Molecules

12 pages, 1845 KiB

Open AccessArticle

Method of Glyphosate, AMPA, and Glufosinate Ammonium Determination in Beebread by Liquid Chromatography—Tandem Mass Spectrometry after Molecularly Imprinted Solid-Phase Extraction

by Marta Małysiak and Tomasz Kiljanek

Molecules 2022, 27(17), 5741; https://doi.org/10.3390/molecules27175741 - 5 Sep 2022

Cited by 6 | Viewed by 3762

Abstract

The aim of this study was to develop a method for the determination of glyphosate, its metabolite aminomethylphosphonic acid (AMPA), and glufosinate ammonium residues in beebread samples, which could then be used to assess bees’ exposure to their residues. The complexity of beebread’s [...] Read more.

The aim of this study was to develop a method for the determination of glyphosate, its metabolite aminomethylphosphonic acid (AMPA), and glufosinate ammonium residues in beebread samples, which could then be used to assess bees’ exposure to their residues. The complexity of beebread’s matrix, combined with the specific properties of glyphosate itself, required careful selection and optimization of each analysis step. The use of molecularly imprinted solid-phase extraction (MIP-SPE) by AFFINIMIP glyphosate as an initial clean-up step significantly eliminated matrix components and ensured an efficient derivatization step. Colorless beebread extracts were derivatized by the addition of 9-fluorenylmethyl chloroformate (FMOC-Cl). After derivatization, in order to remove FMOC-OH and residual borate buffer, a solid-phase extraction (SPE) clean-up step using Oasis HLB was carried out. Instrumental analysis was performed by liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS). The method was validated according to the SANTE/11312/2021 guideline at concentrations of 5, 10, and 100 µg/kg, and satisfactory recovery (trueness) values (76–111%) and precision (RSDr) ≤ 18% were obtained. The limit of quantification (LOQ) was 5 µg/kg for AMPA and glufosinate ammonium and 10 µg/kg for glyphosate. The method was positively verified by the international proficiency test. Analysis of beebread samples showed the method’s usefulness in practice. The developed method could be a reliable tool for the assessment of beebread’s contamination with residues of glyphosate, its metabolite AMPA, and glufosinate ammonium. Full article

(This article belongs to the Special Issue Analysis of Residues in Environmental Samples)

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22 pages, 13598 KiB

Open AccessArticle

Determination and Removal of Selected Pharmaceuticals and Total Organic Carbon from Surface Water by Aluminum Chlorohydrate Coagulant

by Joanna Kuc, Maciej Thomas, Iwona Grochowalska, Rafał Kulczyk, Gabriela Mikosz, Fabian Mrózek, Dagmara Janik, Justyna Korta and Karolina Cwynar

Molecules 2022, 27(17), 5740; https://doi.org/10.3390/molecules27175740 - 5 Sep 2022

Cited by 8 | Viewed by 2502

Abstract

In the present research, the removal of Total Organic Carbon (TOC) and erythromycin (ERY), fluoxetine (FLX), amoxicillin (AMO), colistin (COL), ethynylestradiol (EE), and diclofenac (DIC) from surface water by coagulation is studied. The concentration of selected pharmaceuticals in 24 surface water samples originating [...] Read more.

In the present research, the removal of Total Organic Carbon (TOC) and erythromycin (ERY), fluoxetine (FLX), amoxicillin (AMO), colistin (COL), ethynylestradiol (EE), and diclofenac (DIC) from surface water by coagulation is studied. The concentration of selected pharmaceuticals in 24 surface water samples originating from some rivers located in Lesser Poland Voivodeship and Silesia Voivodeship, Poland, was determined. The removal of TOC and pharmaceuticals was carried out using the application of Design of Experiments (DOE), Response Surface Methodology (RSM), and by addition of aluminum chlorohydrate (ACH) as a coagulant. The study found that the concentration ranges of ERY, FLX, AMO, COL, EE, and DIC in analyzed water samples were 7.58–412.32, 1.21–72.52, 1.22–68.55, 1.28–32.01, 5.36–45.56, 2.20–182.22 ng/L, respectively. In some cases, concentrations lower than 1 ng/L were determined. In optimal conditions of coagulation process of spiked surface water (pH = 6.5 ± 0.1, ACH dose = 0.35 mL/L, Time = 30 min; R² = 0.8799, R²_adj = 0.7998), the concentration of TOC, ERY, FLX, AMO, COL, EE, and DIC was decreased by 88.7, 36.4, 24.7, 29.0, 25.5, 35.4, 30.4%, respectively. Simultaneously, turbidity, color, Total Suspended Solids (TSS), Chemical Oxygen Demand (COD), Total Nitrogen (Total N), and Ammonium-Nitrogen (N-NH₄) were decreased by 96.2%, >98.0%, 97.8%, 70.0%, 88.7%, 37.5%, respectively. These findings suggest that ACH may be an optional reagent to remove studied pharmaceuticals from contaminated water. Full article

(This article belongs to the Special Issue Removal of Pharmaceuticals from Contaminated Water, Wastewater and Sediments)

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10 pages, 3368 KiB

Open AccessArticle

Sequential Processing Enables 17% All-Polymer Solar Cells via Non-Halogen Organic Solvent

by Chaoyue Zhao, Lihong Wang, Guoping Zhang, Yajie Wang, Ruiyu Hu, Hui Huang, Mingxia Qiu, Shunpu Li and Guangye Zhang

Molecules 2022, 27(17), 5739; https://doi.org/10.3390/molecules27175739 - 5 Sep 2022

Cited by 4 | Viewed by 11786

Abstract

All-polymer solar cells (All-PSCs), whose electron donor and acceptors are both polymeric materials, have attracted great research attention in the past few years. However, most all-PSC devices with top-of-the-line efficiencies are processed from chloroform. In this work, we apply the sequential processing (SqP) [...] Read more.

All-polymer solar cells (All-PSCs), whose electron donor and acceptors are both polymeric materials, have attracted great research attention in the past few years. However, most all-PSC devices with top-of-the-line efficiencies are processed from chloroform. In this work, we apply the sequential processing (SqP) method to fabricate All-PSCs from an aromatic hydrocarbon solvent, toluene, and obtain efficiencies up to 17.0%. By conducting a series of characterizations on our films and devices, we demonstrate that the preparation of SqP devices using toluene can effectively reduce carrier recombination, enhance carrier mobility and promote the fill factor of the device. Full article

(This article belongs to the Special Issue Molecular Semiconductors for Organic and Perovskite Solar Cells)

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19 pages, 11165 KiB

Open AccessFeature PaperReview

Electrospun Polymer Materials with Fungicidal Activity: A Review

by Nasko Nachev, Mariya Spasova, Nevena Manolova, Iliya Rashkov and Mladen Naydenov

Molecules 2022, 27(17), 5738; https://doi.org/10.3390/molecules27175738 - 5 Sep 2022

Cited by 5 | Viewed by 2350

Abstract

In recent years, there has been special interest in innovative technologies such as polymer melt or solution electrospinning, electrospraying, centrifugal electrospinning, coaxial electrospinning, and others. Applying these electrokinetic methods, micro- or nanofibrous materials with high specific surface area, high porosity, and various designs [...] Read more.

In recent years, there has been special interest in innovative technologies such as polymer melt or solution electrospinning, electrospraying, centrifugal electrospinning, coaxial electrospinning, and others. Applying these electrokinetic methods, micro- or nanofibrous materials with high specific surface area, high porosity, and various designs for diverse applications could be created. By using these techniques it is possible to obtain fibrous materials from both synthetic and natural biocompatible and biodegradable polymers, harmless to the environment. Incorporation of low-molecular substances with biological activity (e.g., antimicrobial, antifungal) is easily feasible. Moreover, biocontrol agents, able to suppress the development and growth of plant pathogens, have been embedded in the fibrous materials as well. The application of such nanotechnologies for the creation of plant protection products is an extremely promising new direction. This review emphasizes the recent progress in the development of electrospun fungicidal dressings and their potential to be applied in modern agriculture. Full article

(This article belongs to the Special Issue Exclusive Review Papers in Green Chemistry)

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11 pages, 1441 KiB

Open AccessArticle

Simultaneous Determination of Seven Pesticides and Metabolite Residues in Litchi and Longan through High-Performance Liquid Chromatography-Tandem Mass Spectrometry with Modified QuEChERS

by Siwei Wang, Xiaonan Wang, Qiang He, Haidan Lin, Hong Chang, Haibin Sun and Yanping Liu

Molecules 2022, 27(17), 5737; https://doi.org/10.3390/molecules27175737 - 5 Sep 2022

Cited by 11 | Viewed by 2359

Abstract

This study established a QuEChERS high-performance liquid chromatography/tandem triple-quadrupole mass spectrometry method for determining azoxystrobin, pyraclostrobin, picoxystrobin, difenoconazole, chlorantraniliprole, imidacloprid, and cyantraniliprole and its metabolite (IN-J9Z38) in litchi and longan, and applied this method to the real samples. The residues in samples were [...] Read more.

This study established a QuEChERS high-performance liquid chromatography/tandem triple-quadrupole mass spectrometry method for determining azoxystrobin, pyraclostrobin, picoxystrobin, difenoconazole, chlorantraniliprole, imidacloprid, and cyantraniliprole and its metabolite (IN-J9Z38) in litchi and longan, and applied this method to the real samples. The residues in samples were extracted with acetonitrile and purified with nano-ZrO₂, C₁₈, and PSA. The samples were then detected with multireactive ion monitoring and electrospray ionization in the positive ion mode and quantified using the external matrix-matched standard method. The results showed good linearities for the eight analytes in the range of 1–100 μg/L, with correlation coefficients (r²) of >0.99. The limit of quantification was 1–10 μg/kg, and the limit of detection was 0.3–3 μg/kg. Average recovery from litchi and longan was 81–99%, with the relative standard deviation of 3.5–8.4% at fortified concentrations of 1, 10, and 100 μg/kg. The developed method is simple, rapid, efficient, and sensitive. It allowed the rapid screening, monitoring, and confirming of the aforementioned seven pesticides and a metabolite in litchi and longan. Full article

(This article belongs to the Special Issue Food Analysis in the 21st Century: Challenges and Possibilities)

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10 pages, 2545 KiB

Open AccessArticle

Design of Pd–Zn Bimetal MOF Nanosheets and MOF-Derived Pd_3.9Zn_6.1/CNS Catalyst for Selective Hydrogenation of Acetylene under Simulated Front-End Conditions

by Xinxiang Cao, Ruijian Tong, Siye Tang, Ben W. -L. Jang, Arash Mirjalili, Jiayi Li, Xining Guo, Jingyi Zhang, Jiaxue Hu and Xin Meng

Molecules 2022, 27(17), 5736; https://doi.org/10.3390/molecules27175736 - 5 Sep 2022

Cited by 5 | Viewed by 2567

Abstract

Novel zinc–palladium–porphyrin bimetal metal–organic framework (MOF) nanosheets were directly synthesized by coordination chelation between Zn(II) and Pd(II) tetra(4-carboxyphenyl)porphin (TCPP(Pd)) using a solvothermal method. Furthermore, a serial of carbon nanosheets supported Pd–Zn intermetallics (Pd–Zn-ins/CNS) with different Pd: Zn atomic ratios were obtained by one-step [...] Read more.

Novel zinc–palladium–porphyrin bimetal metal–organic framework (MOF) nanosheets were directly synthesized by coordination chelation between Zn(II) and Pd(II) tetra(4-carboxyphenyl)porphin (TCPP(Pd)) using a solvothermal method. Furthermore, a serial of carbon nanosheets supported Pd–Zn intermetallics (Pd–Zn-ins/CNS) with different Pd: Zn atomic ratios were obtained by one-step carbonization under different temperature using the prepared Zn-TCPP(Pd) MOF nanosheets as precursor. In the carbonization process, Pd–Zn-ins went through the transformation from PdZn (650 °C) to Pd_3.9Zn_6.1 (~950 °C) then to Pd_3.9Zn_6.1/Pd (1000 °C) with the temperature increasing. The synthesized Pd–Zn-ins/CNS were further employed as catalysts for selective hydrogenation of acetylene. Pd_3.9Zn_6.1 showed the best catalytic performance compared with other Pd–Zn intermetallic forms. Full article

(This article belongs to the Special Issue Emerging Catalytic, Energetic, and Inorganic Nonmetallic Materials)

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14 pages, 21136 KiB

Open AccessArticle

Extract of Acanthopanax senticosus and Its Components Interacting with Sulfide, Cysteine and Glutathione Increase Their Antioxidant Potencies and Inhibit Polysulfide-Induced Cleavage of Plasmid DNA

by Anton Misak, Marian Grman, Lenka Tomasova, Ondrej Makara, Miroslav Chovanec and Karol Ondrias

Molecules 2022, 27(17), 5735; https://doi.org/10.3390/molecules27175735 - 5 Sep 2022

Cited by 1 | Viewed by 1747

Abstract

Aqueous root extract from Acanthopanax senticosus (ASRE) has a wide range of medicinal effects. The present work was aimed at studying the influence of sulfide, cysteine and glutathione on the antioxidant properties of ASRE and some of its selected phytochemical components. Reduction of [...] Read more.

Aqueous root extract from Acanthopanax senticosus (ASRE) has a wide range of medicinal effects. The present work was aimed at studying the influence of sulfide, cysteine and glutathione on the antioxidant properties of ASRE and some of its selected phytochemical components. Reduction of the 2-(4-carboxyphenyl)-4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazol-1-yloxy-3-oxide (^●cPTIO) stable radical and plasmid DNA (pDNA) cleavage in vitro assays were used to evaluate antioxidant and DNA-damaging properties of ASRE and its individual components. We found that the interaction of ASRE and its two components, caffeic acid and chlorogenic acid (but not protocatechuic acid and eleutheroside B or E), with H₂S/HS⁻, cysteine or glutathione significantly increased the reduction of the ^●cPTIO radical. In contrast, the potency of ASRE and its selected components was not affected by Na₂S₄, oxidized glutathione, cystine or methionine, indicating that the thiol group is a prerequisite for the promotion of the antioxidant effects. ASRE interacting with H₂S/HS⁻ or cysteine displayed a bell-shaped effect in the pDNA cleavage assay. However, ASRE and its components inhibited pDNA cleavage induced by polysulfides. In conclusion, we suggest that cysteine, glutathione and H₂S/HS⁻ increase antioxidant properties of ASRE and that changes of their concentrations and the thiol/disulfide ratio can influence the resulting biological effects of ASRE. Full article

(This article belongs to the Special Issue Bioactive Compounds and Antioxidant Activity of Extracts from Different Natural Plants)

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16 pages, 27982 KiB

Open AccessArticle

Integrating Pharmacological and Computational Approaches for the Phytochemical Analysis of Syzygium cumini and Its Anti-Diabetic Potential

by Fatima Rashid, Anam Javaid, Mahmood-ur-Rahman, Usman Ali Ashfaq, Muhammad Sufyan, Abdulrahman Alshammari, Metab Alharbi, Muhammad Atif Nisar and Mohsin Khurshid

Molecules 2022, 27(17), 5734; https://doi.org/10.3390/molecules27175734 - 5 Sep 2022

Cited by 12 | Viewed by 2559

Abstract

Diabetes mellitus (DM) is a metabolic disease caused by improper insulin secretion leading to hyperglycemia. Syzygium cumini has excellent therapeutic properties due to its high levels of phytochemicals. The current research aimed to evaluate the anti-diabetic potential of S. cumini plant’s seeds and [...] Read more.

Diabetes mellitus (DM) is a metabolic disease caused by improper insulin secretion leading to hyperglycemia. Syzygium cumini has excellent therapeutic properties due to its high levels of phytochemicals. The current research aimed to evaluate the anti-diabetic potential of S. cumini plant’s seeds and the top two phytochemicals (kaempferol and gallic acid) were selected for further analysis. These phytochemicals were selected via computational tools and evaluated for α-Glucosidase inhibitory activity via enzymatic assay. Gallic acid (IC₅₀ 0.37 µM) and kaempferol (IC₅₀ 0.87 µM) have shown a stronger α-glucosidase inhibitory capacity than acarbose (5.26 µM). In addition, these phytochemicals demonstrated the highest binding energy, hydrogen bonding, protein–ligand interaction and the best MD simulation results at 100 ns compared to acarbose. Furthermore, the ADMET properties of gallic acid and kaempferol also fulfilled the safety criteria. Thus, it was concluded that S. cumini could potentially be used to treat DM. The potential bioactive molecules identified in this study (kaempferol and gallic acid) may be used as lead drugs against diabetes. Full article

(This article belongs to the Section Natural Products Chemistry)

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16 pages, 5100 KiB

Open AccessArticle

Synthesis of Cyano-Benzylidene Xanthene Synthons Using a Diprotic Brønsted Acid Catalyst, and Their Application as Efficient Inhibitors of Aluminum Corrosion in Alkaline Solutions

by Mohammed A. Amin, Gaber A. M. Mersal, Morad M. El-Hendawy, Abdallah A. Shaltout, Ali Badawi, Johan Boman, Adil A. Gobouri, Murat Saracoglu, Fatma Kandemirli, Rabah Boukherroub, Jacek Ryl and Mohamed E. Khalifa

Molecules 2022, 27(17), 5733; https://doi.org/10.3390/molecules27175733 - 5 Sep 2022

Cited by 4 | Viewed by 2210

Abstract

Novel cyano-benzylidene xanthene derivatives were synthesized using one-pot and condensation reactions. A diprotic Brønsted acid (i.e., oxalic acid) was used as an effective catalyst for the promotion of the synthesis process of the new starting xanthene–aldehyde compound. Different xanthene concentrations (ca. 0.1–2.0 mM) [...] Read more.

Novel cyano-benzylidene xanthene derivatives were synthesized using one-pot and condensation reactions. A diprotic Brønsted acid (i.e., oxalic acid) was used as an effective catalyst for the promotion of the synthesis process of the new starting xanthene–aldehyde compound. Different xanthene concentrations (ca. 0.1–2.0 mM) were applied as corrosion inhibitors to control the alkaline uniform corrosion of aluminum. Measurements were conducted in 1.0 M NaOH solution using Tafel extrapolation and linear polarization resistance (LPR) methods. The investigated xanthenes acted as mixed-type inhibitors that primarily affect the anodic process. Their inhibition efficiency values were enhanced with inhibitor concentration, and varied according to their chemical structures. At a concentration of 2.0 mM, the best-performing studied xanthene derivative recorded maximum inhibition efficiency values of 98.9% (calculated via the Tafel extrapolation method) and 98.4% (estimated via the LPR method). Scanning electron microscopy (SEM) was used to examine the morphology of the corroded and inhibited aluminum surfaces, revealing strong inhibitory action of each studied compound. High-resolution X-ray photoelectron spectroscopy (XPS) profiles validated the inhibitor compounds’ adsorption on the Al surface. Density functional theory (DFT) and Monte Carlo simulations were applied to investigate the distinction of the anticorrosive behavior among the studied xanthenes toward the Al (111) surface. The non-planarity of xanthenes and the presence of the nitrile group were the key players in the adsorption process. A match between the experimental and theoretical findings was evidenced. Full article

(This article belongs to the Special Issue Chemistry of Corrosion Inhibitors)

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22 pages, 1300 KiB

Open AccessArticle

New Chemicals Suppressing SARS-CoV-2 Replication in Cell Culture

by Alexey Sulimov, Ivan Ilin, Danil Kutov, Khidmet Shikhaliev, Dmitriy Shcherbakov, Oleg Pyankov, Nadezhda Stolpovskaya, Svetlana Medvedeva and Vladimir Sulimov

Molecules 2022, 27(17), 5732; https://doi.org/10.3390/molecules27175732 - 5 Sep 2022

Cited by 6 | Viewed by 2402

Abstract

Candidates to being inhibitors of the main protease (M

^{p r o}

) of SARS-CoV-2 were selected from the database of Voronezh State University using molecular modeling. The database contained approximately 19,000 compounds represented by more than 41,000 ligand conformers. These ligands were [...] Read more.

Candidates to being inhibitors of the main protease (M

^{p r o}

) of SARS-CoV-2 were selected from the database of Voronezh State University using molecular modeling. The database contained approximately 19,000 compounds represented by more than 41,000 ligand conformers. These ligands were docked into M

^{p r o}

using the SOL docking program. For one thousand ligands with best values of the SOL score, the protein–ligand binding enthalpy was calculated by the PM7 quantum-chemical method with the COSMO solvent model. Using the SOL score and the calculated protein–ligand binding enthalpies, eighteen compounds were selected for the experiments. Several of these inhibitors suppressed the replication of the coronavirus in cell culture, and we used the best three among them in the search for chemical analogs. Selection among analogs using the same procedure followed by experiments led to identification of seven inhibitors of the SARS-CoV-2 replication in cell culture with EC

_{50}

values at the micromolar level. The identified inhibitors belong to three chemical classes. The three inhibitors, 4,4-dimethyldithioquinoline derivatives, inhibit SARS-CoV-2 replication in Vero E6 cell culture just as effectively as the best published non-covalent inhibitors, and show low cytotoxicity. These results open up a possibility to develop antiviral drugs against the SARS-CoV-2 coronavirus. Full article

(This article belongs to the Special Issue Recent Trends on Enzymes Inhibitors and Activators in Drug Research 3.0)

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13 pages, 2151 KiB

Open AccessArticle

A Supramolecular Approach to Antimicrobial Surfaces

by Valentina Gazzola, Pietro Grisoli, Valeria Amendola, Giacomo Dacarro, Carlo Mangano, Piersandro Pallavicini, Antonio Poggi, Silvia Rossi, Barbara Vigani and Angelo Taglietti

Molecules 2022, 27(17), 5731; https://doi.org/10.3390/molecules27175731 - 5 Sep 2022

Viewed by 1908

Abstract

In this paper, we report on the preparation of Imidazole-functionalized glass surfaces, demonstrating the ability of a dinuclear Cu(II) complex of a macrocyclic ligand to give a “cascade” interaction with the deprotonated forms of grafted imidazole moieties. In this way, we realized a [...] Read more.

In this paper, we report on the preparation of Imidazole-functionalized glass surfaces, demonstrating the ability of a dinuclear Cu(II) complex of a macrocyclic ligand to give a “cascade” interaction with the deprotonated forms of grafted imidazole moieties. In this way, we realized a prototypal example of an antimicrobial surface based on a supramolecular approach, obtaining a neat microbicidal effect using low amounts of the described copper complex. Full article

(This article belongs to the Special Issue Metal Ions in Supramolecular Chemistry: A Themed Issue in Honor of Professor Luigi Fabbrizzi)

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33 pages, 1408 KiB

Open AccessFeature PaperReview

Prostate Cancer Review: Genetics, Diagnosis, Treatment Options, and Alternative Approaches

by Mamello Sekhoacha, Keamogetswe Riet, Paballo Motloung, Lemohang Gumenku, Ayodeji Adegoke and Samson Mashele

Molecules 2022, 27(17), 5730; https://doi.org/10.3390/molecules27175730 - 5 Sep 2022

Cited by 259 | Viewed by 36293

Abstract

Prostate cancer is one of the malignancies that affects men and significantly contributes to increased mortality rates in men globally. Patients affected with prostate cancer present with either a localized or advanced disease. In this review, we aim to provide a holistic overview [...] Read more.

Prostate cancer is one of the malignancies that affects men and significantly contributes to increased mortality rates in men globally. Patients affected with prostate cancer present with either a localized or advanced disease. In this review, we aim to provide a holistic overview of prostate cancer, including the diagnosis of the disease, mutations leading to the onset and progression of the disease, and treatment options. Prostate cancer diagnoses include a digital rectal examination, prostate-specific antigen analysis, and prostate biopsies. Mutations in certain genes are linked to the onset, progression, and metastasis of the cancer. Treatment for localized prostate cancer encompasses active surveillance, ablative radiotherapy, and radical prostatectomy. Men who relapse or present metastatic prostate cancer receive androgen deprivation therapy (ADT), salvage radiotherapy, and chemotherapy. Currently, available treatment options are more effective when used as combination therapy; however, despite available treatment options, prostate cancer remains to be incurable. There has been ongoing research on finding and identifying other treatment approaches such as the use of traditional medicine, the application of nanotechnologies, and gene therapy to combat prostate cancer, drug resistance, as well as to reduce the adverse effects that come with current treatment options. In this article, we summarize the genes involved in prostate cancer, available treatment options, and current research on alternative treatment options. Full article

(This article belongs to the Special Issue Novel Design and Synthesis of Anticancer Agents)

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1 pages, 451 KiB

Open AccessCorrection

Correction: Wang et al. Cell-Penetrating Peptide and Transferrin Co-Modified Liposomes for Targeted Therapy of Glioma. Molecules 2019, 24, 3540

by Xi Wang, Yarong Zhao, Shiyan Dong, Robert J. Lee, Dongsheng Yang, Huan Zhang and Lesheng Teng

Molecules 2022, 27(17), 5729; https://doi.org/10.3390/molecules27175729 - 5 Sep 2022

Cited by 1 | Viewed by 1184

Abstract

When reviewing our publications, an error in article [...] Full article

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16 pages, 3410 KiB

Open AccessArticle

Nano-Size Characterization and Antifungal Evaluation of Essential Oil Molecules-Loaded Nanoliposomes

by Katya M. Aguilar-Pérez, Dora I. Medina, Roberto Parra-Saldívar and Hafiz M. N. Iqbal

Molecules 2022, 27(17), 5728; https://doi.org/10.3390/molecules27175728 - 5 Sep 2022

Cited by 6 | Viewed by 2806

Abstract

Nanoliposomes, bilayer vesicles at the nanoscale, are becoming popular because of their safety, patient compliance, high entrapment efficiency, and prompt action. Several notable biological activities of natural essential oils (EOs), including fungal inhibition, are of supreme interest. As developed, multi-compositional nanoliposomes loaded with [...] Read more.

Nanoliposomes, bilayer vesicles at the nanoscale, are becoming popular because of their safety, patient compliance, high entrapment efficiency, and prompt action. Several notable biological activities of natural essential oils (EOs), including fungal inhibition, are of supreme interest. As developed, multi-compositional nanoliposomes loaded with various concentrations of clove essential oil (CEO) and tea tree oil (TTO) were thoroughly characterized to gain insight into their nano-size distribution. The present work also aimed to reconnoiter the sustainable synthesis conditions to estimate the efficacy of EOs in bulk and EO-loaded nanoliposomes with multi-functional entities. Following a detailed nano-size characterization of in-house fabricated EO-loaded nanoliposomes, the antifungal efficacy was tested by executing the mycelial growth inhibition (MGI) test using Trichophyton rubrum fungi as a test model. The dynamic light scattering (DLS) profile of as-fabricated EO-loaded nanoliposomes revealed the mean size, polydispersity index (PdI), and zeta potential values as 37.12 ± 1.23 nm, 0.377 ± 0.007, and −36.94 ± 0.36 mV, respectively. The sphere-shaped morphology of CEO and TTO-loaded nanoliposomes was confirmed by a scanning electron microscope (SEM). The existence of characteristic functional bands in all tested counterparts was demonstrated by attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. Compared to TTO-loaded nanoliposomes, the CEO-loaded nanoliposomes exhibited a maximum entrapment efficacy of 91.57 ± 2.5%. The CEO-loaded nanoliposome fraction, prepared using 1.5 µL/mL concentration, showed the highest MGI of 98.4 ± 0.87% tested against T. rubrum strains compared to the rest of the formulations. Full article

(This article belongs to the Special Issue Essential Oils II)

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26 pages, 9134 KiB

Open AccessArticle

Virtual Screening of Alkaloid and Terpenoid Inhibitors of SMT Expressed in Naegleria sp.

by Jason Abraham, Neha Chauhan and Supriyo Ray

Molecules 2022, 27(17), 5727; https://doi.org/10.3390/molecules27175727 - 5 Sep 2022

Cited by 3 | Viewed by 2262

Abstract

The pathogenic form of thermophilic Naegleria sp. i.e., Naegleria fowleri, also known as brain eating amoeba, causes primary amoebic encephalitis (PAM) with a >97% fatality rate. To date, there are no specific drugs identified to treat this disease specifically. The present antimicrobial [...] Read more.

The pathogenic form of thermophilic Naegleria sp. i.e., Naegleria fowleri, also known as brain eating amoeba, causes primary amoebic encephalitis (PAM) with a >97% fatality rate. To date, there are no specific drugs identified to treat this disease specifically. The present antimicrobial combinatorial chemotherapy is hard on many patients, especially children. Interestingly, Naegleria fowleri has complex lipid biosynthesis pathways like other protists and also has a strong preference to utilize absorbed host lipids for generating energy. The ergosterol biosynthesis pathway provides a unique drug target opportunity, as some of the key enzymes involved in this pathway are absent in humans. Sterol 24-C Methyltransferase (SMT) is one such enzyme that is not found in humans. To select novel inhibitors for this enzyme, alkaloids and terpenoids inhibitors were screened and tested against two isozymes of SMT identified in N. gruberi (non-pathogenic) as well as its homolog found in yeast, i.e., ERG6. Five natural product derived inhibitors i.e., Cyclopamine, Chelerythrine, Berberine, Tanshinone 2A, and Catharanthine have been identified as potential drug candidates based on multiple criteria including binding affinity, ADME scores, absorption, and, most importantly, its ability to cross the blood brain barrier. This study provides multiple leads for future drug exploration against Naegleria fowleri. Full article

(This article belongs to the Section Chemical Biology)

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18 pages, 3439 KiB

Open AccessArticle

Modified Protein-Water Interactions in CHARMM36m for Thermodynamics and Kinetics of Proteins in Dilute and Crowded Solutions

by Daiki Matsubara, Kento Kasahara, Hisham M. Dokainish, Hiraku Oshima and Yuji Sugita

Molecules 2022, 27(17), 5726; https://doi.org/10.3390/molecules27175726 - 5 Sep 2022

Cited by 6 | Viewed by 2932

Abstract

Proper balance between protein-protein and protein-water interactions is vital for atomistic molecular dynamics (MD) simulations of globular proteins as well as intrinsically disordered proteins (IDPs). The overestimation of protein-protein interactions tends to make IDPs more compact than those in experiments. Likewise, multiple proteins [...] Read more.

Proper balance between protein-protein and protein-water interactions is vital for atomistic molecular dynamics (MD) simulations of globular proteins as well as intrinsically disordered proteins (IDPs). The overestimation of protein-protein interactions tends to make IDPs more compact than those in experiments. Likewise, multiple proteins in crowded solutions are aggregated with each other too strongly. To optimize the balance, Lennard-Jones (LJ) interactions between protein and water are often increased about 10% (with a scaling parameter, λ = 1.1) from the existing force fields. Here, we explore the optimal scaling parameter of protein-water LJ interactions for CHARMM36m in conjunction with the modified TIP3P water model, by performing enhanced sampling MD simulations of several peptides in dilute solutions and conventional MD simulations of globular proteins in dilute and crowded solutions. In our simulations, 10% increase of protein-water LJ interaction for the CHARMM36m cannot maintain stability of a small helical peptide, (AAQAA)₃ in a dilute solution and only a small modification of protein-water LJ interaction up to the 3% increase (λ = 1.03) is allowed. The modified protein-water interactions are applicable to other peptides and globular proteins in dilute solutions without changing thermodynamic properties from the original CHARMM36m. However, it has a great impact on the diffusive properties of proteins in crowded solutions, avoiding the formation of too sticky protein-protein interactions. Full article

(This article belongs to the Special Issue Frontiers in Protein Folding and Related Areas – in Memory of Professor Sir Christopher M. Dobson (1949–2019))

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10 pages, 3054 KiB

Open AccessArticle

Evolution of Interferon-Gamma Aptamer with Good Affinity and Analytical Utility by a Rational In Silico Base Mutagenesis Post-SELEX Strategy

by Lianhui Zhao, Qionglin Wang, Yingai Yin, Yan Yang, Huifang Cui and Yiyang Dong

Molecules 2022, 27(17), 5725; https://doi.org/10.3390/molecules27175725 - 5 Sep 2022

Cited by 6 | Viewed by 2639

Abstract

The Systematic Evolution of Ligands by EXponential enrichment (SELEX) is conventionally an effective method to identify aptamers, which are oligonucleotide sequences with desired properties to recognize targets specifically and sensitively. However, there are some inherent limitations, e.g., the loss of potential high-affinity sequences [...] Read more.

The Systematic Evolution of Ligands by EXponential enrichment (SELEX) is conventionally an effective method to identify aptamers, which are oligonucleotide sequences with desired properties to recognize targets specifically and sensitively. However, there are some inherent limitations, e.g., the loss of potential high-affinity sequences during biased iterative PCR enrichment processes and the limited structural diversity of the initial library, which seriously restrict their real-world applications. To overcome these limitations, the in silico base mutagenesis post-SELEX strategy based on the low Gibbs free energy (ΔG) and genetic algorithm was developed for the optimization of the interferon-gamma aptamer (B1-4). In the process of evolution, new sequences were created and the aptamer candidates with low ΔG values and advanced structures were produced. After five rounds of selection, systematic studies revealed that the affinity of the newly developed evolutionary aptamer (M5-5) was roughly 10-fold higher than that of the parent aptamer (B1-4), and an aptasensor detection system with a limit-of-detection (LOD) value of 3.17 nM was established based on the evolutionary aptamer. The proposed approach provided an efficient strategy to improve the aptamer with low energy and a high binding ability, and the good analytical utility thereof. Full article

(This article belongs to the Special Issue Aptamer Generation and Bioapplication)

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10 pages, 1827 KiB

Open AccessArticle

Urolithin M5 from the Leaves of Canarium album (Lour.) DC. Inhibits Influenza Virus by Targeting Neuraminidase

by Mengjie Xiao, Fei Cao, Tao Huang, Yun-Sang Tang, Xin Zhao and Pang-Chui Shaw

Molecules 2022, 27(17), 5724; https://doi.org/10.3390/molecules27175724 - 5 Sep 2022

Cited by 6 | Viewed by 2320

Abstract

Ganlanye (GLY), the leaf of Canarium album (Lour.) DC., is a traditional Chinese medicinal herb for warm disease treatment. We found that its aqueous extract could inhibit the influenza A virus. To find and characterize anti-influenza virus phytochemicals from GLY, we performed (1) [...] Read more.

Ganlanye (GLY), the leaf of Canarium album (Lour.) DC., is a traditional Chinese medicinal herb for warm disease treatment. We found that its aqueous extract could inhibit the influenza A virus. To find and characterize anti-influenza virus phytochemicals from GLY, we performed (1) bioassay-guided isolation, (2) a cell and animal assay, and (3) a mechanism study. Bioassay-guided isolation was used to identify the effective components. Influenza virus-infected MDCK cell and BALB/c mouse models were employed to evaluate the anti-influenza virus activities. A MUNANA assay was performed to find the NA inhibitory effect. As a result, urolithin M5 was obtained from the crude extract of GLY. It inhibited influenza virus activities in vitro and in vivo by suppressing the viral NA activity. In the MDCK cell model, urolithin M5 could inhibit an oseltamivir-resistant strain. In a PR8-infected mouse model, 200 mg/kg/d urolithin M5 protected 50% of mice from death and improved lung edema conditions. GLY was recorded as a major traditional herb for warm disease treatment. Our study identified GLY as a potent anti-influenza herb and showed urolithin M5 as the active component. We first report the in vivo activity of urolithin M5 and support the anti-influenza application of GLY. Full article

(This article belongs to the Section Natural Products Chemistry)

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10 pages, 2383 KiB

Open AccessArticle

Robust Laminated Anode with an Ultrathin Titanium Nitride Layer for High-Efficiency Top-Emitting Organic Light-Emitting Diodes

by Jia-Heng Cai, Qi-Sheng Tian, Xiao-Zhao Zhu, Zhi-Hao Qu, Wei He, Dong-Ying Zhou and Liang-Sheng Liao

Molecules 2022, 27(17), 5723; https://doi.org/10.3390/molecules27175723 - 5 Sep 2022

Cited by 2 | Viewed by 2631

Abstract

The effective reflective anode remains a highly desirable component for the fabrication of reliable top-emitting organic light-emitting diodes (TE-OLEDs) which have the potential to be integrated with complementary metal-oxide-semiconductor (CMOS) circuits for microdisplays. This work demonstrates a novel laminated anode consisting of a [...] Read more.

The effective reflective anode remains a highly desirable component for the fabrication of reliable top-emitting organic light-emitting diodes (TE-OLEDs) which have the potential to be integrated with complementary metal-oxide-semiconductor (CMOS) circuits for microdisplays. This work demonstrates a novel laminated anode consisting of a Cr/Al/Cr multilayer stack. Furthermore, we implement an ultra-thin titanium nitride (TiN) layer as a protective layer on the top of the Cr/Al/Cr composite anode, which creates a considerably reflective surface in the visible range, and meanwhile improves the chemical stability of the electrode against the atmosphere or alkali environment. Based on [2-(2-pyridinyl-N)phenyl-C](acetylacetonate)iridium(III) as green emitter and Mg/Ag as transparent cathode, our TE-OLED using the TiN-coated anode achieves the maximum current efficiency of 71.2 cd/A and the maximum power efficiency of 66.7 lm/W, which are 81% and 90% higher than those of the reference device without TiN, respectively. The good device performance shows that the Cr/Al/Cr/TiN could function as a promising reflective anode for the high-resolution microdisplays on CMOS circuits. Full article

(This article belongs to the Special Issue Organic Light-Emitting Diodes 3.0)

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15 pages, 3529 KiB

Open AccessArticle

Unravelling the Polytoxicology of Chlorfenapyr on Non-Target HepG2 Cells: The Involvement of Mitochondria-Mediated Programmed Cell Death and DNA Damage

by Yuanhang Ren, Xuan He, Xiyue Yan, Yanting Yang, Qiang Li, Tian Yao, Lidan Lu, Lianxin Peng and Liang Zou

Molecules 2022, 27(17), 5722; https://doi.org/10.3390/molecules27175722 - 5 Sep 2022

Cited by 6 | Viewed by 2104

Abstract

Chlorfenapyr (CHL) is a type of insecticide with a wide range of insecticidal activities and unique targets. The extensive use of pesticides has caused an increase in potential risks to the environment and human health. However, the potential toxicity of CHL and its [...] Read more.

Chlorfenapyr (CHL) is a type of insecticide with a wide range of insecticidal activities and unique targets. The extensive use of pesticides has caused an increase in potential risks to the environment and human health. However, the potential toxicity of CHL and its mechanisms of action on humans remain unclear. Therefore, human liver cells (HepG2) were used to investigate the cytotoxic effect and mechanism of toxicity of CHL at the cellular level. The results showed that CHL induced cellular toxicity in HepG2 cells and induced mitochondrial damage associated with reactive oxygen species (ROS) accumulation and mitochondrial calcium overload, ultimately leading to apoptosis and autophagy in HepG2 cells. Typical apoptotic changes occurred, including a decline in the mitochondrial membrane potential, the promotion of Bax/Bcl-2 expression causing the release of cyt-c into the cytosol, the activation of cas-9/-3, and the cleavage of PARP. The autophagic effects included the formation of autophagic vacuoles, accumulation of Beclin-1, transformation of LC3-II, and downregulation of p62. Additionally, DNA damage and cell cycle arrest were detected in CHL-treated cells. These results show that CHL induced cytotoxicity associated with mitochondria-mediated programmed cell death (PCD) and DNA damage in HepG2 cells. Full article

(This article belongs to the Section Chemical Biology)

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14 pages, 647 KiB

Open AccessArticle

Chemical Markers and Pharmacological Characters of Pelargonium graveolens Essential Oil from Palestine

by Nidal Jaradat, Mohammed Hawash, Mohammad Qadi, Murad Abualhasan, Aseel Odetallah, Ghfran Qasim, Reem Awayssa, Amna Akkawi, Ibtesam Abdullah and Nawaf Al-Maharik

Molecules 2022, 27(17), 5721; https://doi.org/10.3390/molecules27175721 - 5 Sep 2022

Cited by 19 | Viewed by 3032

Abstract

Pelargonium graveolens leaves are widely used in traditional medicine for relieving some cardiovascular, dental, gastrointestinal, and respiratory disorders. They are also used as food and tea additives in Palestine and many other countries. Consequently, this investigation aimed to describe the chemical markers, cytotoxic, [...] Read more.

Pelargonium graveolens leaves are widely used in traditional medicine for relieving some cardiovascular, dental, gastrointestinal, and respiratory disorders. They are also used as food and tea additives in Palestine and many other countries. Consequently, this investigation aimed to describe the chemical markers, cytotoxic, antioxidant, antimicrobial, metabolic, and cyclooxygenase (COX) enzymes inhibitory characteristics of P. graveolens essential oil (PGEO) from Palestine utilizing reference methods. There were 70 chemicals found in the GCMS analysis, and oxygenated terpenoids were the most abundant group of the total PGEO. Citronellol (24.44%), citronellyl formate (15.63%), γ-eudesmol (7.60%), and iso-menthone (7.66%) were the dominant chemical markers. The EO displayed strong antioxidant activity (IC₅₀ = 3.88 ± 0.45 µg/mL) and weak lipase and α-amylase suppressant effects. Notably, the PGEO displayed high α-glucosidase inhibitory efficacy compared with Acarbose, with IC₅₀ doses of 52.44 ± 0.29 and 37.15 ± 0.33 µg/mL, respectively. PGEO remarkably repressed the growth of methicillin-resistant Staphylococcus aureus (MRSA), even more than Ampicillin and Ciprofloxacin, and strongly inhibited Candida albicans compared with Fluconazole. The highest cytotoxic effect of the PGEO was noticed against MCF-7, followed by Hep3B and HeLa cancer cells, with IC₅₀ doses of 32.71 ± 1.25, 40.71 ± 1.89, and 315.19 ± 20.5 µg/mL, respectively, compared with doxorubicin. Moreover, the screened EO demonstrated selective inhibitory activity against COX-1 (IC₅₀ = 14.03 µg/mL). Additionally, PGEO showed a weak suppressant effect on COX-2 (IC₅₀ = 275.97 µg/mL). The current research can be considered the most comprehensive investigation of the chemical and pharmacological characterization of the PGEO. The results obtained in this study demonstrate, without doubt, that this plant represents a rich source of bioactive substances that can be further investigated and authenticated for their medicinal potential. Full article

(This article belongs to the Special Issue Essential Oils II)

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21 pages, 4827 KiB

Open AccessArticle

6-Formyl Umbelliferone, a Furanocoumarin from Angelica decursiva L., Inhibits Key Diabetes-Related Enzymes and Advanced Glycation End-Product Formation

by Md Yousof Ali, Gerald W. Zamponi, Su Hui Seong, Hyun Ah Jung and Jae Sue Choi

Molecules 2022, 27(17), 5720; https://doi.org/10.3390/molecules27175720 - 5 Sep 2022

Cited by 6 | Viewed by 2176

Abstract

Over the years, great attention has been paid to coumarin derivatives, a set of versatile molecules that exhibit a wide variety of biological activities and have few toxic side effects. In this study, we investigated the antidiabetic potential of 6-formyl umbelliferone (6-FU), a [...] Read more.

Over the years, great attention has been paid to coumarin derivatives, a set of versatile molecules that exhibit a wide variety of biological activities and have few toxic side effects. In this study, we investigated the antidiabetic potential of 6-formyl umbelliferone (6-FU), a novel furanocoumarin isolated from Angelica decursiva. Numerous pharmacological activities of 6-FU have been previously reported; however, the mechanism of its antidiabetic activity is unknown. Therefore, we examined the action of 6-FU on a few candidate-signaling molecules that may underlie its antidiabetic activity, including its inhibition of protein tyrosine phosphatase 1B (PTP1B), α-glucosidase, human recombinant aldose reductase (HRAR), and advanced glycation end-product (AGE) formation (IC₅₀ = 1.13 ± 0.12, 58.36 ± 1.02, 5.11 ± 0.21, and 2.15 ± 0.13 μM, respectively). A kinetic study showed that 6-FU exhibited mixed-type inhibition against α-glucosidase and HRAR and competitive inhibition of PTP1B. Docking simulations of 6-FU demonstrated negative binding energies and close proximity to residues in the binding pockets of those enzymes. We also investigated the molecular mechanisms underlying 6-FU’s antidiabetic effects. 6-FU significantly increased glucose uptake and decreased PTP1B expression in insulin-resistant C2C12 skeletal muscle cells. Moreover, 6-FU (0.8–100 μM) remarkably inhibited the formation of fluorescent AGEs in glucose-fructose-induced human serum albumin glycation over the course of 4 weeks. The findings clearly indicate that 6-FU will be useful in the development of multiple target-oriented therapeutic modalities for the treatment of diabetes and diabetes-related complications. Full article

(This article belongs to the Section Medicinal Chemistry)

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14 pages, 3158 KiB

Open AccessArticle

Wistin Exerts an Anti-Inflammatory Effect via Nuclear Factor-κB and p38 Signaling Pathways in Lipopolysaccharide-Stimulated RAW264.7 Cells

by Jangeun An, Gyoungah Ryu, Seong-Ah Shin, Huiji Kim, Mi-Jeong Ahn, Jun Hyuck Lee and Chang Sup Lee

Molecules 2022, 27(17), 5719; https://doi.org/10.3390/molecules27175719 - 5 Sep 2022

Cited by 6 | Viewed by 2171

Abstract

Inflammation is an immune response to cellular damage caused by various stimuli (internal or external) and is essential to human health. However, excessive inflammatory responses may be detrimental to the host. Considering that the existing drugs for the treatment of inflammatory diseases have [...] Read more.

Inflammation is an immune response to cellular damage caused by various stimuli (internal or external) and is essential to human health. However, excessive inflammatory responses may be detrimental to the host. Considering that the existing drugs for the treatment of inflammatory diseases have various side effects, such as allergic reactions, stomach ulcers, and cardiovascular problems, there is a need for research on new anti-inflammatory agents with low toxicity and fewer side effects. As 4′,6-dimethoxyisoflavone-7-O-β-d-glucopyranoside (wistin) is a phytochemical that belongs to an isoflavonoid family, we investigated whether wistin could potentially serve as a novel anti-inflammatory agent. In this study, we found that wistin significantly reduced the production of nitric oxide and intracellular reactive oxygen species in lipopolysaccharide-stimulated RAW 264.7 cells. Moreover, wistin reduced the mRNA levels of pro-inflammatory enzymes (inducible nitric oxide synthase (iNOS) and cyclooxygenase (COX-2)) and cytokines (interleukin (IL)-1β and IL-6) and significantly reduced the protein expression of pro-inflammatory enzymes (iNOS and COX-2). Furthermore, wistin reduced the activation of the nuclear factor-κB and p38 signaling pathways. Together, these results suggest that wistin is a prospective candidate for the development of anti-inflammatory drugs. Full article

(This article belongs to the Special Issue Natural Polyphenols in Human Health)

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1 pages, 483 KiB

Open AccessCorrection

Correction: Liu et al. Identification of C₂₁ Steroidal Glycosides from Gymnema sylvestre (Retz.) and Evaluation of Their Glucose Uptake Activities. Molecules 2021, 26, 6549

by Meiyu Liu, Tongxi Zhou, Jinyan Zhang, Guangfeng Liao, Rumei Lu and Xinzhou Yang

Molecules 2022, 27(17), 5718; https://doi.org/10.3390/molecules27175718 - 5 Sep 2022

Cited by 1 | Viewed by 1184

Abstract

After careful examination, we found that the structures [...] Full article

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24 pages, 2356 KiB

Open AccessReview

Liquid Chromatography-Mass Spectrometry (LC-MS) Derivatization-Based Methods for the Determination of Fatty Acids in Biological Samples

by Christiana Mantzourani and Maroula G. Kokotou

Molecules 2022, 27(17), 5717; https://doi.org/10.3390/molecules27175717 - 5 Sep 2022

Cited by 16 | Viewed by 7175

Abstract

Fatty acids (FAs) play pleiotropic roles in living organisms, acting as signaling molecules and gene regulators. They are present in plants and foods and may affect human health by food ingestion. As a consequence, analytical methods for their determination in biological fluids, plants [...] Read more.

Fatty acids (FAs) play pleiotropic roles in living organisms, acting as signaling molecules and gene regulators. They are present in plants and foods and may affect human health by food ingestion. As a consequence, analytical methods for their determination in biological fluids, plants and foods have attracted high interest. Undoubtedly, mass spectrometry (MS) has become an indispensable technique for the analysis of FAs. Due to the inherent poor ionization efficiency of FAs, their chemical derivatization prior to analysis is often employed. Usually, the derivatization of the FA carboxyl group aims to charge reversal, allowing detection and quantification in positive ion mode, thus, resulting in an increase in sensitivity in determination. Another approach is the derivatization of the double bond of unsaturated FAs, which aims to identify the double bond location. The present review summarizes the various classes of reagents developed for FA derivatization and discusses their applications in the liquid chromatography-MS (LC-MS) analysis of FAs in various matrices, including plasma and feces. In addition, applications for the determination of eicosanoids and fatty acid esters of hydroxy fatty acids (FAHFAs) are 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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13 pages, 2311 KiB

Open AccessArticle

Plumbagin Suppresses Breast Cancer Progression by Downregulating HIF-1α Expression via a PI3K/Akt/mTOR Independent Pathway under Hypoxic Condition

by Supawan Jampasri, Somrudee Reabroi, Duangjai Tungmunnithum, Warisara Parichatikanond and Darawan Pinthong

Molecules 2022, 27(17), 5716; https://doi.org/10.3390/molecules27175716 - 5 Sep 2022

Cited by 14 | Viewed by 2523

Abstract

Hypoxia-inducible factor-1α (HIF-1α) is a major transcriptional regulator that plays a crucial role in the hypoxic response of rapidly growing tumors. Overexpression of HIF-1α has been associated with breast cancer metastasis and poor clinical prognosis. Plumbagin, the main phytochemical from Plumbago indica, [...] Read more.

Hypoxia-inducible factor-1α (HIF-1α) is a major transcriptional regulator that plays a crucial role in the hypoxic response of rapidly growing tumors. Overexpression of HIF-1α has been associated with breast cancer metastasis and poor clinical prognosis. Plumbagin, the main phytochemical from Plumbago indica, exerts anticancer effects via multiple mechanisms. However, its precise mechanisms on breast cancer cells under hypoxic conditions has never been investigated. This study aims to examine the anticancer effect of plumbagin on MCF-7 cell viability, transcriptional activity, and protein expression of HIF-1α under normoxia and hypoxia-mimicking conditions, as well as reveal the underlying signaling pathways. The results demonstrate that plumbagin decreased MCF-7 cell viability under normoxic conditions, and a greater extent of reduction was observed upon exposure to hypoxic conditions induced by cobalt chloride (CoCl₂). Mechanistically, MCF-7 cells upregulated the expression of HIF-1α protein, mRNA, and the VEGF target gene under CoCl₂-induced hypoxia, which were abolished by plumbagin treatment. In addition, inhibition of HIF-1α and its downstream targets did not affect the signaling transduction of the PI3K/Akt/mTOR pathway under hypoxic state. This study provides mechanistic insight into the anticancer activity of plumbagin in breast cancer cells under hypoxic conditions by abolishing HIF-1α at transcription and post-translational modifications. Full article

(This article belongs to the Special Issue Flavonoids’ and Other Polyphenols’ Pharmacological Activities for Phytopharmaceutical and Medicinal Applications)

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16 pages, 3265 KiB

Open AccessArticle

Ultrasonic-Assisted Efficient Extraction of Coumarins from Peucedanum decursivum (Miq.) Maxim Using Deep Eutectic Solvents Combined with an Enzyme Pretreatment

by Zeyu Li and Qian Li

Molecules 2022, 27(17), 5715; https://doi.org/10.3390/molecules27175715 - 5 Sep 2022

Cited by 5 | Viewed by 2176

Abstract

In this study, the ultrasonic-assisted extraction of total coumarins from Peucedanum decursivum (Miq.) Maxim (P. decursivum) via the combination of deep eutectic solvents (DESs) with cellulase pretreatment was carried out. Among the 15 kinds of DESs with choline chloride as hydrogen [...] Read more.

In this study, the ultrasonic-assisted extraction of total coumarins from Peucedanum decursivum (Miq.) Maxim (P. decursivum) via the combination of deep eutectic solvents (DESs) with cellulase pretreatment was carried out. Among the 15 kinds of DESs with choline chloride as hydrogen bond acceptors, the DES system of choline chloride/1,4-butanediol with a molar ratio of 1:4 showed the best extraction effect. First, single-factor experiments were performed using the following factors: liquid–solid ratio, pH, enzyme dosage and ultrasonic temperature. The Box–Behnken design (BBD) and response surface methodology (RSM) were employed to optimize the extraction conditions and obtain the following optimal parameter values for the extraction of coumarins from P. decursivum: liquid–solid ratio 14:1 mL/g, pH 5.0, enzyme dosage 0.2%, ultrasonic temperature 60 °C and ultrasonic time 50 min. Under these conditions, the extraction yield of total coumarins from P. decursivum could reach 2.65%, which was close to the predicted extraction yield of 2.68%. Furthermore, the contents of six coumarins, namely, umbelliferone, nodakenin, xanthotoxin, bergapten, imperatorin and decursin were determined to be 0.707 mg·g⁻¹, 0.085 mg·g⁻¹, 1.651 mg·g⁻¹, 2.806 mg·g⁻¹, 0.570 mg·g⁻¹ and 0.449 mg·g⁻¹, respectively, using HPLC-MS after the optimization. In addition, the cell fragmentation of P. decursivum powder obtained using ultrasonic-assisted DES extraction with enzyme pretreatment was found to be the most comprehensive using scanning electron microscopy (SEM), which indicated the highest extraction efficiency for P. decursivum. Finally, the in vitro antioxidant activity of the extracts was evaluated via radical scavenging with 1,1-diphenyl-2-picrylhydrazyl (DPPH), which showed that ultrasonic-assisted DES extraction with enzyme pretreatment exhibited significant antioxidant activity with DPPH radical scavenging of up to 97.90%. This work developed a new and efficient extraction method for coumarins. Full article

(This article belongs to the Special Issue Deep Eutectic Solvents: Properties and Applications as Green Solvents)

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18 pages, 1563 KiB

Open AccessArticle

A Branched and Double Alpha-Gal-Bearing Synthetic Neoglycoprotein as a Biomarker for Chagas Disease

by Alba L. Montoya, Elisa G. Carvajal, Uriel Ortega-Rodriguez, Igor L. Estevao, Roger A. Ashmus, Sohan R. Jankuru, Susana Portillo, Cameron C. Ellis, Colin D. Knight, Julio Alonso-Padilla, Luis Izquierdo, Maria-Jesus Pinazo, Joaquim Gascon, Veronica Suarez, Douglas M. Watts, Iliana R. Malo, Janine M. Ramsey, Belkisyolé Alarcón De Noya, Oscar Noya, Igor C. Almeida and Katja Michael Show full author list Hide full author list

Molecules 2022, 27(17), 5714; https://doi.org/10.3390/molecules27175714 - 5 Sep 2022

Cited by 3 | Viewed by 3178

Abstract

Chagas disease (CD) is caused by the parasite Trypanosoma cruzi and affects 6–7 million people worldwide. The diagnosis is still challenging, due to extensive parasite diversity encompassing seven genotypes (TcI-VI and Tcbat) with diverse ecoepidemiological, biological, and pathological traits. Chemotherapeutic intervention is usually [...] Read more.

Chagas disease (CD) is caused by the parasite Trypanosoma cruzi and affects 6–7 million people worldwide. The diagnosis is still challenging, due to extensive parasite diversity encompassing seven genotypes (TcI-VI and Tcbat) with diverse ecoepidemiological, biological, and pathological traits. Chemotherapeutic intervention is usually effective but associated with severe adverse events. The development of safer, more effective therapies is hampered by the lack of biomarker(s) (BMKs) for the early assessment of therapeutic outcomes. The mammal-dwelling trypomastigote parasite stage expresses glycosylphosphatidylinositol-anchored mucins (tGPI-MUC), whose O-glycans are mostly branched with terminal, nonreducing α-galactopyranosyl (α-Gal) glycotopes. These are absent in humans, and thus highly immunogenic and inducers of specific CD anti-α-Gal antibodies. In search for α-Gal-based BMKs, here we describe the synthesis of neoglycoprotein NGP11b, comprised of a carrier protein decorated with the branched trisaccharide Galα(1,2)[Galα(1,6)]Galβ. By chemiluminescent immunoassay using sera/plasma from chronic CD (CCD) patients from Venezuela and Mexico and healthy controls, NGP11b exhibited sensitivity and specificity similar to that of tGPI-MUC from genotype TcI, predominant in those countries. Preliminary evaluation of CCD patients subjected to chemotherapy showed a significant reduction in anti-α-Gal antibody reactivity to NGP11b. Our data indicated that NGP11b is a potential BMK for diagnosis and treatment assessment in CCD patients. Full article

(This article belongs to the Collection Advances in Glycosciences)

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9 pages, 2679 KiB

Open AccessArticle

Controlling the Treatment Time for Ideal Morphology towards Efficient Organic Solar Cells

by Yiwen Hou, Qiuning Wang, Ciyuan Huang, Tao Yang, Shasha Shi, Shangfei Yao, Donglou Ren, Tao Liu, Guangye Zhang and Bingsuo Zou

Molecules 2022, 27(17), 5713; https://doi.org/10.3390/molecules27175713 - 5 Sep 2022

Cited by 2 | Viewed by 1878

Abstract

In this work, we performed a systematic comparison of different duration of solvent vapor annealing (SVA) treatment upon state-of-the-art PM6:SY1 blend film, which is to say for the first time, the insufficient, appropriate, and over-treatment’s effect on the active layer is investigated. The [...] Read more.

In this work, we performed a systematic comparison of different duration of solvent vapor annealing (SVA) treatment upon state-of-the-art PM6:SY1 blend film, which is to say for the first time, the insufficient, appropriate, and over-treatment’s effect on the active layer is investigated. The power conversion efficiency (PCE) of corresponding organic solar cell (OSC) devices is up to 17.57% for the optimized system, surpassing the two counterparts. The properly tuned phase separation and formed interpenetrating network plays an important role in achieving high efficiency, which is also well-discussed by the morphological characterizations and understanding of device physics. Specifically, these improvements result in enhanced charge generation, transport, and collection. This work is of importance due to correlating post-treatment delicacy, thin-film morphology, and device performance in a decent way. Full article

(This article belongs to the Section Materials Chemistry)

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20 pages, 10507 KiB

Open AccessArticle

On the Coexistence of the Carbene⋯H-D Hydrogen Bond and Other Accompanying Interactions in Forty Dimers of N-Heterocyclic-Carbenes (I, IMe₂, IⁱPr₂, I^tBu₂, IMes₂, IDipp₂, IAd₂; I = imidazol-2-ylidene) and Some Fundamental Proton Donors (HF, HCN, H₂O, MeOH, NH₃)

by Mirosław Jabłoński

Molecules 2022, 27(17), 5712; https://doi.org/10.3390/molecules27175712 - 5 Sep 2022

Cited by 8 | Viewed by 2441

Abstract

The subject of research is forty dimers formed by imidazol-2-ylidene (I) or its derivative (IR

_{2}

) obtained by replacing the hydrogen atoms in both N-H bonds with larger important and popular substituents of increasing complexity (methyl = Me, iso-propyl =

^{i}

[...] Read more.

The subject of research is forty dimers formed by imidazol-2-ylidene (I) or its derivative (IR

_{2}

) obtained by replacing the hydrogen atoms in both N-H bonds with larger important and popular substituents of increasing complexity (methyl = Me, iso-propyl =

^{i}

Pr, tert-butyl =

^{t}

Bu, phenyl = Ph, mesityl = Mes, 2,6-diisopropylphenyl = Dipp, 1-adamantyl = Ad) and fundamental proton donor (HD) molecules (HF, HCN, H

_{2}

O, MeOH, NH

_{3}

). While the main goal is to characterize the generally dominant C⋯H-D hydrogen bond engaging a carbene carbon atom, an equally important issue is the often omitted analysis of the role of accompanying secondary interactions. Despite the often completely different binding possibilities of the considered carbenes, and especially HD molecules, several general trends are found. Namely, for a given carbene, the dissociation energy values of the IR

_{2} \dots

HD dimers increase in the following order: NH

_{3}

< H

_{2}

O < HCN ≤ MeOH ≪ HF. Importantly, it is found that, for a given HD molecule, IDipp

_{2}

forms the strongest dimers. This is attributed to the multiplicity of various interactions accompanying the dominant C⋯H-D hydrogen bond. It is shown that substitution of hydrogen atoms in both N-H bonds of the imidazol-2-ylidene molecule by the investigated groups leads to stronger dimers with HF, HCN, H

_{2}

O or MeOH. The presented results should contribute to increasing the knowledge about the carbene chemistry and the role of intermolecular interactions, including secondary ones. Full article

(This article belongs to the Collection Hydrogen Bonds)

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