Molecules

19 pages, 7069 KiB

Open AccessEditor’s ChoiceArticle

Detailed Structural Characterization of Oxidized Sucrose and Its Application in the Fully Carbohydrate-Based Preparation of a Hydrogel from Carboxymethyl Chitosan

by Hiroyuki Kono, Junki Noda and Haruki Wakamori

Molecules 2022, 27(18), 6137; https://doi.org/10.3390/molecules27186137 - 19 Sep 2022

Cited by 4 | Viewed by 2043

Abstract

Oxidized sucrose (OS) is a bio-based cross-linking agent with excellent biological safety and environmental non-toxicity. However, the precise structure of OS has not been elucidated owing to its structural complexity and low purity. Accordingly, in this study, complete chemical shift assignments were performed [...] Read more.

Oxidized sucrose (OS) is a bio-based cross-linking agent with excellent biological safety and environmental non-toxicity. However, the precise structure of OS has not been elucidated owing to its structural complexity and low purity. Accordingly, in this study, complete chemical shift assignments were performed by applying various nuclear magnetic resonance techniques, which permitted the structural and quantitative characterization of the two main OS products, each of which contained four aldehyde groups. In addition, we investigated the use of OS as a cross-linking agent in the preparation of a hydrogel from carboxymethyl chitosan (CMC), one of the most popular polysaccharides for use in biomedical applications. The primary amine groups of CMC were immediately cross-linked with the aldehyde groups of OS to form hydrogels without the requirement for a catalyst. It was found that the degree of cross-linking could be easily controlled by the feed amount of OS during CMC hydrogel preparation and the final cross-linking degree affected the thermal, swelling, and rheological properties of the obtained hydrogel. The results presented in this study are therefore expected to be applicable in the preparation of fully carbohydrate-based hydrogels for medical and pharmaceutical applications. Full article

(This article belongs to the Section Macromolecular Chemistry)

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19 pages, 2622 KiB

Open AccessArticle

Chemical Composition, Enantiomeric Distribution, Antimicrobial and Antioxidant Activities of Origanum majorana L. Essential Oil from Nepal

by Prem Narayan Paudel, Prabodh Satyal, Rakesh Satyal, William N. Setzer and Rajendra Gyawali

Molecules 2022, 27(18), 6136; https://doi.org/10.3390/molecules27186136 - 19 Sep 2022

Cited by 12 | Viewed by 3029

Abstract

This study was conducted to examine the chemical constituents of Origanum majorana L. essential oils (EOs) that originate in Nepal, as well as their biological activities, antioxidant properties, and enantiomeric compositions. The EOs were extracted by the hydro-distillation method using a Clevenger-type apparatus [...] Read more.

This study was conducted to examine the chemical constituents of Origanum majorana L. essential oils (EOs) that originate in Nepal, as well as their biological activities, antioxidant properties, and enantiomeric compositions. The EOs were extracted by the hydro-distillation method using a Clevenger-type apparatus and their chemical compositions were determined through gas chromatography and mass spectrometry (GC-MS). Chiral GC-MS was used to evaluate the enantiomeric compositions of EOs. The minimum inhibitory concentrations (MICs) of the essential oils were determined by the micro-broth dilution method, and the antioxidant activity was evaluated by the 2,2-diphenyl-1-picrylhydrazyl scavenging assay and ferric-reducing antioxidant power (FRAP). GC-MS analysis showed the presence of 50 and 41 compounds in the EO samples, (S₁) and (S₂), respectively, representing the Kathmandu and Bhaktapur districts. The oxygenated monoterpenoids, along with terpinen-4-ol, were predominant constituents in both EO samples. However, the EOs from two locations showed some variations in their major components. The chiral terpenoids for two EO samples of marjoram have also been reported in this study in an elaborative way for the first time in accordance with the literature review. A hierarchical cluster analysis based on the compositions of EOs with 50 compositions reported in the literature revealed at least 5 different chemotypes of marjoram oil. The antioxidant activity for the sample (S₂) was found to be relatively moderate, with an IC₅₀ value of 225.61 ± 0.05 μg/mL and an EC₅₀ value of 372.72 ± 0.84 µg/mL, as compared to the standard used. Furthermore, with an MIC value of 78.1 µg/mL, the EO from sample (S₂) demonstrated effective antifungal activity against Aspergillus niger and Candida albicans. Moreover, both samples displayed considerable antimicrobial activity. The results suggest that EOs of Origanum majorana possess some noteworthy antimicrobial properties as well as antioxidant activity, and hence can be used as a natural preservative ingredient in the food and pharmaceutical industries. Full article

(This article belongs to the Special Issue Biomolecules from Essential Oil Bearing Plants: Biological and Industrial Applications II)

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19 pages, 836 KiB

Open AccessArticle

Graph Neural Network for Protein–Protein Interaction Prediction: A Comparative Study

by Hang Zhou, Weikun Wang, Jiayun Jin, Zengwei Zheng and Binbin Zhou

Molecules 2022, 27(18), 6135; https://doi.org/10.3390/molecules27186135 - 19 Sep 2022

Cited by 7 | Viewed by 3414

Abstract

Proteins are the fundamental biological macromolecules which underline practically all biological activities. Protein–protein interactions (PPIs), as they are known, are how proteins interact with other proteins in their environment to perform biological functions. Understanding PPIs reveals how cells behave and operate, such as [...] Read more.

Proteins are the fundamental biological macromolecules which underline practically all biological activities. Protein–protein interactions (PPIs), as they are known, are how proteins interact with other proteins in their environment to perform biological functions. Understanding PPIs reveals how cells behave and operate, such as the antigen recognition and signal transduction in the immune system. In the past decades, many computational methods have been developed to predict PPIs automatically, requiring less time and resources than experimental techniques. In this paper, we present a comparative study of various graph neural networks for protein–protein interaction prediction. Five network models are analyzed and compared, including neural networks (NN), graph convolutional neural networks (GCN), graph attention networks (GAT), hyperbolic neural networks (HNN), and hyperbolic graph convolutions (HGCN). By utilizing the protein sequence information, all of these models can predict the interaction between proteins. Fourteen PPI datasets are extracted and utilized to compare the prediction performance of all these methods. The experimental results show that hyperbolic graph neural networks tend to have a better performance than the other methods on the protein-related datasets. Full article

(This article belongs to the Special Issue Development and Application of Computational Methods in Antigen Recognition)

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13 pages, 1178 KiB

Open AccessArticle

Evaluation of the Chemical Composition, Bioactive Substance, Gas Production, and Rumen Fermentation Parameters of Four Types of Distiller’s Grains

by Qi Lu, Qingyuan Luo, Jiaxuan Li, Xu Wang, Chao Ban, Jixiao Qin, Yayuan Tian, Xingzhou Tian and Xiang Chen

Molecules 2022, 27(18), 6134; https://doi.org/10.3390/molecules27186134 - 19 Sep 2022

Cited by 7 | Viewed by 1711

Abstract

Distiller’s grain is rich in natural active ingredients and can be used as an excellent antioxidant feed for goats. The current study aimed to assess the feeding value of four different types of distiller’s grains with an in vitro gas production trial. The [...] Read more.

Distiller’s grain is rich in natural active ingredients and can be used as an excellent antioxidant feed for goats. The current study aimed to assess the feeding value of four different types of distiller’s grains with an in vitro gas production trial. The chemical composition, total phenols, total anthocyanins, dry matter degradability, methane, hydrogen, and rumen fermentation parameters were evaluated. The results indicated that red distiller’s grain and glutinous rice distiller’s grain had higher (p < 0.05) levels of crude protein than the other two types. There were significantly (p < 0.05) higher concentrations of dry matter, ether extract, hemicellulose, and total carbohydrate in corn distiller’s grain than in the other three types of distiller’s grain. In addition, red distiller’s grain showed a higher (p < 0.05) gas production rate constant (c) and ruminal outflow rate, as well as higher (p < 0.05) concentrations of total phenol, total anthocyanins and 2,2-diphenyl-1-picrylhydrazyl (DPPH) scavenging activity, than the other three types of distiller’s grains. In contrast, red distiller’s grain displayed the lowest (p < 0.05) immediately soluble fraction (a) and half the time of maximum gas production relative to the other samples. In particular, the levels of methane (%) in white distiller’s grain and glutinous rice distiller’s grain were greater (p < 0.05) than that in red distiller’s grain. Moreover, the ammonia nitrogen content in red distiller’s grain was greater (p < 0.05) than that in white distiller’s grain and corn distiller’s grain. In contrast, red distiller’s grain exhibited a lower (p < 0.05) level of ruminal fluid acetic acid relative to that found in white distiller’s grain and corn distiller’s grain. Taken together, the results showed that red distiller’s grain and glutinous rice distiller’s grain could be used as protein feed, red distiller’s grain had higher levels of total phenols and total anthocyanins and a high DPPH scavenging activity; corn distiller’s grain might be considered as an alternative energy source feed, and white distiller’s grain exhibited higher total gas production. Full article

(This article belongs to the Special Issue Anthocyanins: The Infinite Properties of These Incredible Compounds)

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15 pages, 5102 KiB

Open AccessArticle

Design, Synthesis and Bioactivity of Novel Low Bee-Toxicity Compounds Based on Flupyrimin

by Xingxing Lu, Huan Xu, Xiaoming Zhang, Tengda Sun, Yufan Lin, Yongheng Zhang, Honghong Li, Xuesheng Li, Xinling Yang, Hongxia Duan and Yun Ling

Molecules 2022, 27(18), 6133; https://doi.org/10.3390/molecules27186133 - 19 Sep 2022

Cited by 5 | Viewed by 2035

Abstract

Neonicotinoids are important insecticides for controlling aphids in agriculture. Growing research suggested that neonicotinoid insecticides are a key factor causing the decline of global pollinator insects, such as bees. Flupyrimin (FLP) is a novel nicotinic insecticide with unique biological properties and no cross-resistance, [...] Read more.

Neonicotinoids are important insecticides for controlling aphids in agriculture. Growing research suggested that neonicotinoid insecticides are a key factor causing the decline of global pollinator insects, such as bees. Flupyrimin (FLP) is a novel nicotinic insecticide with unique biological properties and no cross-resistance, and is safe for pollinators. Using FLP as the lead compound, a series of novel compounds were designed and synthesized by replacing the amide fragment with a sulfonamideone. Their structures were confirmed by ¹H NMR, ¹³C NMR and HRMS spectra. Bioassay results showed that compound 2j had good insecticidal activity against Aphis glycines with an LC₅₀ value of 20.93 mg/L. Meanwhile, compound 2j showed significantly lower acute oral and contact toxicity to Apis mellifera. In addition, compound 2j interacted well with the protein in insect acetylcholine binding protein (AChBP). The molecular docking on honeybee nicotinic acetylcholine receptor (nAChR) indicated that the sulfonamide group of compound 2j did not form a hydrogen bond with Arg173 of the β subunit, which conforms to the reported low bee-toxicity conformation. In general, target compound 2j can be regarded as a bee-friendly insecticide candidate. Full article

(This article belongs to the Special Issue Advances in Novel Pesticide Discovery)

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9 pages, 381 KiB

Open AccessArticle

Molecular Dynamics Study of Structural and Transport Properties of Silver Iodide Using Effective Charges

by Diego Peña Lara, Hernando Correa and Jesús Evelio Diosa

Molecules 2022, 27(18), 6132; https://doi.org/10.3390/molecules27186132 - 19 Sep 2022

Viewed by 1106

Abstract

The superionic conductor, solid state, and body-centered cubic structure, silver iodide at room temperature, has been studied via molecular dynamics simulations. The calculated results using pairwise Coulomb-Buckingham potential, zero pressure on the sample, a semi-rigid model system of 1000 Ag and 1000 I [...] Read more.

The superionic conductor, solid state, and body-centered cubic structure, silver iodide at room temperature, has been studied via molecular dynamics simulations. The calculated results using pairwise Coulomb-Buckingham potential, zero pressure on the sample, a semi-rigid model system of 1000 Ag and 1000 I ions, (

N V E

) as a statistical ensemble, and an effective charge of

Z = 0.63

for the pairs Ag-Ag and I-I, were found to be consistent with experimental data and one study using

Z = 0.60

, different potential, and simulation software. For the pair Ag-I, there is a discrepancy due to the high silver ion diffusion. The calculated value of the diffusion constant of the silver ion is greater than iodide ion. The dynamic transport properties (mean square displacement, velocity autocorrelation function) results indicated typical behavior reported by other authors, using different potentials in their DM simulations for iodine and silver ions. Full article

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4 pages, 520 KiB

Open AccessEditorial

New Insights into Thermodynamics of Solutes in Neat and Complex Solvents

by Piotr Cysewski, Tomasz Jeliński and Maciej Przybyłek

Molecules 2022, 27(18), 6131; https://doi.org/10.3390/molecules27186131 - 19 Sep 2022

Viewed by 1273

Abstract

Solubility is one of the most important physicochemical properties, both from a practical and theoretical perspective [...] Full article

(This article belongs to the Special Issue New Insights into Thermodynamics of Solutes in Neat and Complex Solvents)

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16 pages, 2773 KiB

Open AccessArticle

Encapsulation of Vitamin B₁₂ by Complex Coacervation of Whey Protein Concentrate–Pectin; Optimization and Characterization

by Neda Akbari, Elham Assadpour, Mohammad Saeed Kharazmi and Seid Mahdi Jafari

Molecules 2022, 27(18), 6130; https://doi.org/10.3390/molecules27186130 - 19 Sep 2022

Cited by 3 | Viewed by 1978

Abstract

Vitamin B₁₂ (VB₁₂) is one of the essential vitamins for the body, which is sensitive to light, heat, oxidizing agents, and acidic and alkaline substances. Therefore, the encapsulation of VB₁₂ can be one of the ways to protect it [...] Read more.

Vitamin B₁₂ (VB₁₂) is one of the essential vitamins for the body, which is sensitive to light, heat, oxidizing agents, and acidic and alkaline substances. Therefore, the encapsulation of VB₁₂ can be one of the ways to protect it against processing and environmental conditions in food. In this work, the influence of pectin concentration (0.5–1% w/v), whey protein concentrate (WPC) level (4–8% w/v) and pH (3–9) on some properties of VB₁₂-loaded pectin–WPC complex carriers was investigated by response surface methodology (RSM). The findings showed that under optimum conditions (1:6.47, pectin:WPC and pH = 6.6), the encapsulation efficiency (EE), stability, viscosity, particle size and solubility of complex carriers were 80.71%, 85.38%, 39.58 mPa·s, 7.07 µm and 65.86%, respectively. Additionally, the formation of complex coacervate was confirmed by Fourier-transform infrared (FTIR) spectroscopy and atomic force microscopy (AFM). In addition, it was revealed that the most important factor in VB₁₂ encapsulation was pH; at a pH < isoelectric point of WPC (pH = 3), in comparison with higher pH values (6 and 9), a stronger complex was formed between pectin and WPC, which led to an increase in EE, lightness parameter, particle size and water activity, as well as a decrease in the zeta-potential and porosity of complex carriers. Full article

(This article belongs to the Special Issue Nanodelivery of Food Bioactive Compounds)

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15 pages, 3046 KiB

Open AccessArticle

An Experimental and Theoretical Study on Essential Oil of Aethionema sancakense: Characterization, Molecular Properties and RDG Analysis

by Azize Demirpolat, Feride Akman and Aleksandr S. Kazachenko

Molecules 2022, 27(18), 6129; https://doi.org/10.3390/molecules27186129 - 19 Sep 2022

Cited by 21 | Viewed by 2032

Abstract

This study aims to experimentally and theoretically examine the plant Aethionema sancakense, which was determined as a new species and whose essential oil and fatty acid compositions were characterized by GC/GC-MS technique. Linoleic acid (23.1%), α-humulene (19.8%), camphene (13.9%), and heptanal (9.7%) [...] Read more.

This study aims to experimentally and theoretically examine the plant Aethionema sancakense, which was determined as a new species and whose essential oil and fatty acid compositions were characterized by GC/GC-MS technique. Linoleic acid (23.1%), α-humulene (19.8%), camphene (13.9%), and heptanal (9.7%) were found to be the major essential oil components of A. sancakense aerial part structures. The quantum chemical calculations of these four molecules that are very important to this plant were performed using the density functional method (DFT)/B3LYP with the 6-31 G (d, p) basis set in the ground state for the gas phase. The molecular structures, HOMO-LUMO energies, electronic properties, Fukui functions, and molecular electrostatic potential (MEP) surfaces of the major constituents of Aethionema sancakense essential oil were calculated and interpreted. Finally, the RDG-NCI analysis of these molecules was performed to determine the non-covalent interactions present within the molecules. Full article

(This article belongs to the Section Natural Products Chemistry)

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16 pages, 4550 KiB

Open AccessArticle

Helical versus Flat Bis-Ferrocenyl End-Capped Peptides: The Influence of the Molecular Skeleton on Redox Properties

by Saverio Santi, Barbara Biondi, Roberta Cardena, Annalisa Bisello, Renato Schiesari, Silvia Tomelleri, Marco Crisma and Fernando Formaggio

Molecules 2022, 27(18), 6128; https://doi.org/10.3390/molecules27186128 - 19 Sep 2022

Cited by 2 | Viewed by 1487

Abstract

Despite the fact that peptide conjugates with a pendant ferrocenyl (Fc) have been widely investigated, bis-ferrocenyl end-capped peptides are rarely synthetized. In this paper, in addition to the full characterization of the Fc-CO-[_L-Dap(Boc)]_n-NH-Fc series, we report a comparison of [...] Read more.

Despite the fact that peptide conjugates with a pendant ferrocenyl (Fc) have been widely investigated, bis-ferrocenyl end-capped peptides are rarely synthetized. In this paper, in addition to the full characterization of the Fc-CO-[_L-Dap(Boc)]_n-NH-Fc series, we report a comparison of the three series of bis-ferrocenyl homopeptides synthesized to date, to gain insights into the influence of α-amino isobutyric (Aib), 2,3-diamino propionic (Dap) and C^α,β-didehydroalanine (ΔAla) amino acids on the peptide secondary structure and on the ferrocene redox properties. The results obtained by 2D NMR analysis and X-ray crystal structures, and further supported by electrochemical data, evidence different behaviors depending on the nature of the amino acid; that is, the formation of 3₁₀-helices or fully extended (2.0₅-helix) structures. In these foldamers, the orientation of the carbonyl groups in the peptide helix yields a macrodipole with the positive pole on the N-terminal amino acid and the negative pole on the C-terminal amino acid, so that oxidation of the Fc moieties takes place more or less easily depending on the orientation of the macrodipole moment as the peptide chain grows. Conversely, the fully extended conformation adopted by ΔAla flat peptides neither generates a macrodipole nor affects Fc oxidation. The utilization as electrochemical and optical (Circular Dichroism) probes of the two terminal Fc groups, bound to the same peptide chain, makes it possible to study the end-to-end effects of the positive charges produced by single and double oxidations, and to evidence the presence “exciton-coupled” CD among the two intramolecularly interacting Fc groups of the _L-Dap(Boc) series. Full article

(This article belongs to the Special Issue Electrochemistry and Organometallic Catalysis: Themed Issue in Honor of the Great Contribution of Prof. Dr. Christian Amatore and Prof. Dr. Anny Jutand)

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16 pages, 4097 KiB

Open AccessArticle

Identification of SARS-CoV-2 Main Protease Inhibitors from a Library of Minor Cannabinoids by Biochemical Inhibition Assay and Surface Plasmon Resonance Characterized Binding Affinity

by Chang Liu, Tess Puopolo, Huifang Li, Ang Cai, Navindra P. Seeram and Hang Ma

Molecules 2022, 27(18), 6127; https://doi.org/10.3390/molecules27186127 - 19 Sep 2022

Cited by 4 | Viewed by 3205

Abstract

The replication of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is mediated by its main protease (M^pro), which is a plausible therapeutic target for coronavirus disease 2019 (COVID-19). Although numerous in silico studies reported the potential inhibitory effects of natural [...] Read more.

The replication of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is mediated by its main protease (M^pro), which is a plausible therapeutic target for coronavirus disease 2019 (COVID-19). Although numerous in silico studies reported the potential inhibitory effects of natural products including cannabis and cannabinoids on SARS-CoV-2 M^pro, their anti-M^pro activities are not well validated by biological experimental data. Herein, a library of minor cannabinoids belonging to several chemotypes including tetrahydrocannabinols, cannabidiols, cannabigerols, cannabichromenes, cannabinodiols, cannabicyclols, cannabinols, and cannabitriols was evaluated for their anti-M^pro activity using a biochemical assay. Additionally, the binding affinities and molecular interactions between the active cannabinoids and the M^pro protein were studied by a biophysical technique (surface plasmon resonance; SPR) and molecular docking, respectively. Cannabinoids tetrahydrocannabutol and cannabigerolic acid were the most active M^pro inhibitors (IC₅₀ = 3.62 and 14.40 μM, respectively) and cannabigerolic acid had a binding affinity

K_{D} = 2.16 \times 10^{- 4}

M). A preliminary structure and activity relationship study revealed that the anti-

M^{pro}

effects of cannabinoids were influenced by the decarboxylation of cannabinoids and the length of cannabinoids’ alkyl side chain. Findings from the biochemical, biophysical, and computational assays support the growing evidence of cannabinoids’ inhibitory effects on SARS-CoV-2 M^pro. Full article

(This article belongs to the Special Issue Non-Psychotropic Phytocannabinoids: A New Source of Drugs)

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18 pages, 3592 KiB

Open AccessArticle

Novel 4-Azapregnene Derivatives as Potential Anticancer Agents: Synthesis, Antiproliferative Activity and Molecular Docking Studies

by Vanessa Brito, Adriana Oliveira Santos, Gilberto Alves, Paulo Almeida and Samuel Silvestre

Molecules 2022, 27(18), 6126; https://doi.org/10.3390/molecules27186126 - 19 Sep 2022

Cited by 1 | Viewed by 1624

Abstract

A series of novel 21E-arylidene-4-azapregn-5-ene steroids has been successfully designed, synthesized and structurally characterized, and their antiproliferative activity was evaluated in four different cell lines. Within this group, the 21E-(pyridin-3-yl)methylidene derivative exhibited significant cytotoxic activity in hormone-dependent cells LNCaP [...] Read more.

A series of novel 21E-arylidene-4-azapregn-5-ene steroids has been successfully designed, synthesized and structurally characterized, and their antiproliferative activity was evaluated in four different cell lines. Within this group, the 21E-(pyridin-3-yl)methylidene derivative exhibited significant cytotoxic activity in hormone-dependent cells LNCaP (IC₅₀ = 10.20 µM) and T47-D cells (IC₅₀ = 1.33 µM). In PC-3 androgen-independent cells, the steroid 21E-p-nitrophenylidene-4-azapregn-5-ene was the most potent of this series (IC₅₀ = 3.29 µM). Considering these results, the 21E-(pyridin-3-yl)methylidene derivative was chosen for further biological studies on T47-D and LNCaP cells, and it was shown that this azasteroid seems to lead T47-D cells to apoptotic death. Finally, molecular docking studies were performed to explore the affinity of these 4-azapregnene derivatives to several steroid targets, namely 5α-reductase type 2, estrogen receptor α, androgen receptor and CYP17A1. In general, compounds presented higher affinity to 5α-reductase type 2 and estrogen receptor α. Full article

(This article belongs to the Special Issue Steroid Compounds with Potential Biological Activity)

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14 pages, 1753 KiB

Open AccessArticle

Machine Learning for Evaluating the Cytotoxicity of Mixtures of Nano-TiO₂ and Heavy Metals: QSAR Model Apply Random Forest Algorithm after Clustering Analysis

by Leqi Sang, Yunlin Wang, Cheng Zong, Pengfei Wang, Huazhong Zhang, Dan Guo, Beilei Yuan and Yong Pan

Molecules 2022, 27(18), 6125; https://doi.org/10.3390/molecules27186125 - 19 Sep 2022

Cited by 7 | Viewed by 1941

Abstract

With the development and application of nanomaterials, their impact on the environment and organisms has attracted attention. As a common nanomaterial, nano-titanium dioxide (nano-TiO₂) has adsorption properties to heavy metals in the environment. Quantitative structure-activity relationship (QSAR) is often used to [...] Read more.

With the development and application of nanomaterials, their impact on the environment and organisms has attracted attention. As a common nanomaterial, nano-titanium dioxide (nano-TiO₂) has adsorption properties to heavy metals in the environment. Quantitative structure-activity relationship (QSAR) is often used to predict the cytotoxicity of a single substance. However, there is little research on the toxicity of interaction between nanomaterials and other substances. In this study, we exposed human renal cortex proximal tubule epithelial (HK-2) cells to mixtures of eight heavy metals with nano-TiO₂, measured absorbance values by CCK-8, and calculated cell viability. PLS and two ensemble learning algorithms are used to build multiple QSAR models for data sets, and the test set R² is increased from 0.38 to 0.78 and 0.85, and RMSE is decreased from 0.18 to 0.12 and 0.10. After selecting the better random forest algorithm, the K-means clustering algorithm is used to continue to optimize the model, increasing the test set R² to 0.95 and decreasing the RMSE to 0.08 and 0.06. As a reliable machine algorithm, random forest can be used to predict the toxicity of the mixture of nano-metal oxides and heavy metals. The cluster analysis can effectively improve the stability and predictability of the model, and provide a new idea for the prediction of cytotoxicity model in the future. Full article

(This article belongs to the Special Issue QSAR and QSPR: Recent Developments and Applications III)

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16 pages, 2743 KiB

Open AccessArticle

Thermodynamics and Spectroscopy of Halogen- and Hydrogen-Bonded Complexes of Haloforms with Aromatic and Aliphatic Amines

by Emmanuel Adeniyi, Olivia Grounds, Zachary Stephens, Matthias Zeller and Sergiy V. Rosokha

Molecules 2022, 27(18), 6124; https://doi.org/10.3390/molecules27186124 - 19 Sep 2022

Cited by 2 | Viewed by 1727

Abstract

Similarities and differences of halogen and hydrogen bonding were explored via UV–Vis and ¹H NMR measurements, X-ray crystallography and computational analysis of the associations of CHX₃ (X=I, Br, Cl) with aromatic (tetramethyl-p-phenylenediamine) and aliphatic (4-diazabicyclo[2,2,2]octane) amines. When the polarization [...] Read more.

Similarities and differences of halogen and hydrogen bonding were explored via UV–Vis and ¹H NMR measurements, X-ray crystallography and computational analysis of the associations of CHX₃ (X=I, Br, Cl) with aromatic (tetramethyl-p-phenylenediamine) and aliphatic (4-diazabicyclo[2,2,2]octane) amines. When the polarization of haloforms was taken into account, the strengths of these complexes followed the same correlation with the electrostatic potentials on the surfaces of the interacting atoms. However, their spectral properties were quite distinct. While the halogen-bonded complexes showed new intense absorption bands in the UV–Vis spectra, the absorptions of their hydrogen-bonded analogues were close to the superposition of the absorption of reactants. Additionally, halogen bonding led to a shift in the NMR signal of haloform protons to lower ppm values compared with the individual haloforms, whereas hydrogen bonding of CHX₃ with aliphatic amines resulted in a shift in the opposite direction. The effects of hydrogen bonding with aromatic amines on the NMR spectra of haloforms were ambivalent. Titration of all CHX₃ with these nucleophiles produced consistent shifts in their protons’ signals to lower ppm values, whereas calculations of these pairs produced multiple hydrogen-bonded minima with similar structures and energies, but opposite directions of the NMR signals’ shifts. Experimental and computational data were used for the evaluation of formation constants of some halogen- and hydrogen-bonded complexes between haloforms and amines co-existing in solutions. Full article

(This article belongs to the Special Issue Chemical Bond and Intermolecular Interactions)

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15 pages, 1391 KiB

Open AccessArticle

Assessment of the Effects of Chitosan, Chitooligosaccharides and Their Derivatives on Lemna minor

by Bianca-Vanesa Boros, Daniela Dascalu, Vasile Ostafe and Adriana Isvoran

Molecules 2022, 27(18), 6123; https://doi.org/10.3390/molecules27186123 - 19 Sep 2022

Cited by 7 | Viewed by 1647

Abstract

Chitosan, chitooligosaccharides and their derivatives’ production and use in many fields may result in their release to the environment, possibly affecting aquatic organisms. Both an experimental and a computational approach were considered for evaluating the effects of these compounds on Lemna minor. [...] Read more.

Chitosan, chitooligosaccharides and their derivatives’ production and use in many fields may result in their release to the environment, possibly affecting aquatic organisms. Both an experimental and a computational approach were considered for evaluating the effects of these compounds on Lemna minor. Based on the determined EC₅₀ values against L. minor, only D-glucosamine hydrochloride (EC₅₀ = 11.55 mg/L) was considered as “slightly toxic” for aquatic environments, while all the other investigated compounds, having EC₅₀ > 100 mg/L, were considered as “practically non-toxic”. The results obtained in the experimental approach were in good agreement with the predictions obtained using the admetSAR2.0 computational tool, revealing that the investigated compounds were not considered toxic for crustacean, fish and Tetrahymena pyriformis aquatic microorganisms. The ADMETLab2.0 computational tool predicted the values of IGC₅₀ for Tetrahymena pyriformis and the LC₅₀ for fathead minnow and Daphnia magna, with the lowest values of these parameters being revealed by totally acetylated chitooligosaccharides in correlation with their lowest solubility. The effects of the chitooligosaccharides and chitosan on L. minor decreased with increased molecular weight, increased with the degree of deacetylation and were reliant on acetylation patterns. Furthermore, the solubility mainly influenced the effects on the aqueous environment, with a higher solubility conducted to lower toxicity. Full article

(This article belongs to the Special Issue Degradation of Drugs and Organic Pollutants in Wastewater)

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12 pages, 1701 KiB

Open AccessArticle

In Vivo Detection of Tetrodotoxin in Takifugu obscurus Based on Solid-Phase Microextraction Coupled with Ultrahigh-Performance Liquid Chromatography–Tandem Mass Spectrometry

by Hengli Meng, Shui Jiang, Yin Zhang, Yun Hu and Yuan Liu

Molecules 2022, 27(18), 6122; https://doi.org/10.3390/molecules27186122 - 19 Sep 2022

Cited by 2 | Viewed by 1434

Abstract

Pufferfish is nutritious and delicious, but the tetrodotoxin (TTX) that may exist in its body poses a serious safety hazard. It is important to use scientific and effective methods to detect the TTX in pufferfish, but most of the existing methods require complex [...] Read more.

Pufferfish is nutritious and delicious, but the tetrodotoxin (TTX) that may exist in its body poses a serious safety hazard. It is important to use scientific and effective methods to detect the TTX in pufferfish, but most of the existing methods require complex pre-treatment steps and have sample lethality. The solid-phase microextraction (SPME) technology can be used for in vivo detection due to its advantages such as no solvent demand, simple operation, and fast detection speed. In this study, the GO-PAN@PNE SPME fibers were made via a dipping method, and their extraction effect was verified in the TTX aqueous and spiked fish. The established method has good reproducibility, and the limit of detection of TTX in pufferfish was 32 ng·g⁻¹, and the limit of quantitation was 150 ng·g⁻¹, which can meet the detection needs of pufferfish for safe consumption. This method was used to in vivo detect the Takifugu obscurus exposed to the TTX, to determine the content of TTX in the pufferfish muscle. The detection method established in this study can relatively quickly and easily realize the in vivo detection of TTX in the pufferfish, which can provide theoretical support for improvement in the food safety level of the pufferfish. Full article

(This article belongs to the Special Issue Recent Advances of Spectrometric and Spectroscopic Techniques in Food Quality and Safety)

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11 pages, 6392 KiB

Open AccessArticle

Dielectric Responses of (Zn_0.33Nb_0.67)_xTi_1−xO₂ Ceramics Prepared by Chemical Combustion Process: DFT and Experimental Approaches

by Theeranuch Nachaithong, Pairot Moontragoon and Prasit Thongbai

Molecules 2022, 27(18), 6121; https://doi.org/10.3390/molecules27186121 - 19 Sep 2022

Cited by 3 | Viewed by 1058

Abstract

The (Zn, Nb)-codoped TiO₂ (called ZNTO) nanopowder was successfully synthesized by a simple combustion process and then the ceramic from it was sintered with a highly dense microstructure. The doped atoms were consistently distributed, and the existence of oxygen vacancies was verified [...] Read more.

The (Zn, Nb)-codoped TiO₂ (called ZNTO) nanopowder was successfully synthesized by a simple combustion process and then the ceramic from it was sintered with a highly dense microstructure. The doped atoms were consistently distributed, and the existence of oxygen vacancies was verified by a Raman spectrum. It was found that the ZNTO ceramic was a result of thermally activated giant dielectric relaxation, and the outer surface layer had a slight effect on the dielectric properties. The theoretical calculation by using the density functional theory (DFT) revealed that the Zn atoms are energy preferable to place close to the oxygen vacancy (Vo) position to create a triangle shape (called the ZnVoTi defect). This defect cluster was also opposite to the diamond shape (called the 2Nb2Ti defect). However, these two types of defects were not correlated together. Therefore, it theoretically confirms that the electron-pinned defect-dipoles (EPDD) cannot be created in the ZNTO structure. Instead, the giant dielectric property of the (Zn_0.33Nb_0.67)_xTi₁_−xO₂ ceramics could be caused by the interfacial polarization combined with electron hopping between the Zn²⁺/Zn³⁺ and Ti³⁺/Ti⁴⁺ ions, rather than due to the EPDD effect. Additionally, it was also proved that the surface barrier-layer capacitor (SBLC) had a slight influence on the giant dielectric properties of the ZNTO ceramics. The annealing process can cause improved dielectric properties, which are properties with a huge advantage to practical applications and devices. Full article

(This article belongs to the Section Physical Chemistry)

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21 pages, 2134 KiB

Open AccessReview

Propolis: Its Role and Efficacy in Human Health and Diseases

by Nadzirah Zullkiflee, Hussein Taha and Anwar Usman

Molecules 2022, 27(18), 6120; https://doi.org/10.3390/molecules27186120 - 19 Sep 2022

Cited by 45 | Viewed by 7168

Abstract

With technological advancements in the medicinal and pharmaceutical industries, numerous research studies have focused on the propolis produced by stingless bees (Meliponini tribe) and Apis mellifera honeybees as alternative complementary medicines for the potential treatment of various acute and chronic diseases. Propolis [...] Read more.

With technological advancements in the medicinal and pharmaceutical industries, numerous research studies have focused on the propolis produced by stingless bees (Meliponini tribe) and Apis mellifera honeybees as alternative complementary medicines for the potential treatment of various acute and chronic diseases. Propolis can be found in tropical and subtropical forests throughout the world. The composition of phytochemical constituents in propolis varies depending on the bee species, geographical location, botanical source, and environmental conditions. Typically, propolis contains lipid, beeswax, essential oils, pollen, and organic components. The latter include flavonoids, phenolic compounds, polyphenols, terpenes, terpenoids, coumarins, steroids, amino acids, and aromatic acids. The biologically active constituents of propolis, which include countless organic compounds such as artepillin C, caffeic acid, caffeic acid phenethyl ester, apigenin, chrysin, galangin, kaempferol, luteolin, genistein, naringin, pinocembrin, coumaric acid, and quercetin, have a broad spectrum of biological and therapeutic properties such as antidiabetic, anti-inflammatory, antioxidant, anticancer, rheumatoid arthritis, chronic obstruct pulmonary disorders, cardiovascular diseases, respiratory tract-related diseases, gastrointestinal disorders, as well as neuroprotective, immunomodulatory, and immuno-inflammatory agents. Therefore, this review aims to provide a summary of recent studies on the role of propolis, its constituents, its biologically active compounds, and their efficacy in the medicinal and pharmaceutical treatment of chronic diseases. Full article

(This article belongs to the Special Issue Propolis in Human and Bee Health)

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19 pages, 6050 KiB

Open AccessArticle

Oxidized Biomass and Its Usage as Adsorbent for Removal of Heavy Metal Ions from Aqueous Solutions

by Bogdan-Constantin Condurache, Corneliu Cojocaru, Petrisor Samoila, Susana Felicia Cosmulescu, Georgeta Predeanu, Andra-Cristina Enache and Valeria Harabagiu

Molecules 2022, 27(18), 6119; https://doi.org/10.3390/molecules27186119 - 19 Sep 2022

Cited by 13 | Viewed by 1397

Abstract

Nowadays, very coarse wool fibers are considered waste biomass and are discarded at random or burned. Therefore, it is of actual interest to valorize coarse wool fibers as utile products. In this sense, we report herein an environmentally-friendly process for the preparation of [...] Read more.

Nowadays, very coarse wool fibers are considered waste biomass and are discarded at random or burned. Therefore, it is of actual interest to valorize coarse wool fibers as utile products. In this sense, we report herein an environmentally-friendly process for the preparation of a new material based on oxidized wool fibers and designed for efficient adsorption of heavy metals from wastewater. The morphology and the structure of the obtained product were characterized by scanning electron microscopy (SEM) coupled with an X-ray energy-dispersive module (EDX) and by Fourier-transform infrared spectroscopy (FTIR). Likewise, the performances of the oxidized wool fibers for the adsorption of heavy metal cations (Cu²⁺, Cd²⁺, Pb²⁺) from aqueous solutions were tested. The adsorption kinetics data were analyzed by applying the pseudo-first-order (PFO) and pseudo-second-order (PSO) kinetic models. The equilibrium of the adsorption process was investigated by using the Freundlich and Langmuir isotherm models. According to the Langmuir isotherms registered at 300 K, the maximum adsorption capacities of the oxidized wool were found to increase from Cu²⁺ (9.41 mg/g) and Cd²⁺ (10.42 mg/g) to Pb²⁺ (30.71 mg/g). Consequently, the removal efficiency of metal ions was found to vary in the range of 96.8–99.7%. The thermodynamic parameters (e.g., enthalpy, entropy, and Gibbs free energy) were calculated and discussed. Full article

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14 pages, 5228 KiB

Open AccessArticle

Induction of the Prenylated Stilbenoids Arachidin-1 and Arachidin-3 and Their Semi-Preparative Separation and Purification from Hairy Root Cultures of Peanut (Arachis hypogaea L.)

by Amit Raj Sharma, Gaurav Gajurel, Izzeldin Ahmed, Krystian Roedel and Fabricio Medina-Bolivar

Molecules 2022, 27(18), 6118; https://doi.org/10.3390/molecules27186118 - 19 Sep 2022

Cited by 6 | Viewed by 1807

Abstract

Prenylated stilbenoids such as arachidin-1 and arachidin-3 are stilbene derivatives that exhibit multiple pharmacological activities. We report an elicitation strategy using different combinations of cyclodextrin, hydrogen peroxide, methyl jasmonate and magnesium chloride to increase arachidin-1 and arachidin-3 production in peanut hairy root cultures. [...] Read more.

Prenylated stilbenoids such as arachidin-1 and arachidin-3 are stilbene derivatives that exhibit multiple pharmacological activities. We report an elicitation strategy using different combinations of cyclodextrin, hydrogen peroxide, methyl jasmonate and magnesium chloride to increase arachidin-1 and arachidin-3 production in peanut hairy root cultures. The treatment of hairy root cultures with cyclodextrin with hydrogen peroxide selectively enhanced arachidin-1 yield (132.6 ± 20.4 mg/L), which was 1.8-fold higher than arachidin-3. Similarly, cyclodextrin combined with methyl jasmonate selectively enhanced arachidin-3 yield (178.2 ± 6.8 mg/L), which was 5.5-fold higher than arachidin-1. Re-elicitation of the hairy root cultures further increased the levels of arachidin-1 and arachidin-3 by 24% and 42%, respectively. The ethyl acetate extract of the culture medium was consecutively fractionated by normal- and reversed-phase column chromatography, followed by semi-preparative HPLC purification on a C18 column to yield arachidin-1 with a recovery rate of 32% and arachidin-3 with a recovery rate of 39%, both at higher than 95% purity. This study provided a sustainable strategy to produce high-purity arachidin-1 and arachidin-3 using hairy root cultures of peanuts combined with column chromatography and semi-preparative HPLC. Full article

(This article belongs to the Section Medicinal Chemistry)

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15 pages, 1825 KiB

Open AccessReview

Targeting Ceramides and Adiponectin Receptors in the Islet of Langerhans for Treating Diabetes

by Wen-hong Li

Molecules 2022, 27(18), 6117; https://doi.org/10.3390/molecules27186117 - 19 Sep 2022

Cited by 3 | Viewed by 2098

Abstract

Ceramides belong to the sphingolipid family and represent the central hub of the sphingolipid network. In obesity, oversupply of saturated fatty acids including palmitate raises ceramide levels which can be detrimental to cells. Elevated ceramides can cause insulin resistance, endoplasmic reticulum stress, and [...] Read more.

Ceramides belong to the sphingolipid family and represent the central hub of the sphingolipid network. In obesity, oversupply of saturated fatty acids including palmitate raises ceramide levels which can be detrimental to cells. Elevated ceramides can cause insulin resistance, endoplasmic reticulum stress, and mitochondrial dysfunction. Studies over the last few decades have highlighted the role played by ceramides in pancreatic islet β-cell apoptosis, especially under glucolipotoxic and inflammatory conditions. This review focuses on ceramides and adiponectin receptor signaling, summarizing recent advancements in our understanding of their roles in islet β-cells and the discovery of zinc-dependent lipid hydrolase (ceramidase) activity of adiponectin receptors. The therapeutic potential of targeting these events to prevent islet β-cell loss for treating diabetes is discussed. Full article

(This article belongs to the Special Issue Lipids–Lipolytic Enzymes–Lipid Analysis: A Themed Issue Dedicated to Prof. Edward A. Dennis for His 80th Birthday)

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28 pages, 5389 KiB

Open AccessReview

Role of Sulfur Compounds in Vegetable and Mushroom Aroma

by Monika A. Marcinkowska and Henryk H. Jeleń

Molecules 2022, 27(18), 6116; https://doi.org/10.3390/molecules27186116 - 19 Sep 2022

Cited by 18 | Viewed by 3492

Abstract

At the base of the food pyramid is vegetables, which should be consumed most often of all food products, especially in raw and unprocessed form. Vegetables and mushrooms are rich sources of bioactive compounds that can fulfill various functions in plants, starting from [...] Read more.

At the base of the food pyramid is vegetables, which should be consumed most often of all food products, especially in raw and unprocessed form. Vegetables and mushrooms are rich sources of bioactive compounds that can fulfill various functions in plants, starting from protection against herbivores and being natural insecticides to pro-health functions in human nutrition. Many of these compounds contain sulfur in their structure. From the point of view of food producers, it is extremely important to know that some of them have flavor properties. Volatile sulfur compounds are often potent odorants, and in many vegetables, belonging mainly to Brassicaeae and Allium (Amaryllidaceae), sulfur compounds determine their specific flavor. Interestingly, some of the pathways that form volatile sulfur compounds in vegetables are also found in selected edible mushrooms. The most important odor-active organosulfur compounds can be divided into isothiocyanates, nitriles, epithionitriles, thiols, sulfides, and polysulfides, as well as others, such as sulfur containing carbonyl compounds and esters, R-L-cysteine sulfoxides, and finally heterocyclic sulfur compounds found in shiitake mushrooms or truffles. This review paper summarizes their precursors and biosynthesis, as well as their sensory properties and changes in selected technological processes. Full article

(This article belongs to the Special Issue Volatile Sulfur Compounds in Food Flavours)

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16 pages, 2422 KiB

Open AccessArticle

NMR-Based Metabolomic Analysis of Cardiac Tissues Clarifies Molecular Mechanisms of CVB3-Induced Viral Myocarditis and Dilated Cardiomyopathy

by Qing Kong, Jinping Gu, Ruohan Lu, Caihua Huang, Lili Chen, Weifeng Wu and Donghai Lin

Molecules 2022, 27(18), 6115; https://doi.org/10.3390/molecules27186115 - 19 Sep 2022

Cited by 2 | Viewed by 2260

Abstract

Viral myocarditis (VMC), which is defined as inflammation of the myocardium with consequent myocardial injury, may develop chronic disease eventually leading to dilated cardiomyopathy (DCM). Molecular mechanisms underlying the progression from acute VMC (aVMC), to chronic VMC (cVMC) and finally to DCM, are [...] Read more.

Viral myocarditis (VMC), which is defined as inflammation of the myocardium with consequent myocardial injury, may develop chronic disease eventually leading to dilated cardiomyopathy (DCM). Molecular mechanisms underlying the progression from acute VMC (aVMC), to chronic VMC (cVMC) and finally to DCM, are still unclear. Here, we established mouse models of VMC and DCM with Coxsackievirus B3 infection and conducted NMR-based metabolomic analysis of aqueous metabolites extracted from cardiac tissues of three histologically classified groups including aVMC, cVMC and DCM. We showed that these three pathological groups were metabolically distinct from their normal counterparts and identified three impaired metabolic pathways shared by these pathological groups relative to normal controls, including nicotinate and nicotinamide metabolism; alanine, aspartate and glutamate metabolism; and D-glutamine and D-glutamate metabolism. We also identified two extra impaired metabolic pathways in the aVMC group, including glycine, serine and threonine metabolism; and taurine and hypotaurine metabolism Furthermore, we identified potential cardiac biomarkers for metabolically distinguishing these three pathological stages from normal controls. Our results indicate that the metabolomic analysis of cardiac tissues can provide valuable insights into the molecular mechanisms underlying the progression from acute VMC to DCM. Full article

(This article belongs to the Special Issue NMR-Based Metabolomics and Human Health)

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18 pages, 2122 KiB

Open AccessArticle

Antioxidant, Antibacterial, and Antifungal Activities of the Ethanolic Extract Obtained from Berberis vulgaris Roots and Leaves

by Khaled Meghawry El-Zahar, Mubarak Eid Al-Jamaan, Faisal Rasmi Al-Mutairi, Abdallah Mohamed Al-Hudiab, Mohamed Saleh Al-Einzi and Ahmed Abdel-Zaher Mohamed

Molecules 2022, 27(18), 6114; https://doi.org/10.3390/molecules27186114 - 19 Sep 2022

Cited by 14 | Viewed by 3559

Abstract

This work assessed the phenolic and flavonoid components and their antioxidant, antifungal, and antibacterial effects in the ethanolic extract of barberry leaf and roots. The antibactericidal activity of root and leaf extracts against pathogenic bacteria was tested using agar diffusion and microdilution broth [...] Read more.

This work assessed the phenolic and flavonoid components and their antioxidant, antifungal, and antibacterial effects in the ethanolic extract of barberry leaf and roots. The antibactericidal activity of root and leaf extracts against pathogenic bacteria was tested using agar diffusion and microdilution broth production for the lowest inhibitory concentration (MIC). Berberis vulgaris root and leaf extracts inhibited Staphylococcus aureus ATCC9973, Escherichia coli HB101, Staphylococcus enteritis, and Escherichia coli Cip812. The disc assay technique was used to assess the bactericidal activity of the extracts versus both pathogenic Gram-positive and Gram-negative strains. Hydro alcoholic extract was more effective against bacterial than fungal strains. The results showed that Berberis vulgaris leaf and roots extract had similar antifungal activities. Berberis vulgaris root extract inhibited the mycelial growth of Penicillium verrucosum, Fusarium proliferatum, Aspergillus ochraceous, Aspergillus niger, and Aspergillus flavus. Berberis vulgaris root extract has excellent antioxidant, antibacterial, and antifungal effects. Berberis vulgaris exhibited antimicrobial activity in vitro, and MIC showed that Berberis vulgaris parts efficiently affected pathogens in vitro. In conclusion, both Berberis vulgaris roots and leaves have considerable antibacterial activity and can be used as a source of antibacterial, antioxidant, and bioactive compounds to benefit human health. Full article

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8 pages, 1854 KiB

Open AccessArticle

Introducing Polar Groups in Porous Aromatic Framework for Achieving High Capacity of Organic Molecules and Enhanced Self-Cleaning Applications

by Zhuojun Yan, Yimin Qiao, Qiqi Sun, Bo Cui, Bin Feng, Naishun Bu, Kuo Chu, Xianghui Ruan, Ye Yuan, Yajie Yang and Lixin Xia

Molecules 2022, 27(18), 6113; https://doi.org/10.3390/molecules27186113 - 19 Sep 2022

Cited by 1 | Viewed by 1453

Abstract

Due to the frequent oil/organic solvent leakage, efficient oil/water separation has attracted extensive concern. However, conventional porous materials possess nonpolar building units, which reveal relatively weak affinity for polar organic molecules. Here, two different polarities of superhydrophobic porous aromatic frameworks (PAFs) were synthesized [...] Read more.

Due to the frequent oil/organic solvent leakage, efficient oil/water separation has attracted extensive concern. However, conventional porous materials possess nonpolar building units, which reveal relatively weak affinity for polar organic molecules. Here, two different polarities of superhydrophobic porous aromatic frameworks (PAFs) were synthesized with respective orthoposition and paraposition C=O groups in the PAF linkers. The conjugated structure formed by a large number of alkynyl and benzene ring structures enabled porous and superhydrophobic quality of PAFs. After the successful preparation of the PAF solids, PAF powders were coated on polyester fabrics by a simple dip-coating method, which endowed the resulting polyester fabrics with superhydrophobicity, porosity, and excellent stability. Based on the unique structure, the oil/water separation efficiency of two superhydrophobic flexible fabrics was more than 90% for various organic solvents. Polar LNU-26 PAF showed better separation performance for the polar oils. This work takes the lead in adopting the polar groups as building units for the preparation of porous networks, which has great guiding significance for the construction of advanced oil/water separation materials. Full article

(This article belongs to the Special Issue Potential Applications of Functional Porous Organic Frameworks)

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12 pages, 1181 KiB

Open AccessArticle

Ultrasound-Assisted Dispersive Liquid-Liquid Microextraction Using Deep Eutectic Solvents (DESs) for Neutral Red Dye Spectrophotometric Determination

by Sana Ullah, Hameed Ul Haq, Muhammad Salman, Faheem Jan, Faisal Safi, Muhammad Balal Arain, Muhammad Shahzeb Khan, Roberto Castro-Muñoz and Grzegorz Boczkaj

Molecules 2022, 27(18), 6112; https://doi.org/10.3390/molecules27186112 - 19 Sep 2022

Cited by 7 | Viewed by 2005

Abstract

Deep eutectic solvents (DES), which have low toxicity and are low cost, biodegradable, and easily synthesized, were used for the extraction of neutral red (NR) dye before its spectrophotometric analysis. DES, containing choline chloride as a hydrogen bond acceptor and phenol as a [...] Read more.

Deep eutectic solvents (DES), which have low toxicity and are low cost, biodegradable, and easily synthesized, were used for the extraction of neutral red (NR) dye before its spectrophotometric analysis. DES, containing choline chloride as a hydrogen bond acceptor and phenol as a hydrogen bond donor with a molar ratio of 1:2, was used for the extraction of NR dye from aqueous media. The possible interaction of different DESs with NR was studied using density functional theory (DFT) calculations. Experimentally, a UV-visible spectrophotometer was used for the quantitative analysis. The most important parameters affecting method performance, such as pH, extraction temperature, DES type, its volume, THF volume, sonication time, and centrifugation time, were optimized. The developed method provides exceptional sensitivity in terms of LOD and LOQ, which were 2.2 and 7.3 µg/L respectively. The relative standard deviation was 1.35–1.5% (n = 10), and the pre-concentration factor was 40. The method was found to be linear in the range of 2–300 µg/L (R2 = 0.9967). The method was successfully used for the determination of NR in wastewater samples. Finally, the DES-based method presents operational simplicity, high sensitivity, and rapid determination (<5 min) compared with other analytical procedures. Full article

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

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20 pages, 1763 KiB

Open AccessArticle

Coordination Sites for Sodium and Potassium Ions in Nucleophilic Adeninate Contact ion-Pairs: A Molecular-Wide and Electron Density-Based (MOWED) Perspective

by Dominique M. S. Buyens, Lynne A. Pilcher and Ignacy Cukrowski

Molecules 2022, 27(18), 6111; https://doi.org/10.3390/molecules27186111 - 19 Sep 2022

Viewed by 1706

Abstract

The adeninate anion (Ade⁻) is a useful nucleophile used in the synthesis of many prodrugs (including those for HIV AIDS treatment). It exists as a contact ion-pair (CIP) with Na⁺ and K⁺ (M⁺) but the site of [...] Read more.

The adeninate anion (Ade⁻) is a useful nucleophile used in the synthesis of many prodrugs (including those for HIV AIDS treatment). It exists as a contact ion-pair (CIP) with Na⁺ and K⁺ (M⁺) but the site of coordination is not obvious from spectroscopic data. Herein, a molecular-wide and electron density-based (MOWED) computational approach implemented in the implicit solvation model showed a strong preference for bidentate ion coordination at the N3 and N9 atoms. The N3N9-CIP has (i) the strongest inter-ionic interaction, by −30 kcal mol⁻¹, with a significant (10–15%) covalent contribution, (ii) the most stabilized bonding framework for Ade⁻, and (iii) displays the largest ion-induced polarization of Ade⁻, rendering the N3 and N9 the most negative and, hence, most nucleophilic atoms. Alkylation of the adeninate anion at these two positions can therefore be readily explained when the metal coordinated complex is considered as the nucleophile. The addition of explicit DMSO solvent molecules did not change the trend in most nucleophilic N-atoms of Ade⁻ for the in-plane M-Ade complexes in M-Ade-(DMSO)₄ molecular systems. MOWED-based studies of the strength and nature of interactions between DMSO solvent molecules and counter ions and Ade⁻ revealed an interesting and unexpected chemistry of intermolecular chemical bonding. Full article

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

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14 pages, 1404 KiB

Open AccessArticle

Influence of the Degree of Hydrolysis on Functional Properties and Antioxidant Activity of Enzymatic Soybean Protein Hydrolysates

by Monirul Islam, Yatao Huang, Serajul Islam, Bei Fan, Litao Tong and Fengzhong Wang

Molecules 2022, 27(18), 6110; https://doi.org/10.3390/molecules27186110 - 19 Sep 2022

Cited by 20 | Viewed by 3260

Abstract

Soybean protein hydrolysates were prepared using two proteolytic enzymes (Alcalase and Protamex) and the degree of hydrolysis (DH) and their functional and antioxidant properties were evaluated. The highest DH value was 20%, with a yield of 19.77% and protein content of 51.64%. The [...] Read more.

Soybean protein hydrolysates were prepared using two proteolytic enzymes (Alcalase and Protamex) and the degree of hydrolysis (DH) and their functional and antioxidant properties were evaluated. The highest DH value was 20%, with a yield of 19.77% and protein content of 51.64%. The total amino acid content was more than 41% for all protein hydrolysates. The protein hydrolysates from Protamex at pH 2.0 had excellent solubility, emulsifying activity, and foaming capacity, at 83.83%, 95.03 m²/g, and 93.84%, respectively. The water-holding capacity was 4.52 g/g for Alcalase, and the oil-holding capacity was 4.91 g/g for Protamex. The antioxidant activity (62.07%), as measured by the samples’ reaction with DPPH (2,2-diphenyl-1-picrylhydrazyl) and the reducing power (0.27) were the strongest for Protamex. An ABTS activity rate of 70.21% was recorded for Alcalase. These findings indicated a strong potential for the utilization of soybean protein hydrolysates to improve the functional properties and antioxidant activity of soybeans as well as their nutritional values. Full article

(This article belongs to the Special Issue Extraction, Modification, Functionality and Bioactivity of Plant Proteins for a Healthy and Sustainable Food System)

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21 pages, 5612 KiB

Open AccessArticle

Zika Virus Inhibitors Based on a 1,3-Disubstituted 1H-Pyrazolo[3,4-d]pyrimidine-amine Scaffold

by Eunkyung Jung, Ruben Soto-Acosta, Robert J. Geraghty and Liqiang Chen

Molecules 2022, 27(18), 6109; https://doi.org/10.3390/molecules27186109 - 19 Sep 2022

Cited by 3 | Viewed by 1371

Abstract

To search for Zika virus (ZIKV) antivirals, we have further explored previously reported 7H-pyrrolo[2,3-d]pyrimidines by examining an alternative substitution pattern of their central scaffold, leading to compound 5 with low micromolar antiviral activity. To circumvent the synthetic difficulties associated [...] Read more.

To search for Zika virus (ZIKV) antivirals, we have further explored previously reported 7H-pyrrolo[2,3-d]pyrimidines by examining an alternative substitution pattern of their central scaffold, leading to compound 5 with low micromolar antiviral activity. To circumvent the synthetic difficulties associated with compound 5, we have exploited a 1H-pyrazolo[3,4-d]pyrimidine scaffold and performed structure-activity relationship studies on its peripheral rings A and B. While ring B is less sensitive to structural modifications, an electron-withdrawing group at the para position of ring A is preferred for enhanced antiviral activity. Overall, we have not only discovered an alternative substitution pattern centered on a 1H-pyrazolo[3,4-d]pyrimidine scaffold but also generated anti-ZIKV compounds including 6 and 13, which possess low micromolar antiviral activity and relatively low cytotoxicity. These compounds represent new chemotypes that will be further optimized in our continued efforts to discover anti-ZIKV agents. Full article

(This article belongs to the Special Issue Recent Advances in Antiviral Drugs Discovery)

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12 pages, 2239 KiB

Open AccessArticle

Identification of Novel Natural Inhibitors to Human 3-Phosphoglycerate Dehydrogenase (PHGDH) for Cancer Treatment

by Ayesha Sadiqa, Azhar Rasul, Mudassir Hassan, Salma Sultana and Farhat Jabeen

Molecules 2022, 27(18), 6108; https://doi.org/10.3390/molecules27186108 - 19 Sep 2022

Cited by 3 | Viewed by 1980

Abstract

Targeting the serine biosynthesis pathway enzymes has turned up as a novel strategy for anti-cancer therapeutics. 3- Phosphoglycerate dehydrogenase (PHGDH) is the rate-limiting enzyme that catalyzes the conversion of 3-Phosphoglyceric acid (3-PG) into 3-Phosphohydroxy pyruvate (3-PPyr) in the first step of serine synthesis [...] Read more.

Targeting the serine biosynthesis pathway enzymes has turned up as a novel strategy for anti-cancer therapeutics. 3- Phosphoglycerate dehydrogenase (PHGDH) is the rate-limiting enzyme that catalyzes the conversion of 3-Phosphoglyceric acid (3-PG) into 3-Phosphohydroxy pyruvate (3-PPyr) in the first step of serine synthesis pathway and perform a critical role in cancer progression. PHGDH has been reported to be overexpressed in different types of cancers and emerged as a novel target for cancer therapeutics. During this study, virtual screening tools were used for the identification of inhibitors of PHGDH. A library of phenolic compounds was docked against two binding sites of PHGDH using Molegro Virtual Docker (MVD) software. Out of 169 virtually tested compounds, Salvianolic acid C and Schizotenuin F possess good binding potential to co-factor binding site of PHGDH while Salvianolic acid I and Chicoric acid were identified as the best binding compounds toward the substrate binding site of PHGDH. The top selected compounds were evaluated for different physiochemical and ADMET properties, the obtained results showed that none of these hit compounds violated the Pfizer Rule and they possess acceptable ADMET profiles. Further, a commercially available hit compound, Chicoric acid, was evaluated for its anti-cancer potential against PHGDH-expressing gastric cancer cell lines (MGC-803 and SGC-7901) as well as cell lines with low expression of PHGDH (MCF-7 and MDA-MB2-31), which demonstrated that Chicoric acid possesses selective cytotoxicity toward PHGDH expressing cancer cell lines. Thus, this study has unveiled the potential of phenolic compounds, which could serve as novel candidates for the development of PHGDH inhibitors as anti-cancer agents. Full article

(This article belongs to the Special Issue Bioactive Compounds from Natural Sources II)

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