inhabiting raw chicken meat. Hence, this study indicates that urgent interventions are necessary to improve hygiene for safer meat in Egyptian markets. Moreover, hydroquinone could be a natural phenolic compound for inhibiting foodborne pathogens. Full article

(This article belongs to the Special Issue Chemical Composition and Bioactivities of Essential Oils, 2nd Edition)

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22 pages, 8588 KiB

Open AccessReview

Recent Advances in the Synthesis of Aromatic Azo Compounds

by Meng-Yun Zhao, Yue-Feng Tang and Guo-Zhi Han

Molecules 2023, 28(18), 6741; https://doi.org/10.3390/molecules28186741 - 21 Sep 2023

Cited by 10 | Viewed by 5577

Abstract

Aromatic azo compounds have -N=N- double bonds as well as a larger π electron conjugation system, which endows aromatic azo compounds with wide applications in the fields of functional materials. The properties of aromatic azo compounds are closely related to the substituents on [...] Read more.

Aromatic azo compounds have -N=N- double bonds as well as a larger π electron conjugation system, which endows aromatic azo compounds with wide applications in the fields of functional materials. The properties of aromatic azo compounds are closely related to the substituents on their aromatic rings. However, traditional synthesis methods, such as the coupling of diazo salts, have a significant limitation with respect to the structural design of aromatic azo compounds. Therefore, many scientists have devoted their efforts to developing new synthetic methods. Moreover, recent advances in the synthesis of aromatic azo compounds have led to improvements in the design and preparation of light-response materials at the molecular level. This review summarizes the important synthetic progress of aromatic azo compounds in recent years, with an emphasis on the pioneering contribution of functional nanomaterials to the field. Full article

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20 pages, 2806 KiB

Open AccessReview

Ubiquitin-Dependent and Independent Proteasomal Degradation in Host-Pathogen Interactions

by Wojciech Bialek, James F. Collawn and Rafal Bartoszewski

Molecules 2023, 28(18), 6740; https://doi.org/10.3390/molecules28186740 - 21 Sep 2023

Cited by 3 | Viewed by 2122

Abstract

Ubiquitin, a small protein, is well known for tagging target proteins through a cascade of enzymatic reactions that lead to protein degradation. The ubiquitin tag, apart from its signaling role, is paramount in destabilizing the modified protein. Here, we explore the complex role [...] Read more.

Ubiquitin, a small protein, is well known for tagging target proteins through a cascade of enzymatic reactions that lead to protein degradation. The ubiquitin tag, apart from its signaling role, is paramount in destabilizing the modified protein. Here, we explore the complex role of ubiquitin-mediated protein destabilization in the intricate proteolysis process by the 26S proteasome. In addition, the significance of the so-called ubiquitin-independent pathway and the role of the 20S proteasome are considered. Next, we discuss the ubiquitin–proteasome system’s interplay with pathogenic microorganisms and how the microorganisms manipulate this system to establish infection by a range of elaborate pathways to evade or counteract host responses. Finally, we focus on the mechanisms that rely either on (i) hijacking the host and on delivering pathogenic E3 ligases and deubiquitinases that promote the degradation of host proteins, or (ii) counteracting host responses through the stabilization of pathogenic effector proteins. Full article

(This article belongs to the Special Issue Protein Folding, towards the Comprehensive Understanding from Various Aspects)

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13 pages, 8193 KiB

Open AccessArticle

Decomposition of SO₂ on Ni(111) Surface and the Effect of Metal Doping: A First-Principles Study

by Lingtao Liu, Chenxin Zhang, Wenshou Wang, Genghong Li and Bingtian Zhu

Molecules 2023, 28(18), 6739; https://doi.org/10.3390/molecules28186739 - 21 Sep 2023

Cited by 1 | Viewed by 1107

Abstract

Sulfides poisoning of metallic Ni is an important issue in catalyst deactivation. SO₂, similar to H₂S and other sulfides, is an impurity presented in reactants or during the regeneration steps. Herein, spin-polarized density functional theory calculations were used to [...] Read more.

Sulfides poisoning of metallic Ni is an important issue in catalyst deactivation. SO₂, similar to H₂S and other sulfides, is an impurity presented in reactants or during the regeneration steps. Herein, spin-polarized density functional theory calculations were used to study the adsorption and decomposition of SO₂ on a pristine and metal-doped Ni(111) surface. The adsorption energy, transition state energy, and partial density of state (PDOS) were calculated. On the pristine Ni(111) surface, ten different configurations were considered, and three typical ones were selected for transition state searching. It was found that the reaction barrier of the first S-O bond dissociation was much higher than that of the second one. Doping the top layer with a second metal could strongly change the adsorption and decomposition behavior. Doping with 3/9ML Co slightly increases the adsorption energy of SO₂ for most configurations and decreases the reaction barriers of the SO₂-tht-2 decomposition, while the others decrease the adsorption ability and increase the barriers. The order of adsorption energy for the most stable configurations is Co > Ni > Cu > Rh > Pd. The order of the first S-O bond dissociation reaction barriers is Pd > Rh > Cu = Ni > Co, and the order of the second bond dissociation barrier is Rh > Pd > Cu > Ni > Co. Full article

(This article belongs to the Topic Theoretical, Quantum and Computational Chemistry)

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19 pages, 4010 KiB

Open AccessArticle

A Novel and Efficient Phthalate Hydrolase from Acinetobacter sp. LUNF3: Molecular Cloning, Characterization and Catalytic Mechanism

by Shuanghu Fan, Jingjing Guo, Shaoyan Han, Haina Du, Zimeng Wang, Yajuan Fu, Hui Han, Xiaoqiang Hou and Weixuan Wang

Molecules 2023, 28(18), 6738; https://doi.org/10.3390/molecules28186738 - 21 Sep 2023

Cited by 4 | Viewed by 1471

Abstract

Phthalic acid esters (PAEs), which are widespread environmental contaminants, can be efficiently biodegraded, mediated by enzymes such as hydrolases. Despite great advances in the characterization of PAE hydrolases, which are the most important enzymes in the process of PAE degradation, their molecular catalytic [...] Read more.

Phthalic acid esters (PAEs), which are widespread environmental contaminants, can be efficiently biodegraded, mediated by enzymes such as hydrolases. Despite great advances in the characterization of PAE hydrolases, which are the most important enzymes in the process of PAE degradation, their molecular catalytic mechanism has rarely been systematically investigated. Acinetobacter sp. LUNF3, which was isolated from contaminated soil in this study, demonstrated excellent PAE degradation at 30 °C and pH 5.0–11.0. After sequencing and annotating the complete genome, the gene dphAN1, encoding a novel putative PAE hydrolase, was identified with the conserved motifs catalytic triad (Ser²⁰¹-Asp²⁹⁵-His³²⁵) and oxyanion hole (H¹²⁷GGG¹³⁰). DphAN1 can hydrolyze DEP (diethyl phthalate), DBP (dibutyl phthalate) and BBP (benzyl butyl phthalate). The high activity of DphAN1 was observed under a wide range of temperature (10–40 °C) and pH (6.0–9.0). Moreover, the metal ions (Fe²⁺, Mn²⁺, Cr²⁺ and Fe³⁺) and surfactant TritonX-100 significantly activated DphAN1, indicating a high adaptability and tolerance of DphAN1 to these chemicals. Molecular docking revealed the catalytic triad, oxyanion hole and other residues involved in binding DBP. The mutation of these residues reduced the activity of DphAN1, confirming their interaction with DBP. These results shed light on the catalytic mechanism of DphAN1 and may contribute to protein structural modification to improve catalytic efficiency in environment remediation. Full article

(This article belongs to the Special Issue Biomolecules Interactions with Small Molecules)

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19 pages, 8355 KiB

Open AccessReview

Nonlinear Optical Properties from Engineered 2D Materials

by Jia Shi, Shifeng Feng, Peng He, Yulan Fu and Xinping Zhang

Molecules 2023, 28(18), 6737; https://doi.org/10.3390/molecules28186737 - 21 Sep 2023

Cited by 7 | Viewed by 3063

Abstract

Two-dimensional (2D) materials with atomic thickness, tunable light-matter interaction, and significant nonlinear susceptibility are emerging as potential candidates for new-generation optoelectronic devices. In this review, we briefly cover the recent research development of typical nonlinear optic (NLO) processes including second harmonic generation (SHG), [...] Read more.

Two-dimensional (2D) materials with atomic thickness, tunable light-matter interaction, and significant nonlinear susceptibility are emerging as potential candidates for new-generation optoelectronic devices. In this review, we briefly cover the recent research development of typical nonlinear optic (NLO) processes including second harmonic generation (SHG), third harmonic generation (THG), as well as two-photon photoluminescence (2PPL) of 2D materials. Nonlinear light-matter interaction in atomically thin 2D materials is important for both fundamental research and future optoelectronic devices. The NLO performance of 2D materials can be greatly modulated with methods such as carrier injection tuning, strain tuning, artificially stacking, as well as plasmonic resonant enhancement. This review will discuss various nonlinear optical processes and corresponding tuning methods and propose its potential NLO application of 2D materials. Full article

(This article belongs to the Special Issue Chemical Functionalization of Two-Dimensional Materials)

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14 pages, 4268 KiB

Open AccessArticle

Effects of Me–Solvent Interactions on the Structure and Infrared Spectra of MeTFSI (Me = Li, Na) Solutions in Carbonate Solvents—A Test of the GFN2-xTB Approach in Molecular Dynamics Simulations

by Piotr Wróbel and Andrzej Eilmes

Molecules 2023, 28(18), 6736; https://doi.org/10.3390/molecules28186736 - 21 Sep 2023

Cited by 3 | Viewed by 1425

Abstract

We investigated the performance of the computationally effective GFN2-xTB approach in molecular dynamics (MD) simulations of liquid electrolytes for lithium/sodium batteries. The studied systems were LiTFSI and NaTFSI solutions in ethylene carbonate or fluoroethylene carbonate and the neat solvents. We focused on the [...] Read more.

We investigated the performance of the computationally effective GFN2-xTB approach in molecular dynamics (MD) simulations of liquid electrolytes for lithium/sodium batteries. The studied systems were LiTFSI and NaTFSI solutions in ethylene carbonate or fluoroethylene carbonate and the neat solvents. We focused on the structure of the electrolytes and on the manifestations of ion–solvent interactions in the vibrational spectra. The IR spectra were calculated from MD trajectories as Fourier transforms of the dipole moment. The results were compared to the data obtained from ab initio MD. The spectral shifts of the carbonyl stretching mode calculated from the GFN2-xTB simulations were in satisfactory agreement with the ab initio MD data and the experimental results for similar systems. The performance in the region of molecular ring vibrations was significantly worse. We also found some differences in structural data, suggesting that the GFN2-xTB overestimates interactions of Me ions with TFSI anions and Na⁺ binding to solvent molecules. We conclude that the GFN2-xTB method is an alternative worth considering for MD simulations of liquids, but it requires testing of its applicability for new systems. Full article

(This article belongs to the Section Computational and Theoretical Chemistry)

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24 pages, 1571 KiB

Open AccessReview

Bacterial and Fungal Biocontrol Agents for Plant Disease Protection: Journey from Lab to Field, Current Status, Challenges, and Global Perspectives

by Muhammad Ayaz, Cai-Hong Li, Qurban Ali, Wei Zhao, Yuan-Kai Chi, Muhammad Shafiq, Farman Ali, Xi-Yue Yu, Qing Yu, Jing-Tian Zhao, Jing-Wen Yu, Ren-De Qi and Wen-Kun Huang

Molecules 2023, 28(18), 6735; https://doi.org/10.3390/molecules28186735 - 21 Sep 2023

Cited by 38 | Viewed by 11574

Abstract

Plants are constantly exposed to various phytopathogens such as fungi, Oomycetes, nematodes, bacteria, and viruses. These pathogens can significantly reduce the productivity of important crops worldwide, with annual crop yield losses ranging from 20% to 40% caused by various pathogenic diseases. While the [...] Read more.

Plants are constantly exposed to various phytopathogens such as fungi, Oomycetes, nematodes, bacteria, and viruses. These pathogens can significantly reduce the productivity of important crops worldwide, with annual crop yield losses ranging from 20% to 40% caused by various pathogenic diseases. While the use of chemical pesticides has been effective at controlling multiple diseases in major crops, excessive use of synthetic chemicals has detrimental effects on the environment and human health, which discourages pesticide application in the agriculture sector. As a result, researchers worldwide have shifted their focus towards alternative eco-friendly strategies to prevent plant diseases. Biocontrol of phytopathogens is a less toxic and safer method that reduces the severity of various crop diseases. A variety of biological control agents (BCAs) are available for use, but further research is needed to identify potential microbes and their natural products with a broad-spectrum antagonistic activity to control crop diseases. This review aims to highlight the importance of biocontrol strategies for managing crop diseases. Furthermore, the role of beneficial microbes in controlling plant diseases and the current status of their biocontrol mechanisms will be summarized. The review will also cover the challenges and the need for the future development of biocontrol methods to ensure efficient crop disease management for sustainable agriculture. Full article

(This article belongs to the Special Issue Fighting Against Phytopathogens: New Approaches)

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13 pages, 2880 KiB

Open AccessArticle

Photoprotective Effects of Processed Ginseng Leaf Administration against UVB-Induced Skin Damage in Hairless Mice

by Eunjung Son, Yun Mi Lee, Seung-Hyung Kim and Dong-Seon Kim

Molecules 2023, 28(18), 6734; https://doi.org/10.3390/molecules28186734 - 21 Sep 2023

Cited by 2 | Viewed by 1485

Abstract

Although ginseng leaves contain a larger amount of ginsenosides than the roots, studies on the protective effect of oral administration of ginseng leaves against photoaging are lacking. Processed ginseng leaves (PGL) prepared by acid reaction to increase effective ginsenoside content showed higher levels [...] Read more.

Although ginseng leaves contain a larger amount of ginsenosides than the roots, studies on the protective effect of oral administration of ginseng leaves against photoaging are lacking. Processed ginseng leaves (PGL) prepared by acid reaction to increase effective ginsenoside content showed higher levels of Rg3 (29.35 mg/g) and Rk1 (35.16 mg/g) than ginseng leaves (Rg3 (2.14 mg/g) and Rk1 (ND)), and ginsenosides Rg3 and Rk1 were evaluated as active ingredients that protected human keratinocytes against UVB-induced cell damage by increasing cell proliferation and decreasing matrix metalloproteinase (MMP)-2 and 9 secretion. Herein, the effect of oral PGL administration (50, 100, or 200 mg/kg, daily) against photoaging in HR-1 hairless mice was assessed by measuring wrinkle depth, epidermal thickness, and trans-epidermal water loss for 16 weeks. The PGL treatment group showed reduced skin wrinkles, inhibited MMP-2 and MMP-9 expression, and decreased IL-6 and cyclooxygenase-2 levels. These data suggest that oral PGL administration inhibits photoaging by inhibiting the expression of MMPs, which degrade collagen, and inhibiting cytokines, which induce inflammatory responses. These results reveal that ginseng leaves processed by acid reaction may serve as potential functional materials with anti-photoaging activities. Full article

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17 pages, 2808 KiB

Open AccessArticle

Simultaneous Analysis of Cyanotoxins β-N-methylamino-L-alanine (BMAA) and Microcystins-RR, -LR, and -YR Using Liquid Chromatography–Tandem Mass Spectrometry (LC-MS/MS)

by Sercan Pravadali-Cekic, Aleksandar Vojvodic, Jake P. Violi, Simon M. Mitrovic, Kenneth J. Rodgers and David P. Bishop

Molecules 2023, 28(18), 6733; https://doi.org/10.3390/molecules28186733 - 21 Sep 2023

Cited by 4 | Viewed by 1846

Abstract

β-N-methylamino-L-alanine (BMAA) and its isomers, 2,4-diaminobutyric acid (2,4-DAB) and N-(2-aminoethyl)-glycine (AEG), along with microcystins (MCs)-RR, -LR, and -YR (the major MC congeners), are cyanotoxins that can cause detrimental health and environmental impacts during toxic blooms. Currently, there are no reverse-phase (RP) LC-MS/MS methods [...] Read more.

β-N-methylamino-L-alanine (BMAA) and its isomers, 2,4-diaminobutyric acid (2,4-DAB) and N-(2-aminoethyl)-glycine (AEG), along with microcystins (MCs)-RR, -LR, and -YR (the major MC congeners), are cyanotoxins that can cause detrimental health and environmental impacts during toxic blooms. Currently, there are no reverse-phase (RP) LC-MS/MS methods for the simultaneous detection and quantification of BMAA, its isomers, and the major MCs in a single analysis; therefore, multiple analyses are required to assess the toxic load of a sample. Here, we present a newly developed and validated method for the detection and quantification of BMAA, 2,4-DAB, AEG, MC-LR, MC-RR, and MC-YR using RP LC-MS/MS. Method validation was performed, assessing linearity (r² > 0.996), accuracy (>90% recovery for spiked samples), precision (7% relative standard deviation), and limits of detection (LODs) and quantification (LOQs) (ranging from 0.13 to 1.38 ng mL⁻¹). The application of this combined cyanotoxin analysis on a culture of Microcystis aeruginosa resulted in the simultaneous detection of 2,4-DAB (0.249 ng mg⁻¹ dry weight (DW)) and MC-YR (4828 ng mg⁻¹ DW). This study provides a unified method for the quantitative analysis of BMAA, its isomers, and three MC congeners in natural environmental samples. Full article

(This article belongs to the Special Issue Analytical Techniques in Environmental Chemistry)

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12 pages, 649 KiB

Open AccessArticle

Antioxidant and Hypolipidemic Activities of Cinnamic Acid Derivatives

by Christina Nouni, Panagiotis Theodosis-Nobelos and Eleni A. Rekka

Molecules 2023, 28(18), 6732; https://doi.org/10.3390/molecules28186732 - 21 Sep 2023

Cited by 6 | Viewed by 1708

Abstract

Oxidative stress and hyperlipidemia are important factors for the initiation and progression of various cell degenerative pathological conditions, including cardiovascular and neurological diseases. A series of cinnamic acid-derived acids, such as ferulic acid, sinapic acid, 3,4-dimethoxycinnamic acid, p-coumaric acid, and (E [...] Read more.

Oxidative stress and hyperlipidemia are important factors for the initiation and progression of various cell degenerative pathological conditions, including cardiovascular and neurological diseases. A series of cinnamic acid-derived acids, such as ferulic acid, sinapic acid, 3,4-dimethoxycinnamic acid, p-coumaric acid, and (E)-3-(3,5-di-tert-butyl-4-hydroxyphenyl)acrylic acid, were esterified or amidated with various moieties, bearing different biological activities, and evaluated. The antioxidant and radical scavenging abilities of the compounds via inhibition of rat hepatic microsomal membrane lipid peroxidation, as well as their interaction with the stable radical 2,2-diphenyl-1-picrylhydrazyl (DPPH), were assessed. Further, their hypolipidemic activity in vivo was tested. The majority of the obtained compounds demonstrated considerable radical scavenging and antioxidant action, with a parallel decrease in Triton-induced hyperlipidemia in rats. The (E)-3-(3,5-di-tert-butyl-4-hydroxyphenyl)acrylic acid derivative with morpholine and 4-methylpiperidine (compounds 4 and 13, respectively) significantly decreased triglycerides and total cholesterol in the plasma of hyperlipidemic rats, with an antioxidant capacity similar to that of the antioxidant Trolox. The compounds were designed to exhibit antioxidant and hypolipidemic pharmacological actions, and this succeeded for the majority of them. Thus, such agents may be of interest in conditions and diseases implicating oxidative stress and dyslipidemia. Full article

(This article belongs to the Special Issue Antioxidants from Natural Sources: Separation and Characterization Ⅱ)

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18 pages, 6179 KiB

Open AccessArticle

Synthesis and Characterization of Phosphorus-Containing Sorbent for Basic Dye Removal

by Monika Wawrzkiewicz, Sławomir Frynas and Beata Podkościelna

Molecules 2023, 28(18), 6731; https://doi.org/10.3390/molecules28186731 - 21 Sep 2023

Cited by 3 | Viewed by 1102

Abstract

A new phosphorus-containing sorbent was prepared by copolymerizing ethylene glycol dimethacrylate (EGDMA) and trimethylvinyl silane (TMVS) with diphenylvinylphoshine oxide (DPVO). It was characterized and applied in the removal of cationic dyes such as C.I. Basic Yellow 2 (BY2), C.I. Basic Blue 3 (BB3) [...] Read more.

A new phosphorus-containing sorbent was prepared by copolymerizing ethylene glycol dimethacrylate (EGDMA) and trimethylvinyl silane (TMVS) with diphenylvinylphoshine oxide (DPVO). It was characterized and applied in the removal of cationic dyes such as C.I. Basic Yellow 2 (BY2), C.I. Basic Blue 3 (BB3) and C.I. Basic Red 46 (BR46) using the batch method. Spectroscopic analysis indicated that the phosphinoyl group was introduced into the sorbent structure. Equilibrium adsorption data were fitted to the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models. The Freundlich model is the most suitable to describe the adsorption of BB3 (the Freundlich constant k_F = 32.3 mg^1−1/nL^1/n/g) and BY2 on the sorbent (13.8 mg^1−1/nL^1/n/g), while the Langmuir model is the most adequate to describe the adsorption of BR46 (the monolayer capacity Q₀ = 2.7 mg/g). The kinetics of the dye adsorption follows the assumptions of the pseudo-second-order (the rate constants k₂ = 0.087 ÷ 0.738 g/mg min) model rather than pseudo-first-order or intraparticle diffusion. The presence of Na₂SO₄ and cationic surfactant in the aqueous solutions inhibited dye retention by the DPVO–EGDMA–TMVS. Adsorbent regeneration efficiency does not exceed 60% using 1 M NaCl and 1 M HCl solutions in the presence of 50% v/v methanol. Full article

(This article belongs to the Special Issue Research on Green Adsorbents)

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12 pages, 3426 KiB

Open AccessArticle

GeO₂ Nanoparticles Decorated in Amorphous Carbon Nanofiber Framework as Highly Reversible Lithium Storage Anode

by Wenhe Xie, Congcong Liu, Chen Hu, Yuanxiao Ma, Xuefeng Li, Qian Wang, Zhe An, Shenghong Liu, Haibin Sun and Xiaolei Sun

Molecules 2023, 28(18), 6730; https://doi.org/10.3390/molecules28186730 - 21 Sep 2023

Cited by 3 | Viewed by 1448

Abstract

Germanium oxide (GeO₂) is a high theoretical capacity electrode material due to its alloying and conversion reaction. However, the actual cycling capacity is rather poor on account of suffering low electron/ion conductivity, enormous volume change and agglomeration in the repeated lithiation/delithiation [...] Read more.

Germanium oxide (GeO₂) is a high theoretical capacity electrode material due to its alloying and conversion reaction. However, the actual cycling capacity is rather poor on account of suffering low electron/ion conductivity, enormous volume change and agglomeration in the repeated lithiation/delithiation process, which renders quite a low reversible electrochemical lithium storage reaction. In this work, highly amorphous GeO₂ particles are uniformly distributed in the carbon nanofiber framework, and the amorphous carbon nanofiber not only improves the conduction and buffers the volume changes but also prevents active material agglomeration. As a result, the present GeO₂ and carbon composite electrode exhibits highly reversible alloying and conversion processes during the whole cycling process. The two reversible electrochemical reactions are verified by differential capacity curves and cyclic voltammetry measurements during the whole cycling process. The corresponding reversible capacity is 747 mAh g⁻¹ after 300 cycles at a current density of 0.3 A g⁻¹. The related reversible capacities are 933, 672, 487 and 302 mAh g⁻¹ at current densities of 0.2, 0.4, 0.8 and 1.6 A g⁻¹, respectively. The simple strategy for the design of amorphous GeO₂/carbon composites enables potential application for high-performance LIBs. Full article

(This article belongs to the Special Issue Advanced Electrode Materials for Electrochemical Energy Storage and Conversion)

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10 pages, 861 KiB

Open AccessBrief Report

A UPLC-MS/MS Based Rapid, Sensitive, and Non-Enzymatic Methodology for Quantitation of Dietary Isoflavones in Biological Fluids

by Faraz Rashid, Sudeep Ghimire, Ashutosh K. Mangalam and Shailendra Giri

Molecules 2023, 28(18), 6729; https://doi.org/10.3390/molecules28186729 - 21 Sep 2023

Cited by 1 | Viewed by 1467

Abstract

Dietary isoflavones, a type of phytoestrogens, have gained importance owing to their health-promoting benefits. However, the beneficial effects of isoflavones are mediated by smaller metabolites produced with the help of gut bacteria that are known to metabolize these phytoestrogenic compounds into Daidzein and [...] Read more.

Dietary isoflavones, a type of phytoestrogens, have gained importance owing to their health-promoting benefits. However, the beneficial effects of isoflavones are mediated by smaller metabolites produced with the help of gut bacteria that are known to metabolize these phytoestrogenic compounds into Daidzein and Genistein and biologically active molecules such as S-Equol. Identifying and measuring these phytoestrogens and their metabolites is an important step towards understanding the significance of diet and gut microbiota in human health and diseases. We have overcome the reported difficulties in quantitation of these isoflavones and developed a simplified, sensitive, non-enzymatic, and sulfatases-free extraction methodology. We have subsequently used this method to quantify these metabolites in the urine of mice using UPLC-MS/MS. The extraction and quantitation method was validated for precision, linearity, accuracy, recoveries, limit of detection (LOD), and limit of quantification (LOQ). Linear calibration curves for Daidzein, Genistein, and S-Equol were set up by performing linear regression analysis and checked using the correlation coefficient (r² > 0.995). LOQs for Daidzein, Genistein, and S-Equol were 2, 4, and 2 ng/mL, respectively. This UPLC-MS/MS swift method is suitable for quantifying isoflavones and the microbial-derived metabolite S-Equol in mice urine and is particularly useful for large numbers of samples. Full article

(This article belongs to the Special Issue Development of Analytical Methods in Food, Biological and Environmental Samples Determination II)

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16 pages, 7394 KiB

Open AccessArticle

Myrcene: A Natural Compound Showing Anticancer Activity in HeLa Cells

by Luca Pincigher, Francesca Valenti, Christian Bergamini, Cecilia Prata, Romana Fato, Riccardo Amorati, Zongxin Jin, Giovanna Farruggia, Diana Fiorentini, Natalia Calonghi and Chiara Zalambani

Molecules 2023, 28(18), 6728; https://doi.org/10.3390/molecules28186728 - 21 Sep 2023

Cited by 2 | Viewed by 2280

Abstract

γ-terpinene, α-terpinene, p-cymene, and myrcene are monoterpenes found in many essential oils extracted from a variety of plants and spices. Myrcene also occurs naturally in plants such as hops, cannabis, lemongrass, and verbena and is used as a flavoring agent in food and [...] Read more.

γ-terpinene, α-terpinene, p-cymene, and myrcene are monoterpenes found in many essential oils extracted from a variety of plants and spices. Myrcene also occurs naturally in plants such as hops, cannabis, lemongrass, and verbena and is used as a flavoring agent in food and beverage manufacturing. In this research, the biological efficacy of γ-terpinene, α-terpinene, p-cymene, and myrcene was studied in human cell lines (HeLa, SH-SY5Y, and HDFa). Cytotoxicity, cell proliferation, cell migration, and morphology assays were performed to obtain detailed information on the anticancer properties. Our results show that myrcene has potential biological activity, especially in HeLa cells. In this cell line, it leads to an arrest of proliferation, a decrease in motility and morphological changes with loss of sphericity and thickness, and DNA damage. In addition, the interaction of γ-terpinene, α-terpinene, p-terpinene, and myrcene with calf thymus DNA (ct-DNA) was studied by UV-visible spectrophotometry. DNA binding experiments show that only myrcene can interact with DNA with an apparent dissociation constant (K_d) of 29 × 10⁻⁶ M. Full article

(This article belongs to the Special Issue Biological Activity of Natural and Synthetic Compounds 2.0)

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13 pages, 3734 KiB

Open AccessArticle

First-Principles Study of Atomic Diffusion by Vacancy Defect of the L1₂-Al₃M (M = Sc, Zr, Er, Y) Phase

by Shuai Liu, Binbin Liao, Baohua Nie, Touwen Fan, Dongchu Chen, Jianglong Zhang and Yu Song

Molecules 2023, 28(18), 6727; https://doi.org/10.3390/molecules28186727 - 21 Sep 2023

Cited by 1 | Viewed by 983

Abstract

Atomic diffusion by the vacancy defect of L1₂-Al₃M (M = Sc, Zr, Er, Y) was investigated based on a first-principles calculation. The point defect formation energies were firstly evaluated. Then, the migration energy for different diffusion paths was obtained [...] Read more.

Atomic diffusion by the vacancy defect of L1₂-Al₃M (M = Sc, Zr, Er, Y) was investigated based on a first-principles calculation. The point defect formation energies were firstly evaluated. Then, the migration energy for different diffusion paths was obtained by the climbing-image nudged elastic band (CI-NEB) method. The results showed that Al atomic and M atomic diffusions through nearest-neighbor jump (NNJ) mediated by Al vacancy (V_Al) were, respectively, the preferred diffusion paths in Al₃M phases under both Al-rich and M-rich conditions. The other mechanisms, such as six-jump cycle (6JC) and next-nearest-neighbor jump (NNNJ), were energetically inhibited. The order of activation barriers for NNJ(Al-V_Al) was Al₃Zr < Al₃Y < Al₃Er < Al₃Sc. The Al₃Sc phase had high stability with a high self-diffusion activation barrier, while the Al₃Zr and Al₃Y phases were relatively unstable with a low self-diffusion activation energy. Moreover, the atomic-diffusion behavior between the core and shell layers of L1₂-Al₃M was also further investigated. Zr atoms were prone to diffusion into the Al₃Y core layer, resulting in no stable core-shelled Al₃(Y,Zr), which well agreed with experimental observation. Full article

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24 pages, 11744 KiB

Open AccessArticle

Ethanolic Extract of Polygonum minus Protects Differentiated Human Neuroblastoma Cells (SH-SY5Y) against H₂O₂-Induced Oxidative Stress

by Nor Hafiza Sayuti, Nabilah Zulkefli, Jen Kit Tan, Norazalina Saad, Syarul Nataqain Baharum, Hamizah Shahirah Hamezah, Hamidun Bunawan, Qamar Uddin Ahmed, Humaira Parveen, Sayeed Mukhtar, Meshari A. Alsharif and Murni Nazira Sarian

Molecules 2023, 28(18), 6726; https://doi.org/10.3390/molecules28186726 - 20 Sep 2023

Cited by 3 | Viewed by 2156

Abstract

Neuronal models are an important tool in neuroscientific research. Hydrogen peroxide (H₂O₂), a major risk factor of neuronal oxidative stress, initiates a cascade of neuronal cell death. Polygonum minus Huds, known as ‘kesum’, is widely used in traditional medicine. [...] Read more.

Neuronal models are an important tool in neuroscientific research. Hydrogen peroxide (H₂O₂), a major risk factor of neuronal oxidative stress, initiates a cascade of neuronal cell death. Polygonum minus Huds, known as ‘kesum’, is widely used in traditional medicine. P. minus has been reported to exhibit a few medicinal and pharmacological properties. The current study aimed to investigate the neuroprotective effects of P. minus ethanolic extract (PMEE) on H₂O₂-induced neurotoxicity in SH-SY5Y cells. LC–MS/MS revealed the presence of 28 metabolites in PMEE. Our study showed that the PMEE provided neuroprotection against H₂O₂-induced oxidative stress by activating the Nrf2/ARE, NF-κB/IκB and MAPK signaling pathways in PMEE pre-treated differentiated SH-SY5Y cells. Meanwhile, the acetylcholine (ACH) level was increased in the oxidative stress-induced treatment group after 4 h of exposure with H₂O₂. Molecular docking results with acetylcholinesterase (AChE) depicted that quercitrin showed the highest docking score at −9.5 kcal/mol followed by aloe-emodin, afzelin, and citreorosein at −9.4, −9.3 and −9.0 kcal/mol, respectively, compared to the other PMEE’s identified compounds, which show lower docking scores. The results indicate that PMEE has neuroprotective effects on SH-SY5Y neuroblastoma cells in vitro. In conclusion, PMEE may aid in reducing oxidative stress as a preventative therapy for neurodegenerative diseases. Full article

(This article belongs to the Special Issue Neuroprotective Potential of Bioactive Natural Compounds in Oxidative Stress Conditions, 3rd Edition)

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22 pages, 5271 KiB

Open AccessArticle

Shikonin Causes an Apoptotic Effect on Human Kidney Cancer Cells through Ras/MAPK and PI3K/AKT Pathways

by József Király, Erzsébet Szabó, Petra Fodor, Zsolt Fejes, Béla Nagy, Jr., Éva Juhász, Anna Vass, Mahua Choudhury, Gábor Kónya, Gábor Halmos and Zsuzsanna Szabó

Molecules 2023, 28(18), 6725; https://doi.org/10.3390/molecules28186725 - 20 Sep 2023

Cited by 7 | Viewed by 1934

Abstract

(1) Background: Shikonin, the main ingredient in Chinese herbal medicine, is described as a novel angiogenesis inhibitor, and its anticancer effects have already been studied. Shikonin and its derivatives induce apoptosis and suppress metastasis, which further enhance the effectiveness of chemotherapy. However, their [...] Read more.

(1) Background: Shikonin, the main ingredient in Chinese herbal medicine, is described as a novel angiogenesis inhibitor, and its anticancer effects have already been studied. Shikonin and its derivatives induce apoptosis and suppress metastasis, which further enhance the effectiveness of chemotherapy. However, their mechanism of function has not been completely elucidated on human renal cancer cells. (2) Methods: In our study, CAKI-2 and A-498 cells were treated with increasing concentrations (2.5–40 µM) of shikonin, when colony formation ability and cytotoxic activity were tested. The changes in the expression of the main targets of apoptotic pathways were measured by RT-qPCR and Western blot. The intracellular levels of miR-21 and miR-155 were quantified by RT-qPCR. (3) Results: Shikonin exerted a dose-dependent effect on the proliferation of the cell lines examined. In 5 µM concentration of shikonin in vitro elevated caspase-3 and -7 levels, the proteins of the Ras/MAPK and PI3K/AKT pathways were activated. However, no significant changes were detected in the miR-21 and miR-155 expressions. (4) Conclusions: Our findings indicated that shikonin causes apoptosis of renal cancer cells by activating the Ras/MAPK and PI3K/AKT pathways. These effects of shikonin on renal cancer cells may bear important potential therapeutic implications for the treatment of renal cancer. Full article

(This article belongs to the Special Issue Natural Products Based Anticancer Drugs)

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15 pages, 3404 KiB

Open AccessArticle

New Biotinylated GHK and Related Copper(II) Complex: Antioxidant and Antiglycant Properties In Vitro against Neurodegenerative Disorders

by Rita Tosto, Graziella Vecchio and Francesco Bellia

Molecules 2023, 28(18), 6724; https://doi.org/10.3390/molecules28186724 - 20 Sep 2023

Viewed by 1830

Abstract

Neurodegenerative diseases affect millions of people worldwide. The failure of the enzymatic degradation, the oxidative stress, the dyshomeostasis of metal ions, among many other biochemical events, might trigger the pathological route, but the onset of these pathologies is unknown. Multi-target and multifunctional molecules [...] Read more.

Neurodegenerative diseases affect millions of people worldwide. The failure of the enzymatic degradation, the oxidative stress, the dyshomeostasis of metal ions, among many other biochemical events, might trigger the pathological route, but the onset of these pathologies is unknown. Multi-target and multifunctional molecules could address several biomolecular issues of the pathologies. The tripeptide GHK, a bioactive fragment of several proteins, and the related copper(II) complex have been largely used for many purposes, from cosmetic to therapeutic applications. GHK derivatives were synthesized to increase the peptide stability and improve the target delivery. Herein we report the synthesis of a new biotin–GHK conjugate (BioGHK) through orthogonal reactions. BioGHK is still capable of coordinating copper(II), as observed by spectroscopic and spectrometric measurements. The spectroscopic monitoring of the copper-induced ascorbate oxidation was used to measure the antioxidant activity Cu(II)-BioGHK complex, whereas antiglycant activity of the ligand towards harmful reactive species was investigated using MALDI-TOF. The affinity of BioGHK for streptavidin was evaluated using a spectrophotometric assay and compared to that of biotin. Finally, the antiaggregant activity towards amyloid-β was evaluated using a turn-on fluorescent dye. BioGHK could treat and/or prevent several adverse biochemical reactions that characterize neurodegenerative disorders, such as Alzheimer’s disease. Full article

(This article belongs to the Special Issue Recent Advances in Understanding and Treating Amyloidosis)

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18 pages, 6041 KiB

Open AccessArticle

Extractive Spectrophotometric Determination and Theoretical Investigations of Two New Vanadium(V) Complexes

by Kiril B. Gavazov, Petya V. Racheva, Antoaneta D. Saravanska, Galya K. Toncheva and Vasil B. Delchev

Molecules 2023, 28(18), 6723; https://doi.org/10.3390/molecules28186723 - 20 Sep 2023

Cited by 3 | Viewed by 1139

Abstract

Two new vanadium (V) complexes involving 6-hexyl-4-(2-thiazolylazo)resorcinol (HTAR) and tetrazolium cation were studied. The following commercially available tetrazolium salts were used as the cation source: tetrazolium red (2,3,5-triphenyltetrazol-2-ium;chloride, TTC) and neotetrazolium chloride (2-[4-[4-(3,5-diphenyltetrazol-2-ium-2-yl)phenyl]phenyl]-3,5-diphenyltetrazol-2-ium;dichloride, NTC). The cations (abbreviated as TT⁺ and NTC⁺ [...] Read more.

Two new vanadium (V) complexes involving 6-hexyl-4-(2-thiazolylazo)resorcinol (HTAR) and tetrazolium cation were studied. The following commercially available tetrazolium salts were used as the cation source: tetrazolium red (2,3,5-triphenyltetrazol-2-ium;chloride, TTC) and neotetrazolium chloride (2-[4-[4-(3,5-diphenyltetrazol-2-ium-2-yl)phenyl]phenyl]-3,5-diphenyltetrazol-2-ium;dichloride, NTC). The cations (abbreviated as TT⁺ and NTC⁺) impart high hydrophobicity to the ternary complexes, allowing vanadium to be easily extracted and preconcentrated in one step. The complexes have different stoichiometry. The V(V)–HTAR–TTC complex dimerizes in the organic phase (chloroform) and can be represented by the formula [(TT⁺)[VO₂(HTAR)]]₂. The other complex is monomeric (NTC⁺)[VO₂(HTAR)]. The cation has a +1 charge because one of the two chloride ions remains undissociated: NTC⁺ = (NT²⁺Cl⁻)⁺. The ground-state equilibrium geometries of the constituent cations and final complexes were optimized at the B3LYP and HF levels of theory. The dimer [(TT⁺)[VO₂(HTAR)]]₂ is more suitable for practical applications due to its better extraction characteristics and wider pH interval of formation and extraction. It was used for cheap and reliable extraction–spectrophotometric determination of V(V) traces in real samples. The absorption maximum, molar absorptivity coefficient, limit of detection, and linear working range were 549 nm, 5.2 × 10⁴ L mol⁻¹ cm⁻¹, 4.6 ng mL⁻¹, and 0.015–2.0 μg mL⁻¹, respectively. Full article

(This article belongs to the Special Issue Advances in Vanadium Complexes)

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18 pages, 2427 KiB

Open AccessArticle

Ternary Mixed Micelle Hexadecyltrimethylammonium Bromide—Dodecyltrimethylammonium Bromide—Sodium Deoxycholate: Gibbs Free Energy of Mixing and Excess Gibbs Energy of Mixing

by Ana Pilipović, Ivana Vapa, Vesna Tepavčević, Gorana Puača and Mihalj Poša

Molecules 2023, 28(18), 6722; https://doi.org/10.3390/molecules28186722 - 20 Sep 2023

Cited by 2 | Viewed by 1054

Abstract

Pharmaceutical, food, and cosmetic formulations often contain binary or ternary surfactant mixtures with synergistic interactions amongst micellar building blocks. Here, a ternary mixture of the surfactants hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, and sodium deoxycholate is examined to see if the molar fractions of the [...] Read more.

Pharmaceutical, food, and cosmetic formulations often contain binary or ternary surfactant mixtures with synergistic interactions amongst micellar building blocks. Here, a ternary mixture of the surfactants hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, and sodium deoxycholate is examined to see if the molar fractions of the surfactants in the ternary mixed micellar pseudophase are determined by the interaction coefficients between various pairs of the surfactants or by their propensity to self-associate. Critical micelle concentrations (CMC) of the analyzed ternary mixtures are determined experimentally (spectrofluorimetrically using pyrene as the probe molecule). Thermodynamic parameters of ternary mixtures are calculated from CMC values using the Regular Solution protocol. The tendency for monocomponent surfactants to self-associate (lower value of CMC) determines the molar fractions of surfactant in the mixed micelle if there is no issue with the packing of the micelle building units of the ternary mixed micelle. If a more hydrophobic surfactant is incorporated into the mixed micelle, the system (an aqueous solution of surfactants) is then the most thermodynamically stabilized. Full article

(This article belongs to the Section Physical Chemistry)

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11 pages, 2855 KiB

Open AccessArticle

Effects of 2,2′-Azobis(2-methylpropionamidine) Dihydrochloride Stress on the Gel Properties of Duck Myofibrillar Protein Isolate

by Xueshen Zhu, Jin Zhang, Xinyu Zhang, Qun Dai and Qingquan Fu

Molecules 2023, 28(18), 6721; https://doi.org/10.3390/molecules28186721 - 20 Sep 2023

Cited by 1 | Viewed by 1098

Abstract

The aim of this study was to investigate the biochemical properties and gel-forming capacity of duck myofibrillar proteins under the effects of 2,2′-azobis(2-methylpropionamidine) dihydrochloride (AAPH)-mediated oxidation. Duck myofibrillar proteins were extracted and treated with different concentrations of AAPH solutions (0, 1, 3, 5, [...] Read more.

The aim of this study was to investigate the biochemical properties and gel-forming capacity of duck myofibrillar proteins under the effects of 2,2′-azobis(2-methylpropionamidine) dihydrochloride (AAPH)-mediated oxidation. Duck myofibrillar proteins were extracted and treated with different concentrations of AAPH solutions (0, 1, 3, 5, 10 mmol/L) and then analysed for carbonyl content, dynamic rheology, protein profiles and gel-forming properties (colour, water holding capacity, gel strength and microstructure). The results showed that with increasing AAPH concentration, the carbonyl content of the proteins exhibited an increasing trend (p < 0.05); SDS-PAGE pattern changes indicated that moderate oxidation (3 mmol/L AAPH) induced myosin aggregation via covalent bonds including disulfide, enhanced protein–protein interactions, and thus affected the gel strength of the DMPs’ heat-induced gels. However, high oxidation (5 and 10 mmol/L AAPH) led to the partial degradation of the myosin heavy chain (MHC) isoforms, as evidenced by lower storage modulus and irregular microstructures, which significantly reduced gelation ability. These results suggest that the internal relationship between alkylperoxyl radical-induced oxidation should be taken into account in the processing of duck meat, as mild protein oxidation is conducive to improving gel quality. Full article

(This article belongs to the Collection Advances in Food Chemistry)

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14 pages, 8843 KiB

Open AccessArticle

Metformin-Loaded Chitosan Hydrogels Suppress Bladder Tumor Growth in an Orthotopic Mouse Model via Intravesical Administration

by Xingjian Zhang, Xin Hu, Yijun Xie, Lejing Xie, Xiangyi Chen, Mei Peng, Duo Li, Jun Deng, Di Xiao and Xiaoping Yang

Molecules 2023, 28(18), 6720; https://doi.org/10.3390/molecules28186720 - 20 Sep 2023

Cited by 1 | Viewed by 1462

Abstract

Our previous study found that the intravesical perfusion of metformin has excellent inhibitory effects against bladder cancer (BC). However, this administration route allows the drug to be diluted and excreted in urine. Therefore, increasing the adhesion of metformin to the bladder mucosal layer [...] Read more.

Our previous study found that the intravesical perfusion of metformin has excellent inhibitory effects against bladder cancer (BC). However, this administration route allows the drug to be diluted and excreted in urine. Therefore, increasing the adhesion of metformin to the bladder mucosal layer may prolong the retention time and increase the pharmacological activity. It is well known that chitosan (Cs) has a strong adhesion to the bladder mucosal layer. Thus, this study established a novel formulation of metformin to enhance its antitumor activity by extending its retention time. In this research, we prepared Cs freeze-dried powder and investigated the effect of metformin-loaded chitosan hydrogels (MLCH) in vitro and in vivo. The results showed that MLCH had a strong inhibitory effect against proliferation and colony formation in vitro. The reduction in BC weight and the expression of tumor biomarkers in orthotopic mice showed the robust antitumor activity of MLCH via intravesical administration in vivo. The non-toxic profile of MLCH was observed as well, using histological examinations. Mechanistically, MLCH showed stronger functional activation of the AMPKα/mTOR signaling pathway compared with metformin alone. These findings aim to make this novel formulation an efficient candidate for managing BC via intravesical administration. Full article

(This article belongs to the Special Issue Nanomaterials in Cancer Therapy: Synthesis, Mechanisms, and Applications)

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30 pages, 6747 KiB

Open AccessReview

Strategies and Applications of Graphene and Its Derivatives-Based Electrochemical Sensors in Cancer Diagnosis

by Li Fu, Yuhong Zheng, Xingxing Li, Xiaozhu Liu, Cheng-Te Lin and Hassan Karimi-Maleh

Molecules 2023, 28(18), 6719; https://doi.org/10.3390/molecules28186719 - 20 Sep 2023

Cited by 19 | Viewed by 3426

Abstract

Graphene is an emerging nanomaterial increasingly being used in electrochemical biosensing applications owing to its high surface area, excellent conductivity, ease of functionalization, and superior electrocatalytic properties compared to other carbon-based electrodes and nanomaterials, enabling faster electron transfer kinetics and higher sensitivity. Graphene [...] Read more.

Graphene is an emerging nanomaterial increasingly being used in electrochemical biosensing applications owing to its high surface area, excellent conductivity, ease of functionalization, and superior electrocatalytic properties compared to other carbon-based electrodes and nanomaterials, enabling faster electron transfer kinetics and higher sensitivity. Graphene electrochemical biosensors may have the potential to enable the rapid, sensitive, and low-cost detection of cancer biomarkers. This paper reviews early-stage research and proof-of-concept studies on the development of graphene electrochemical biosensors for potential future cancer diagnostic applications. Various graphene synthesis methods are outlined along with common functionalization approaches using polymers, biomolecules, nanomaterials, and synthetic chemistry to facilitate the immobilization of recognition elements and improve performance. Major sensor configurations including graphene field-effect transistors, graphene modified electrodes and nanocomposites, and 3D graphene networks are highlighted along with their principles of operation, advantages, and biosensing capabilities. Strategies for the immobilization of biorecognition elements like antibodies, aptamers, peptides, and DNA/RNA probes onto graphene platforms to impart target specificity are summarized. The use of nanomaterial labels, hybrid nanocomposites with graphene, and chemical modification for signal enhancement are also discussed. Examples are provided to illustrate applications for the sensitive electrochemical detection of a broad range of cancer biomarkers including proteins, circulating tumor cells, DNA mutations, non-coding RNAs like miRNA, metabolites, and glycoproteins. Current challenges and future opportunities are elucidated to guide ongoing efforts towards transitioning graphene biosensors from promising research lab tools into mainstream clinical practice. Continued research addressing issues with reproducibility, stability, selectivity, integration, clinical validation, and regulatory approval could enable wider adoption. Overall, graphene electrochemical biosensors present powerful and versatile platforms for cancer diagnosis at the point of care. Full article

(This article belongs to the Special Issue Synthesis, Functionalization, and Sensing Applications of Diverse Dimensional Graphene Materials)

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