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Molecules, Volume 24, Issue 9 (May-1 2019)

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Cover Story (view full-size image) 4-Hydroxycyanobenzene (4HCB) is a dipolar molecule with both π–π and hydrogen-bonding interactions [...] Read more.
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Open AccessReview
A Review on Daphnane-Type Diterpenoids and Their Bioactive Studies
Molecules 2019, 24(9), 1842; https://doi.org/10.3390/molecules24091842
Received: 16 April 2019 / Revised: 6 May 2019 / Accepted: 7 May 2019 / Published: 13 May 2019
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Abstract
Natural daphnane diterpenoids, mainly distributed in plants of the Thymelaeaceae and Euphorbiaceae families, usually include a 5/7/6-tricyclic ring system with poly-hydroxyl groups located at C-3, C-4, C-5, C-9, C-13, C-14, or C-20, while some special types have a characteristic orthoester motif triaxially connectedat [...] Read more.
Natural daphnane diterpenoids, mainly distributed in plants of the Thymelaeaceae and Euphorbiaceae families, usually include a 5/7/6-tricyclic ring system with poly-hydroxyl groups located at C-3, C-4, C-5, C-9, C-13, C-14, or C-20, while some special types have a characteristic orthoester motif triaxially connectedat C-9, C-13, and C-14. The daphnane-type diterpenoids can be classified into five types: 6-epoxy daphnane diterpenoids, resiniferonoids, genkwanines, 1-alkyldaphnanes and rediocides, based on the oxygen-containing functions at rings B and C, as well as the substitution pattern of ring A. Up to now, nearly 200 daphnane-type diterpenoids have been isolated and elucidated from the Thymelaeaceae and Euphorbiaceae families. In-vitro and in-vivo experiments of these compounds have shown that they possess a wide range of biological activities, including anti-HIV, anti-cancer, anti-leukemic, neurotrophic, pesticidal and cytotoxic effects. A comprehensive account of the structural diversity is given in this review, along with the cytotoxic activities of daphnane-type diterpenoids, up to April 2019. Full article
(This article belongs to the collection Bioactive Compounds)
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Open AccessArticle
1H-NMR Metabolomics Analysis of the Effects of Sulfated Polysaccharides from Masson Pine Pollen in RAW264.7 Macrophage Cells
Molecules 2019, 24(9), 1841; https://doi.org/10.3390/molecules24091841
Received: 8 April 2019 / Revised: 2 May 2019 / Accepted: 7 May 2019 / Published: 13 May 2019
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Abstract
Many polysaccharides have been shown to be bioactive, with the addition of sulfate often enhancing or altering this bioactivity. In previous studies, masson pine pollen polysaccharides, to include a sulfate derivative, have been shown to promote macrophage proliferation similarly to LPS. However, the [...] Read more.
Many polysaccharides have been shown to be bioactive, with the addition of sulfate often enhancing or altering this bioactivity. In previous studies, masson pine pollen polysaccharides, to include a sulfate derivative, have been shown to promote macrophage proliferation similarly to LPS. However, the exact metabolic mechanisms promoting this proliferation remain unclear. In this study, RAW264.7 macrophage cells were treated with a purified masson pine pollen polysaccharide (PPM60-D), a sulfate derivative (SPPM60-D), or LPS. Proliferation levels at a variety of concentrations were examined using MTT assay, with optimal concentration used when performing metabolomic analysis via 1H nuclear magnetic resonance (1H-NMR). This process resulted in the identification of thirty-five intracellular metabolites. Subsequent multivariate statistical analysis showed that both LPS and SPPM60-D promote RAW264.7 proliferation by promoting aerobic respiration processes and reducing processes associated with glycolysis. While some insight was gained regarding the mechanistic differences between SPPM60-D and LPS, the specific mechanisms governing the effect of SPPM60 on RAW264.7 cells will require further elucidation. These findings show that both LPS and SPPM60-D effectively promote RAW264.7 proliferation and may have beneficial uses in maintaining cellular vitality or inhibiting cancer. Full article
(This article belongs to the Special Issue Carbohydrate Chemistry)
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Open AccessArticle
Structural Transformations in the Thermal Dehydration of [Cu2(bpa)(btec)(H2O)4]n Coordination Polymer
Molecules 2019, 24(9), 1840; https://doi.org/10.3390/molecules24091840
Received: 17 April 2019 / Revised: 3 May 2019 / Accepted: 11 May 2019 / Published: 13 May 2019
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Abstract
Reactions between pyridinic ligands such as 1,2-bis(4-pyridyl)ethane (bpa) and transition metal cations are a very widespread technique to produce extended coordination polymers such as Metal-Organic Frameworks. In combination with a second ligand these systems could present different topologies and behaviors. In [...] Read more.
Reactions between pyridinic ligands such as 1,2-bis(4-pyridyl)ethane (bpa) and transition metal cations are a very widespread technique to produce extended coordination polymers such as Metal-Organic Frameworks. In combination with a second ligand these systems could present different topologies and behaviors. In this context, the use of 1,2,4,5-benzenetetracarboxylic acid (H4btec) gave us a novel 2D compound, [Cu2(bpa)(btec)(H2O)4]n (1), which was prepared by microwave-assisted synthesis and structurally characterized by means of single crystal X-ray diffraction. Its thermal behavior was analyzed through thermogravimetric analysis and variable temperature powder X-ray diffraction, concluding that thermal stability is influenced by the coordination water molecules, allowing two sequential thermochromic phase transformations to take place. These transformations were monitored by electronic paramagnetic resonance spectroscopy and magnetic susceptibility measurements. In addition, the crystal structure of the anhydrous compound [Cu2(bpa)(btec)]n (1.ah) was determined. Finally, a topological study was carried out for the bpa ligand considering all the structures deposited in the Cambridge Structural Databased. More than 1000 structures were analyzed and classified into 17 different topologies, according to the role of the ligand. Full article
(This article belongs to the Special Issue Functional Metal-Organic Framework Based Materials)
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Open AccessArticle
Isolation of Myricitrin and 3,5-di-O-Methyl Gossypetin from Syzygium samarangense and Evaluation of their Involvement in Protecting Keratinocytes against Oxidative Stress via Activation of the Nrf-2 Pathway
Molecules 2019, 24(9), 1839; https://doi.org/10.3390/molecules24091839
Received: 23 April 2019 / Revised: 8 May 2019 / Accepted: 10 May 2019 / Published: 13 May 2019
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Abstract
The wax apple (Syzygium samarangense) is traditionally employed as an antibacterial and immunostimulant drug in traditional medicine. This plant is rich in different flavonoids and tannins. In this study, we isolated two compounds from S. samarangense leaves: myricitrin and 3,5-di-O [...] Read more.
The wax apple (Syzygium samarangense) is traditionally employed as an antibacterial and immunostimulant drug in traditional medicine. This plant is rich in different flavonoids and tannins. In this study, we isolated two compounds from S. samarangense leaves: myricitrin and 3,5-di-O-methyl gossypetin. Then, we investigated the mechanisms of action of the two compounds against oxidative stress (induced by sodium arsenite) and inflammation (induced by UV light) on human keratinocytes. We could clearly demonstrate that the pre-treatment of cells with both compounds was able to mitigate the negative effects induced by oxidative stress, as no alteration in reactive oxygen species (ROS) production, glutathione (GSH) level, or protein oxidation was observed. Additionally, both compounds were able to modulate mitogen-activated protein kinase (MAPK) signaling pathways to counteract oxidative stress activation. Finally, we showed that 3,5-di-O-methyl gossypetin exerted its antioxidant activity through the nuclear transcription factor-2 (Nrf-2) pathway, stimulating the expression of antioxidant proteins, such as HO-1 and Mn-SOD-3. Full article
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Open AccessArticle
The Role of Astragaloside IV against Cerebral Ischemia/Reperfusion Injury: Suppression of Apoptosis via Promotion of P62-LC3-Autophagy
Molecules 2019, 24(9), 1838; https://doi.org/10.3390/molecules24091838
Received: 2 April 2019 / Revised: 4 May 2019 / Accepted: 8 May 2019 / Published: 13 May 2019
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Abstract
Background: Ischemia/reperfusion (I/R) caused by ischemic stroke treatments leads to brain injury, and autophagy plays a role in the pathology. Astragaloside IV is a potential neuroprotectant, but its underlying mechanism on cerebral I/R injury needs to be explored. The objective of this study [...] Read more.
Background: Ischemia/reperfusion (I/R) caused by ischemic stroke treatments leads to brain injury, and autophagy plays a role in the pathology. Astragaloside IV is a potential neuroprotectant, but its underlying mechanism on cerebral I/R injury needs to be explored. The objective of this study is to investigate the neuroprotective mechanism of Astragaloside IV against cerebral I/R injury. Methods: Middle cerebral artery occlusion method (MCAO) and oxygen and glucose deprivation/reoxygenation (OGD/R) method were used to simulate cerebral I/R injury in Sprague-Dawley (SD) rats and HT22 cells, respectively. The neurological score, 2,3,5-Triphe-nyltetrazolium chloride (TTC) staining, and transmission electron microscope were used to detect cerebral damage in SD rats. Cell viability and cytotoxicity assay were tested in vitro. Fluorescent staining and flow cytometry were applied to detect the level of apoptosis. Western blotting was conducted to examine the expression of proteins associated with autophagy. Results: This study found that Astragaloside IV could decrease the neurological score, reduce the infarct volume in the brain, and alleviate cerebral I/R injury in MCAO rats. Astragaloside IV promoted cell viability and balanced Bcl-2 and Bax expression in vitro, reduced the rate of apoptosis, decreased the expression of P62, and increased the expression of LC3II/LC3I in HT22 cells after OGD/R. Conclusions: These data suggested that Astragaloside IV plays a neuroprotective role by down-regulating apoptosis by promoting the degree of autophagy. Full article
(This article belongs to the Special Issue Discovery of Active Ingredients from Natural Products)
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Open AccessArticle
Calcium-Dependent Protein Kinase Genes in Glycyrrhiza Uralensis Appear to be Involved in Promoting the Biosynthesis of Glycyrrhizic Acid and Flavonoids under Salt Stress
Molecules 2019, 24(9), 1837; https://doi.org/10.3390/molecules24091837
Received: 11 April 2019 / Revised: 4 May 2019 / Accepted: 5 May 2019 / Published: 13 May 2019
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Abstract
As calcium signal sensors, calcium-dependent protein kinases (CPKs) play vital roles in stimulating the production of secondary metabolites to participate in plant development and response to environmental stress. However, investigations of the Glycyrrhiza uralensis CPK family genes and their multiple functions are rarely [...] Read more.
As calcium signal sensors, calcium-dependent protein kinases (CPKs) play vital roles in stimulating the production of secondary metabolites to participate in plant development and response to environmental stress. However, investigations of the Glycyrrhiza uralensis CPK family genes and their multiple functions are rarely reported. In this study, a total of 23 GuCPK genes in G. uralensis were identified, and their phylogenetic relationships, evolutionary characteristics, gene structure, motif distribution, and promoter cis-acting elements were analyzed. Ten GuCPKs showed root-specific preferential expressions, and GuCPKs indicated different expression patterns under treatments of CaCl2 and NaCl. In addition, under 2.5 mM of CaCl2 and 30 mM of NaCl treatments, the diverse, induced expression of GuCPKs and significant accumulations of glycyrrhizic acid and flavonoids suggested the possible important function of GuCPKs in regulating the production of glycyrrhizic acid and flavonoids. Our results provide a genome-wide characterization of CPK family genes in G. uralensis, and serve as a foundation for understanding the potential function and regulatory mechanism of GuCPKs in promoting the biosynthesis of glycyrrhizic acid and flavonoids under salt stress. Full article
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Open AccessReview
Terrestrial Microorganisms: Cell Factories of Bioactive Molecules with Skin Protecting Applications
Molecules 2019, 24(9), 1836; https://doi.org/10.3390/molecules24091836
Received: 28 March 2019 / Revised: 18 April 2019 / Accepted: 23 April 2019 / Published: 13 May 2019
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Abstract
It is well known that terrestrial environments host an immense microbial biodiversity. Exposed to different types of stress, such as UV radiation, temperature fluctuations, water availability and the inter- / intra-specific competition for resources, terrestrial microorganisms have been evolved to produce a large [...] Read more.
It is well known that terrestrial environments host an immense microbial biodiversity. Exposed to different types of stress, such as UV radiation, temperature fluctuations, water availability and the inter- / intra-specific competition for resources, terrestrial microorganisms have been evolved to produce a large spectrum of bioactive molecules. Bacteria, archaea, protists, fungi and algae have shown a high potential of producing biomolecules for pharmaceutical or other industrial purposes as they combine a sustainable, relatively low-cost and fast-production process. Herein, we provide an overview of the different bioactive molecules produced by terrestrial microorganisms with skin protecting applications. The high content in polyphenolic and carotenoid compounds produced by several strains, as well as the presence of exopolysaccharides, melanins, indole and pyrrole derivatives, mycosporines, carboxylic acids and other molecules, are discussed in the context of their antioxidant, photo-protective and skin-whitening activity. Relevant biotechnological tools developed for the enhanced production of high added value natural products, as well as the protecting effect of some antioxidant, hydrolytic and degrading enzymes are also discussed. Furthermore, we describe classes of microbial compounds that are used or have the potential to be used as antimicrobials, moisturizers, biosurfactants, pigments, flavorings and fragrances. Full article
(This article belongs to the Special Issue Microbial Natural Products)
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Open AccessArticle
Antiviral Effects of Houttuynia cordata Polysaccharide Extract on Murine Norovirus-1 (MNV-1)—A Human Norovirus Surrogate
Molecules 2019, 24(9), 1835; https://doi.org/10.3390/molecules24091835
Received: 4 March 2019 / Revised: 7 May 2019 / Accepted: 9 May 2019 / Published: 13 May 2019
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Abstract
Houttuynia cordata is an herbal plant rich in polysaccharides and with several pharmacological activities. Human noroviruses (HuNoVs) are the most common cause of foodborne viral gastroenteritis throughout the world. In this study, H. cordata polysaccharide (HP), with a molecular weight of ~43 kDa, [...] Read more.
Houttuynia cordata is an herbal plant rich in polysaccharides and with several pharmacological activities. Human noroviruses (HuNoVs) are the most common cause of foodborne viral gastroenteritis throughout the world. In this study, H. cordata polysaccharide (HP), with a molecular weight of ~43 kDa, was purified from H. cordata water extract (HWE). The polysaccharide HP was composed predominantly of galacturonic acid, galactose, glucose, and xylose in a molar ratio of 1.56:1.49:1.26:1.11. Methylation and NMR analyses revealed that HP was a pectin-like acidic polysaccharide mainly consisting of α-1,4-linked GalpA, β-1,4-linked Galp, β-1,4-linked Glcp, and β-1,4-linked Xylp residues. To evaluate the antiviral activity of H. cordata extracts, we compared the anti-norovirus potential of HP with HWE and ethanol extract (HEE) from H. cordata by plaque assay (plaque forming units (PFU)/mL) for murine norovirus-1 (MNV-1), a surrogate of HuNoVs. Viruses at high (8.09 log10 PFU/mL) or low (4.38 log10 PFU/mL) counts were mixed with 100, 250, and 500 μg/mL of HP, HWE or HEE and incubated for 30 min at room temperature. H. cordata polysaccharide (HP) was more effective than HEE in reducing MNV-1 plaque formation, but less effective than HWE. When MNV-1 was treated with 500 μg/mL HP, the infectivity of MNV-1 decreased to an undetectable level. The selectivity indexes of each sample were 1.95 for HEE, 5.74 for HP, and 16.14 for HWE. The results of decimal reduction time and transmission electron microscopic revealed that HP has anti-viral effects by deforming and inflating virus particles, thereby inhibiting the penetration of viruses in target cells. These findings suggest that HP might have potential as an antiviral agent in the treatment of viral diseases. Full article
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Open AccessArticle
The Effect of Hemicellulose and Lignin on Properties of Polysaccharides in Lentinus edodes and Their Antioxidant Evaluation
Molecules 2019, 24(9), 1834; https://doi.org/10.3390/molecules24091834
Received: 30 March 2019 / Revised: 24 April 2019 / Accepted: 24 April 2019 / Published: 13 May 2019
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Abstract
Lentinus edodes, whose polysaccharides possess diverse bioactivities, commonly grows on hardwood sawdust composed of hemicellulose, lignin and cellulose. In this study the effect of hemicellulose and lignin on the growth of mycelia, as well as the physicochemical properties of polysaccharides from L. [...] Read more.
Lentinus edodes, whose polysaccharides possess diverse bioactivities, commonly grows on hardwood sawdust composed of hemicellulose, lignin and cellulose. In this study the effect of hemicellulose and lignin on the growth of mycelia, as well as the physicochemical properties of polysaccharides from L. edodes mycelia (LEPs) were investigated. The antioxidant properties of LEPs were evaluated through radical scavenging assays in vitro and through the Caenorhabditis elegans model in vivo. The results showed that hemicellulose at a concentration of 4% increased the yield of the mycelia biomass to twice that of the control group. Meanwhile, when cultured with 4.0% hemicellulose, the polysaccharide content of the mycelia was raised by 112.2%. In addition, the appropriate concentration of lignin could stimulate mycelia growth and polysaccharide biosynthesis in L. edodes. Monosaccharide composition analysis showed that a higher content of xylose was found when mycelia were cultured with higher concentrations of hemicellulose. The molecular structure, including the molecular weight distribution and configuration type, was affected by hemicellulose and lignin. Antioxidant assays indicated that LEPs supplemented with hemicellulose and/or lignin possessed higher radical scavenging abilities in vitro and exhibited a thermal resistance effect on C. elegans, implying that the antioxidant effect is potent in vivo. In summary, the addition of hemicellulose and lignin improved the biosynthesis and bioactivity of LEPs. Full article
(This article belongs to the Special Issue Herbal Carbohydrates: Chemistry, Biology and Application)
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Open AccessArticle
Autophagy-Related Proteins GABARAP and LC3B Label Structures of Similar Size but Different Shape in Super-Resolution Imaging
Molecules 2019, 24(9), 1833; https://doi.org/10.3390/molecules24091833
Received: 20 March 2019 / Revised: 7 May 2019 / Accepted: 7 May 2019 / Published: 13 May 2019
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Abstract
Subcellular structures containing autophagy-related proteins of the Atg8 protein family have been investigated with conventional wide-field fluorescence and single molecule localisation microscopy. Fusion proteins of GABARAP and LC3B, respectively, with EYFP were overexpressed in HEK293 cells. While size distributions of structures labelled by [...] Read more.
Subcellular structures containing autophagy-related proteins of the Atg8 protein family have been investigated with conventional wide-field fluorescence and single molecule localisation microscopy. Fusion proteins of GABARAP and LC3B, respectively, with EYFP were overexpressed in HEK293 cells. While size distributions of structures labelled by the two proteins were found to be similar, shape distributions appeared quite disparate, with EYFP-GABARAP favouring circular structures and elliptical structures being dominant for EYFP-LC3B. The latter also featured a nearly doubled fraction of U-shape structures. The experimental results point towards highly differential localisation of the two proteins, which appear to label structures representing distinct stages or even specific channels of vesicular trafficking pathways. Our data also demonstrate that the application of super-resolution techniques expands the possibilities of fluorescence-based methods in autophagy studies and in some cases can rectify conclusions obtained from conventional fluorescence microscopy with diffraction-limited resolution. Full article
(This article belongs to the Special Issue Single-Molecule Fluorescence Spectroscopy)
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Open AccessArticle
Eco-Friendly Ca-Montmorillonite Grafted by Non-Acidic Ionic Liquid Used as A Solid Acid Catalyst in Cellulose Hydrolysis to Reducing Sugars
Molecules 2019, 24(9), 1832; https://doi.org/10.3390/molecules24091832
Received: 19 April 2019 / Revised: 8 May 2019 / Accepted: 13 May 2019 / Published: 13 May 2019
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Abstract
An effective and friendly method was developed for the production of reducing sugars (RS) from the hydrolysis of cellulose over the solid catalyst of Ca-montmorillonite (Mt) grafted by non-acidic ionic liquid (Mt-IL) in water. The effect of mass ratio, water dosage, reaction temperature, [...] Read more.
An effective and friendly method was developed for the production of reducing sugars (RS) from the hydrolysis of cellulose over the solid catalyst of Ca-montmorillonite (Mt) grafted by non-acidic ionic liquid (Mt-IL) in water. The effect of mass ratio, water dosage, reaction temperature, and time were investigated in a batch reactor. Raw Mt showed only a 7.9% total reducing sugars (TRS) yield for the catalytic hydrolysis of cellulose in water. As the Mt was grafted by -SO3H and IL, the TRS yield greatly increased under the same reaction conditions. The highest TRS yield of 35.7% was obtained on the catalyst of Mt grafted by non-acidic IL at 200 °C with the mass ratio of catalyst to cellulose of 0.2 for 120 min. The high TRS yield for Mt-IL should be attributed to the synergistic effect of the dissolution of cellulose by IL and the exposed metal ions on the layer with water. Although the yield of TRS on Mt-IL decreased gradually with recycling runs, the decrease after the first run was not very serious compared to the fresh catalyst. This work provides a promising strategy for efficient cellulose hydrolysis into fine chemicals by Mt with non-acidic IL. Full article
(This article belongs to the Section Natural Products Chemistry)
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Open AccessArticle
A NMR-Based Metabonomics Approach to Determine Protective Effect of a Combination of Multiple Components Derived from Naodesheng on Ischemic Stroke Rats
Molecules 2019, 24(9), 1831; https://doi.org/10.3390/molecules24091831
Received: 6 March 2019 / Revised: 24 April 2019 / Accepted: 10 May 2019 / Published: 13 May 2019
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Abstract
Naodesheng (NDS) is a widely used traditional Chinese medicine (TCM) prescription for the treatment of ischemic stroke. A combination of 10 components is derived from NDS. They are: Notoginsenoside R1, ginsenoside Rg1, ginsenoside b1, ginsenoside Rd, hydroxysafflor yellow A, senkyunolide I, puerarin, daidzein, [...] Read more.
Naodesheng (NDS) is a widely used traditional Chinese medicine (TCM) prescription for the treatment of ischemic stroke. A combination of 10 components is derived from NDS. They are: Notoginsenoside R1, ginsenoside Rg1, ginsenoside b1, ginsenoside Rd, hydroxysafflor yellow A, senkyunolide I, puerarin, daidzein, vitexin, and ferulic acid. This study aimed to investigate the protective effect of the ten-component combination derived from NDS (TCNDS) on ischemic stroke rats with a middle cerebral artery occlusion (MCAO) model by integrating an NMR-based metabonomics approach with biochemical assessment. Our results showed that TCNDS could improve neurobehavioral function, decrease the cerebral infarct area, and ameliorate pathological features in MCAO model rats. In addition, TCNDS was found to decrease plasma lactate dehydrogenase (LDH) and malondialdehyde (MDA) production and increase plasma superoxide dismutase (SOD) production. Furthermore, 1H-NMR metabonomic analysis indicated that TCNDS could regulate the disturbed metabolites in the plasma, urine, and brain tissue of MCAO rats, and the possible mechanisms were involved oxidative stress, energy metabolism, lipid metabolism, amino acid metabolism, and inflammation. Correlation analysis were then performed to further confirm the metabolites involved in oxidative stress. Correlation analysis showed that six plasma metabolites had high correlations with plasma LDH, MDA, and SOD. This study provides evidence that an NMR-based metabonomics approach integrated with biochemical assessment can help to better understand the underlying mechanisms as well as the holistic effect of multiple compounds from TCM. Full article
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Open AccessArticle
Development of an Accelerated Solvent Extraction-Ultra-Performance Liquid Chromatography-Fluorescence Detection Method for Quantitative Analysis of Thiamphenicol, Florfenicol and Florfenicol Amine in Poultry Eggs
Molecules 2019, 24(9), 1830; https://doi.org/10.3390/molecules24091830
Received: 13 April 2019 / Revised: 5 May 2019 / Accepted: 10 May 2019 / Published: 13 May 2019
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Abstract
A simple, rapid and novel method for the detection of residues of thiamphenicol (TAP), florfenicol (FF) and its metabolite, florfenicol amine (FFA), in poultry eggs by ultra-performance liquid chromatography-fluorescence detection (UPLC-FLD) was developed. The samples were extracted with acetonitrile-ammonia (98:2, v/v) using [...] Read more.
A simple, rapid and novel method for the detection of residues of thiamphenicol (TAP), florfenicol (FF) and its metabolite, florfenicol amine (FFA), in poultry eggs by ultra-performance liquid chromatography-fluorescence detection (UPLC-FLD) was developed. The samples were extracted with acetonitrile-ammonia (98:2, v/v) using accelerated solvent extraction (ASE) and purified by manual degreasing with acetonitrile-saturated n-hexane. The target compounds were separated on an ACQUITY UPLC® BEH C18 (2.1 mm × 100 mm, 1.7 μm) chromatographic column using a mobile phase composed of 0.005 mol/L NaH2PO4, 0.003 mol/L sodium lauryl sulfate and 0.05% trimethylamine, adjusted to pH 5.3 ± 0.1 by phosphoric acid and acetonitrile (64:36, v/v). The limits of detection (LODs) and limits of quantification (LOQs) of the three target compounds in poultry eggs were 1.8–4.9 µg/kg and 4.3–11.7 µg/kg, respectively. The recoveries of the three target compounds in poultry eggs were above 80.1% when the spiked concentrations of three phenicols were the LOQ, 0.5 maximum residue limit (MRL), 1.0 MRL and 2.0 MRL. The intraday relative standard deviations (RSDs) were less than 5.5%, and the interday RSDs were less than 6.6%. Finally, this new detection method was successfully applied to the quantitative analysis of TAP, FF and FFA in 150 commercial poultry eggs. Full article
(This article belongs to the Special Issue Advances in Food Analysis)
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Open AccessArticle
RA-XII Suppresses the Development and Growth of Liver Cancer by Inhibition of Lipogenesis via SCAP-dependent SREBP Supression
Molecules 2019, 24(9), 1829; https://doi.org/10.3390/molecules24091829
Received: 9 April 2019 / Revised: 29 April 2019 / Accepted: 1 May 2019 / Published: 12 May 2019
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Abstract
Lipogenesis plays a critical role in the growth and metastasis of tumors, which is becoming an attractive target for anti-tumor drugs. RA-XII, one of the cyclopeptide glycosides isolated from Rubia yunnanensis, exerts anti-tumor effects on liver cancer. However, the underlying mechanisms are [...] Read more.
Lipogenesis plays a critical role in the growth and metastasis of tumors, which is becoming an attractive target for anti-tumor drugs. RA-XII, one of the cyclopeptide glycosides isolated from Rubia yunnanensis, exerts anti-tumor effects on liver cancer. However, the underlying mechanisms are not clear. In the present study, the effects of RA-XII on lipogenesis were evaluated and the underlying mechanisms were investigated. The results indicated that RA-XII strongly inhibited tumor growth and lipogenesis (triglycerides and lipid droplets) in HepG2 cells, and the expression of key factors involved in lipogenesis (SREBP, SCD, FASN) was also obviously downregulated. Further investigation showed that the anti-tumor effects of RA-XII were attenuated by SREBP knockdown. Moreover, RA-XII downregulated the expression of SREBP cleavage-activating protein (SCAP), an upstream regulator of SREBP, and siRNA of SCAP prevented its restrained effects on tumor growth and lipogenesis. In addition, the in vivo experiment showed that RA-XII strongly restrained the lipogenesis and growth of liver tumor in nude mice xenograft model. Taken together, these results indicate that RA-XII suppresses the liver cancer growth by inhibition of lipogenesis via SCAP-dependent SREBP suppression. The findings reveal the potentials of RA-XII to be used in a novel therapeutic approach for treating liver cancer. Full article
(This article belongs to the Special Issue Recent Advances in Anticancer Drugs)
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Open AccessArticle
Optical Resolution of Rimantadine
Molecules 2019, 24(9), 1828; https://doi.org/10.3390/molecules24091828
Received: 20 April 2019 / Revised: 6 May 2019 / Accepted: 11 May 2019 / Published: 12 May 2019
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Abstract
This work discloses a new procedure for the resolution of commercially available racemic rimantadine hydrochloride to enantiomerically pure (S)-rimantadine using (R)-phenoxypropionic acid as a recyclable resolving reagent. Good chemical yields, operational ease, and low-cost structure underscore the preparative value [...] Read more.
This work discloses a new procedure for the resolution of commercially available racemic rimantadine hydrochloride to enantiomerically pure (S)-rimantadine using (R)-phenoxypropionic acid as a recyclable resolving reagent. Good chemical yields, operational ease, and low-cost structure underscore the preparative value of this method for the production of enantiomerically pure rimantadine for medicinal or synthetic studies. Full article
(This article belongs to the Section Bioorganic Chemistry)
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Open AccessArticle
Targeting Caspase 8: Using Structural and Ligand-Based Approaches to Identify Potential Leads for the Treatment of Multi-Neurodegenerative Diseases
Molecules 2019, 24(9), 1827; https://doi.org/10.3390/molecules24091827
Received: 11 April 2019 / Revised: 7 May 2019 / Accepted: 11 May 2019 / Published: 12 May 2019
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Abstract
Caspase 8 is a central player in the apoptotic cell death pathway and is also essential for cytokine processing. The critical role of this protease in cell death pathways has generated research interest because its activation has also been linked with neural cell [...] Read more.
Caspase 8 is a central player in the apoptotic cell death pathway and is also essential for cytokine processing. The critical role of this protease in cell death pathways has generated research interest because its activation has also been linked with neural cell death. Thus, blocking the activity of caspase 8 is considered a potential therapy for neurodegenerative diseases. To extend the repertoire of caspase 8 inhibitors, we employed several computational approaches to identify potential caspase 8 inhibitors. Based on the structural information of reported inhibitors, we designed several individual and consensus pharmacophore models and then screened the ZINC database, which contains 105,480 compounds. Screening generated 5332 candidates, but after applying stringent criteria only two candidate compounds, ZINC19370490 and ZINC04534268, were evaluated by molecular dynamics simulations and subjected to Molecular Mechanics/Poisson Boltzmann Surface Area (MM-PBSA) analysis. These compounds were stable throughout simulations and interacted with targeted protein by forming hydrogen and van der Waal bonds. MM-PBSA analysis showed that these compounds were comparable or better than reported caspase 8 inhibitors. Furthermore, their physical properties were found to be acceptable, and they are non-toxic according to the ADMET online server. We suggest that the inhibitory efficacies of ZINC19370490 and ZINC04534268 be subjected to experimental validation. Full article
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Open AccessArticle
Exogenous Melatonin Enhances Cold, Salt and Drought Stress Tolerance by Improving Antioxidant Defense in Tea Plant (Camellia sinensis (L.) O. Kuntze)
Molecules 2019, 24(9), 1826; https://doi.org/10.3390/molecules24091826
Received: 25 April 2019 / Revised: 9 May 2019 / Accepted: 10 May 2019 / Published: 12 May 2019
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Abstract
Melatonin is a biological hormone that plays crucial roles in stress tolerance. In this study, we investigated the effect of exogenous melatonin on abiotic stress in the tea plant. Under cold, salt and drought stress, increasing malondialdehyde levels and decreasing maximum photochemical efficiency [...] Read more.
Melatonin is a biological hormone that plays crucial roles in stress tolerance. In this study, we investigated the effect of exogenous melatonin on abiotic stress in the tea plant. Under cold, salt and drought stress, increasing malondialdehyde levels and decreasing maximum photochemical efficiency of PSII were observed in tea leaves. Meanwhile, the levels of reactive oxygen species (ROS) increased significantly under abiotic stress. Interestingly, pretreatment with melatonin on leaves alleviated ROS burst, decreased malondialdehyde levels and maintain high photosynthetic efficiency. Moreover, 100 μM melatonin-pretreated tea plants showed high levels of glutathione and ascorbic acid and increased the activities of superoxide dismutase, peroxidase, catalase and ascorbate peroxidase under abiotic stress. Notably, melatonin treatments can positively up-regulate the genes (CsSOD, CsPOD, CsCAT and CsAPX) expression of antioxidant enzyme biosynthesis. Taken together, our results confirmed that melatonin protects tea plants against abiotic stress-induced damages through detoxifying ROS and regulating antioxidant systems. Full article
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Open AccessArticle
ICAM3-Fc Outperforms Receptor-Specific Antibodies Targeted Nanoparticles to Dendritic Cells for Cross-Presentation
Molecules 2019, 24(9), 1825; https://doi.org/10.3390/molecules24091825
Received: 9 April 2019 / Revised: 7 May 2019 / Accepted: 8 May 2019 / Published: 12 May 2019
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Abstract
Optimal targeting of nanoparticles (NP) to dendritic cells (DCs) receptors to deliver cancer-specific antigens is key to the efficient induction of anti-tumour immune responses. Poly (lactic-co-glycolic acid) (PLGA) nanoparticles containing tètanus toxoid and gp100 melanoma-associated antigen, toll-like receptor adjuvants were targeted to the [...] Read more.
Optimal targeting of nanoparticles (NP) to dendritic cells (DCs) receptors to deliver cancer-specific antigens is key to the efficient induction of anti-tumour immune responses. Poly (lactic-co-glycolic acid) (PLGA) nanoparticles containing tètanus toxoid and gp100 melanoma-associated antigen, toll-like receptor adjuvants were targeted to the DC-SIGN receptor in DCs by specific humanized antibodies or by ICAM3-Fc fusion proteins, which acts as the natural ligand. Despite higher binding and uptake efficacy of anti-DC-SIGN antibody-targeted NP vaccines than ICAM3-Fc ligand, no difference were observed in DC activation markers CD80, CD83, CD86 and CCR7 induced. DCs loaded with NP coated with ICAM3-Fc appeared more potent in activating T cells via cross-presentation than antibody-coated NP vaccines. This fact could be very crucial in the design of new cancer vaccines. Full article
(This article belongs to the Section Nanochemistry)
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Open AccessArticle
The Effect of Furanocoumarin Derivatives on Induction of Apoptosis and Multidrug Resistance in Human Leukemic Cells
Molecules 2019, 24(9), 1824; https://doi.org/10.3390/molecules24091824
Received: 30 April 2019 / Revised: 8 May 2019 / Accepted: 9 May 2019 / Published: 12 May 2019
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Abstract
Background: The insensitivity of cancer cells to therapeutic agents is considered to be the main cause of failure of therapy and mortality of patients with cancer. A particularly important problem in these patients is the phenomenon of multidrug resistance, consisting of abnormal, elevated [...] Read more.
Background: The insensitivity of cancer cells to therapeutic agents is considered to be the main cause of failure of therapy and mortality of patients with cancer. A particularly important problem in these patients is the phenomenon of multidrug resistance, consisting of abnormal, elevated expression of transport proteins (ABC family). The aim of this research included determination of IC50 values of selected furanocoumarins in the presence and absence of mitoxantrone in leukemia cells and analysis of changes in apoptosis using anexinV/IP and Casp3/IP after 24 h exposure of cell lines to selected coumarins in the presence and absence of mitoxantrone in IC50 concentrations. Methods: Research was conducted on 3 cell lines derived from the human hematopoietic system: HL-60, HL-60/MX1 and HL-60/MX2. After exposure to coumarin compounds, cells were subjected to cytometric analysis to determine the induction of apoptosis by two methods: the Annexin V test with propidium iodide and the PhiPhiLux-G1D2 reagent containing caspase 3 antibodies. Results: All of the furanocoumarin derivatives studied were found to induce apoptosis in leukemia cell lines. Conclusions: Our results clearly show that the furanocoumarin derivatives are therapeutic substances with antitumor activity inducing apoptosis in human leukemia cells with phenotypes of resistance. Full article
(This article belongs to the Special Issue Coumarins and Coumarin Derivatives: From Chemistry to Drug)
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Open AccessArticle
Evaluation of Transition Metal Catalysts in Electrochemically Induced Aromatic Phosphonation
Molecules 2019, 24(9), 1823; https://doi.org/10.3390/molecules24091823
Received: 22 April 2019 / Revised: 8 May 2019 / Accepted: 9 May 2019 / Published: 11 May 2019
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Abstract
Voltammetry provides important information on the redox properties of catalysts (transition metal complexes of Ni, Co, Mn, etc.) and their activity in electrocatalytic reactions of aromatic C–H phosphonation in the presence of a phosphorus precursor, for example, dialkyl-H-phosphonate. Based on catalytic [...] Read more.
Voltammetry provides important information on the redox properties of catalysts (transition metal complexes of Ni, Co, Mn, etc.) and their activity in electrocatalytic reactions of aromatic C–H phosphonation in the presence of a phosphorus precursor, for example, dialkyl-H-phosphonate. Based on catalytic current growth of oxidation or reduction of the metal catalysts (CoII, MnII, NiII, MnII/NiII, MnII/CoII, and CoII/NiII), quantitative characteristics of the regeneration of catalysts were determined, for example, for MnII, NiII and MnII/NiII, CoII/NiII pairs. Calculations confirmed the previously made synthetic observations on the synergistic effect of certain metal ions in binary catalytic systems (MnIIbpy/NiIIbpy and NiIIbpy/CoIIbpy); for mixtures, the observed rate constants, or TOF, were 690 s−1 and 721 s−1, respectively, and product yields were higher for monometallic catalytic systems (up to 71% for bimetallic catalytic systems and ~30% for monometallic catalytic systems). In some cases, the appearance of pre-waves after adding H-phosphonates confirmed the preceding chemical reaction. It also confirmed the formation of metal phosphonates in the time scale of voltammetry, oxidizing or reducing at lower potentials than the original (RO)2P(O)H and metal complex, which could be used for fast diagnostics of metal ion and dialkyl-H-phosphonate interactions. Electrochemical transfer of an electron to (from) metal phosphonate generates a phosphonyl radical, which can then react with different arenes to give the products of aromatic C–H phosphonation. Full article
(This article belongs to the Special Issue Organic Electrochemistry 2019)
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Open AccessArticle
Selective Adsorption-Based Separation of Flue Gas and Natural Gas in Zirconium Metal-Organic Frameworks Nanocrystals
Molecules 2019, 24(9), 1822; https://doi.org/10.3390/molecules24091822
Received: 6 May 2019 / Accepted: 8 May 2019 / Published: 11 May 2019
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Abstract
Carbon capture from flue gas and natural gas offers a green path to construct a net-zero emissions economic system. Selective adsorption-based gas separation by employing metal-organic frameworks (MOFs) is regarded as a promising technology due to the advantages of simple processing, easy regeneration [...] Read more.
Carbon capture from flue gas and natural gas offers a green path to construct a net-zero emissions economic system. Selective adsorption-based gas separation by employing metal-organic frameworks (MOFs) is regarded as a promising technology due to the advantages of simple processing, easy regeneration and high efficiency. We synthesized two Zirconium MOFs (UiO-66 and UiO-66-NH2) nanocrystals for selective capture and further removal of CO2 from flue gas and natural gas. In particular, UiO-66-NH2 nanocrystals have a smaller grain size, a large amount of defects, and pending –NH2 groups inside their pores which display effective CO2 selective adsorption abilities over CH4 and N2 with the theoretical separation factors of 20 and 7. This breakthrough experiment further verified the selective adsorption-based separation process of natural gas and flue gas. In one further step, we used the Monte Carlo simulation to investigate the optimized adsorption sites and energy of CO2, N2 and CH4 molecules in the gas mixture. The significantly large adsorption energy of CO2 (0.32 eV) over N2 (0.19 eV) and N2 (0.2 eV) may help us to reveal the selective adsorption mechanism. Full article
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Open AccessArticle
Symbiotic Aerogel Fibers Made via In-Situ Gelation of Aramid Nanofibers with Polyamidoxime for Uranium Extraction
Molecules 2019, 24(9), 1821; https://doi.org/10.3390/molecules24091821
Received: 16 April 2019 / Revised: 4 May 2019 / Accepted: 9 May 2019 / Published: 11 May 2019
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Abstract
The uranium reserve in seawater is enormous, but its concentration is extremely low and plenty of interfering ions exist; therefore, it is a great challenge to extract uranium from seawater with high efficiency and high selectivity. In this work, a symbiotic aerogel fiber [...] Read more.
The uranium reserve in seawater is enormous, but its concentration is extremely low and plenty of interfering ions exist; therefore, it is a great challenge to extract uranium from seawater with high efficiency and high selectivity. In this work, a symbiotic aerogel fiber (i.e., [email protected]) based on polyamidoxime (PAO) and aramid nanofiber (ANF) is designed and fabricated via in-situ gelation of ANF with PAO in dimethyl sulfoxide and subsequent freeze-drying of the corresponding fibrous gel precursor. The resulting flexible porous aerogel fiber possesses high specific surface area (up to 165 m2·g−1), excellent hydrophilicity and high tensile strength (up to 4.56 MPa) as determined by BET, contact angle, and stress-strain measurements. The batch adsorption experiments indicate that the [email protected] aerogel fibers possess a maximal adsorption capacity of uranium up to 262.5 mg·g−1, and the absorption process is better fitted by the pseudo-second-order kinetics model and Langmuir isotherm model, indicating an adsorption mechanism of the monolayer chemical adsorption. Moreover, the [email protected] aerogel fibers exhibit selective adsorption to uranium in the presence of coexisting ions, and they could well maintain good adsorption ability and integrated porous architecture after five cycles of adsorption–desorption process. It would be expected that the symbiotic aerogel fiber could be produced on a large scale and would find promising application in uranium ion extraction from seawater. Full article
(This article belongs to the Special Issue Engineering of Aerogels and Their Applications)
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Open AccessArticle
Exploring the Use of Amine Modified Mesoporous Magnesium Carbonate for the Delivery of Salicylic Acid in Topical Formulations: In Vitro Cytotoxicity and Drug Release Studies
Molecules 2019, 24(9), 1820; https://doi.org/10.3390/molecules24091820
Received: 10 April 2019 / Revised: 9 May 2019 / Accepted: 10 May 2019 / Published: 11 May 2019
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Abstract
Salicylic acid (SA) has for a long time been used to treat various skin disorders due to its anti-inflammatory, bacteriostatic, and antifungal properties. In the present work, mesoporous magnesium carbonate (MMC), a promising drug carrier, was modified with 3-aminopropyl-triethoxysilane to enable loading of [...] Read more.
Salicylic acid (SA) has for a long time been used to treat various skin disorders due to its anti-inflammatory, bacteriostatic, and antifungal properties. In the present work, mesoporous magnesium carbonate (MMC), a promising drug carrier, was modified with 3-aminopropyl-triethoxysilane to enable loading of SA. The amine modified MMC (aMMC) was successfully loaded with 8 wt.% of SA via a solvent evaporation method. SA was later completely released from the carrier in less than 15 min. Furthermore, the cytotoxicity of the functionalized material was evaluated. aMMC was found to be non-toxic for human dermal fibroblast cells with particle concentration of up to 1000 µg/mL when exposed for 48 h. The presented results form the basis of future development of aMMC as a potential carrier for SA in dermatological applications. Full article
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Open AccessArticle
Study on the Emulsifying Properties of Pomegranate Peel Pectin from Different Cultivation Areas
Molecules 2019, 24(9), 1819; https://doi.org/10.3390/molecules24091819
Received: 10 April 2019 / Revised: 1 May 2019 / Accepted: 8 May 2019 / Published: 10 May 2019
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Abstract
Pomegranate peel pectin is an important acidic anionic plant polysaccharide which can be used as a natural emulsifier. In order to study its emulsifying properties, this paper systematically analyses pomegranate peel pectin samples from Chinese Xinjiang, Sichuan and Yunnan provinces, through rheometer, interfacial [...] Read more.
Pomegranate peel pectin is an important acidic anionic plant polysaccharide which can be used as a natural emulsifier. In order to study its emulsifying properties, this paper systematically analyses pomegranate peel pectin samples from Chinese Xinjiang, Sichuan and Yunnan provinces, through rheometer, interfacial rheometer, Zetasizer Nano-ZS and mastersizer. It is shown that pomegranate peel pectin can effectively reduce the oil-water interfacial tension, reaching an emulsion droplet size of only 0.507 μm, 0.669 μm and 0.569 μm, respectively, while the pectin concentration is 1.5% and the oil phase (MCT) is 10%. It has also shown that the extreme conditions of pH and ion strength can not significantly change its emulsion stability. However, freeze-thaw cycles can cause the pomegranate peel pectin emulsion to become less stable. Furthermore, the effects of decolourization, protein removal and dialysis on the emulsifying properties of pomegranate peel pectin are investigated using mastersizer rheometer and interfacial rheometer. It is found that the protein and pigment in pomegranate peel pectin have little effect on its emulsifying properties, while the results from dialyzed pectin show that the small molecule substances can reduce the emulsion particle size and increase the emulsion stability. The research outcomes of this study provide technical support for the further application of pomegranate peel pectin in the food industry. Full article
(This article belongs to the Special Issue Natural Products Used as Foods and Food Ingredients)
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Open AccessArticle
Cardanol and Eugenol Based Flame Retardant Epoxy Monomers for Thermostable Networks
Molecules 2019, 24(9), 1818; https://doi.org/10.3390/molecules24091818
Received: 10 April 2019 / Revised: 3 May 2019 / Accepted: 7 May 2019 / Published: 10 May 2019
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Abstract
Epoxy materials have attracted attention for many applications that require fireproof performance; however, the utilization of hazardous reagents brings about potential damage to human health. Eugenol and cardanol are renewable, harmless resources (according to ECHA) that allow the achievement of synthesis of novel [...] Read more.
Epoxy materials have attracted attention for many applications that require fireproof performance; however, the utilization of hazardous reagents brings about potential damage to human health. Eugenol and cardanol are renewable, harmless resources (according to ECHA) that allow the achievement of synthesis of novel phosphorylated epoxy monomers to be used as reactive flame retardants. These epoxy building blocks are characterized by 1H NMR and 31P NMR (nuclear magnetic resonance) and reacted with a benzylic diamine to give bio-based flame-retardant thermosets. Compared to DGEBA (Bisphenol A Diglycidyl Ether)-based material, these biobased thermosets differ by their cross-linking ratio, the nature of the phosphorylated function and the presence of an aliphatic chain. Eugenol has led to thermosets with higher glass transition temperatures due to a higher aromatic density. The flame-retardant properties were tested by thermogravimetric analyses (TGA), a pyrolysis combustion flow calorimeter (PCFC) and a cone calorimeter. These analyses demonstrated the efficiency of phosphorus by reducing significantly the peak heat release rate (pHRR), the total heat release (THR) and the effective heat of combustion (EHC). Moreover, the cone calorimeter test exhibited an intumescent phenomenon with the residues of phosphorylated eugenol thermosets. Lastly, the higher flame inhibition potential was highlighted for the phosphonate thermoset. Full article
(This article belongs to the Special Issue Innovative Flame Retardants)
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Open AccessArticle
Seven New Drimane-Type Sesquiterpenoids from a Marine-Derived Fungus Paraconiothyrium sporulosum YK-03
Molecules 2019, 24(9), 1817; https://doi.org/10.3390/molecules24091817
Received: 9 April 2019 / Revised: 29 April 2019 / Accepted: 30 April 2019 / Published: 10 May 2019
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Abstract
Seven new drimane-type sesquiterpenoids, namely the sporulositols AD (14), 6-hydroxydiaporol (5), seco-sporulositol (6) and sporuloside (7) were isolated from the ethyl acetate extract of fermentation broth for a marine-derived fungus [...] Read more.
Seven new drimane-type sesquiterpenoids, namely the sporulositols AD (14), 6-hydroxydiaporol (5), seco-sporulositol (6) and sporuloside (7) were isolated from the ethyl acetate extract of fermentation broth for a marine-derived fungus Paraconiothyrium sporulosum YK-03. Their structures were elucidated by analysis of extensive spectroscopic data, and the absolute configurations were established by crystal X-ray diffraction analysis and comparisons of circular dichroism data. Among them, sporulositols AE (14) and seco-sporulositol (6) represent the first five examples of a unique class of drimanic mannitol derivatives, while compounds 6 and 7 may represent two new series of natural drimanes, possessing an aromatic ring with a rare 4,5-secodrimanic skeleton and an unusual CH3-15 rearranged drimanic α-D-glucopyranside, respectively. Furthermore, the origin of mannitol moiety was investigated by reliable HPLC and NMR analyses. Full article
(This article belongs to the Section Natural Products Chemistry)
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Open AccessArticle
Simultaneous Determination and Pharmacokinetic Characterization of Glycyrrhizin, Isoliquiritigenin, Liquiritigenin, and Liquiritin in Rat Plasma Following Oral Administration of Glycyrrhizae Radix Extract
Molecules 2019, 24(9), 1816; https://doi.org/10.3390/molecules24091816
Received: 12 April 2019 / Revised: 6 May 2019 / Accepted: 9 May 2019 / Published: 10 May 2019
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Abstract
Glycyrrhizae Radix is widely used as herbal medicine and is effective against inflammation, various cancers, and digestive disorders. We aimed to develop a sensitive and simultaneous analytical method for detecting glycyrrhizin, isoliquiritigenin, liquiritigenin, and liquiritin, the four marker components of Glycyrrhizae Radix extract [...] Read more.
Glycyrrhizae Radix is widely used as herbal medicine and is effective against inflammation, various cancers, and digestive disorders. We aimed to develop a sensitive and simultaneous analytical method for detecting glycyrrhizin, isoliquiritigenin, liquiritigenin, and liquiritin, the four marker components of Glycyrrhizae Radix extract (GRE), in rat plasma using liquid chromatography-tandem mass spectrometry and to apply this analytical method to pharmacokinetic studies. Retention times for glycyrrhizin, isoliquiritigenin, liquiritigenin, and liquiritin were 7.8 min, 4.1 min, 3.1 min, and 2.0 min, respectively, suggesting that the four analytes were well separated without any interfering peaks around the peak elution time. The lower limit of quantitation was 2 ng/mL for glycyrrhizin and 0.2 ng/mL for isoliquiritigenin, liquiritigenin, and liquiritin; the inter- and intra-day accuracy, precision, and stability were less than 15%. Plasma concentrations of glycyrrhizin, isoliquiritigenin, liquiritigenin, and liquiritin were quantified for 24 h after a single oral administration of 1 g/kg GRE to four rats. Among the four components, plasma concentration of glycyrrhizin was the highest and exhibited a long half-life (23.1 ± 15.5 h). Interestingly, plasma concentrations of isoliquiritigenin and liquiritigenin were restored to the initial concentration at 4–10 h after the GRE administration, as evidenced by liquiritin biotransformation into isoliquiritigenin and liquiritigenin, catalyzed by fecal lysate and gut wall enzymes. In conclusion, our analytical method developed for detecting glycyrrhizin, isoliquiritigenin, liquiritigenin, and liquiritin could be successfully applied to investigate their pharmacokinetic properties in rats and would be useful for conducting further studies on the efficacy, toxicity, and biopharmaceutics of GREs and their marker components. Full article
(This article belongs to the Special Issue Method Development and Validation in Food and Pharmaceutical Analysis)
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Open AccessOpinion
An Opinion Paper on Aerogels for Biomedical and Environmental Applications
Molecules 2019, 24(9), 1815; https://doi.org/10.3390/molecules24091815
Received: 2 April 2019 / Revised: 2 May 2019 / Accepted: 8 May 2019 / Published: 10 May 2019
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Abstract
Aerogels are a special class of nanostructured materials with very high porosity and tunable physicochemical properties. Although a few types of aerogels have already reached the market in construction materials, textiles and aerospace engineering, the full potential of aerogels is still to be [...] Read more.
Aerogels are a special class of nanostructured materials with very high porosity and tunable physicochemical properties. Although a few types of aerogels have already reached the market in construction materials, textiles and aerospace engineering, the full potential of aerogels is still to be assessed for other technology sectors. Based on current efforts to address the material supply chain by a circular economy approach and longevity as well as quality of life with biotechnological methods, environmental and life science applications are two emerging market opportunities where the use of aerogels needs to be further explored and evaluated in a multidisciplinary approach. In this opinion paper, the relevance of the topic is put into context and the corresponding current research efforts on aerogel technology are outlined. Furthermore, key challenges to be solved in order to create materials by design, reproducible process technology and society-centered solutions specifically for the two abovementioned technology sectors are analyzed. Overall, advances in aerogel technology can yield innovative and integrated solutions for environmental and life sciences which in turn can help improve both the welfare of population and to move towards cleaner and smarter supply chain solutions. Full article
(This article belongs to the Special Issue Engineering of Aerogels and Their Applications)
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Open AccessArticle
Dioxygen Activation with Molybdenum Complexes Bearing Amide-Functionalized Iminophenolate Ligands
Molecules 2019, 24(9), 1814; https://doi.org/10.3390/molecules24091814
Received: 17 April 2019 / Revised: 7 May 2019 / Accepted: 9 May 2019 / Published: 10 May 2019
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Abstract
Two novel iminophenolate ligands with amidopropyl side chains (HL2 and HL3) on the imine functionality have been synthesized in order to prepare dioxidomolybdenum(VI) complexes of the general structure [MoO2L2] featuring pendant internal hydrogen bond donors. For reasons [...] Read more.
Two novel iminophenolate ligands with amidopropyl side chains (HL2 and HL3) on the imine functionality have been synthesized in order to prepare dioxidomolybdenum(VI) complexes of the general structure [MoO2L2] featuring pendant internal hydrogen bond donors. For reasons of comparison, a previously published complex featuring n-butyl side chains (L1) was included in the investigation. Three complexes (13) obtained using these ligands (HL1HL3) were able to activate dioxygen in an in situ approach: The intermediate molybdenum(IV) species [MoO(PMe3)L2] is first generated by treatment with an excess of PMe3. Subsequent reaction with dioxygen leads to oxido peroxido complexes of the structure [MoO(O2)L2]. For the complex employing the ligand with the n-butyl side chain, the isolation of the oxidomolybdenum(IV) phosphino complex [MoO(PMe3)(L1)2] (4) was successful, whereas the respective Mo(IV) species employing the ligands with the amidopropyl side chains were found to be not stable enough to be isolated. The three oxido peroxido complexes of the structure [MoO(O2)L2] (911) were systematically compared to assess the influence of internal hydrogen bonds on the geometry as well as the catalytic activity in aerobic oxidation. All complexes were characterized by spectroscopic means. Furthermore, molecular structures were determined by single-crystal X-ray diffraction analyses of HL3, 13, 911 together with three polynuclear products {[MoO(L2)2]2(µ-O)} (7), {[MoO(L2)]4(µ-O)6} (8) and [C9H13N2O]4[Mo8O26]·6OPMe3 (12) which were obtained during the synthesis of reduced complexes of the type [MoO(PMe3)L2] (46). Full article
(This article belongs to the Special Issue Schiff Base and Its Metal Complexes)
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Open AccessArticle
Rapid Discovery of Illuminating Peptides for Instant Detection of Opioids in Blood and Body Fluids
Molecules 2019, 24(9), 1813; https://doi.org/10.3390/molecules24091813
Received: 15 April 2019 / Revised: 3 May 2019 / Accepted: 5 May 2019 / Published: 10 May 2019
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Abstract
The United States is currently experiencing an opioid crisis, with more than 47,000 deaths in 2017 due to opioid overdoses. Current approaches for opioid identification and quantification in body fluids include immunoassays and chromatographic methods (e.g., LC-MS, GC-MS), which require expensive instrumentation and [...] Read more.
The United States is currently experiencing an opioid crisis, with more than 47,000 deaths in 2017 due to opioid overdoses. Current approaches for opioid identification and quantification in body fluids include immunoassays and chromatographic methods (e.g., LC-MS, GC-MS), which require expensive instrumentation and extensive sample preparation. Our aim was to develop a portable point-of-care device that can be used for the instant detection of opioids in body fluids. Here, we reported the development of a morphine-sensitive fluorescence-based sensor chip to sensitively detect morphine in the blood using a homogeneous immunoassay without any washing steps. Morphine-sensitive illuminating peptides were identified using a high throughput one-bead one-compound (OBOC) combinatorial peptide library approach. The OBOC libraries contain a large number of random peptides with a molecular rotor dye, malachite green (MG), that are coupled to the amino group on the side chain of lysine at different positions of the peptides. The OBOC libraries were then screened for fluorescent activation under a confocal microscope, using an anti-morphine monoclonal antibody as the screening probe, in the presence and absence of free morphine. Using this novel three-step fluorescent screening assay, we were able to identify the peptide-beads that fluoresce in the presence of an anti-morphine antibody, but lost fluorescence when the free morphine was present. After the positive beads were decoded using automatic Edman microsequencing, the morphine-sensitive illuminating peptides were then synthesized in soluble form, functionalized with an azido group, and immobilized onto microfabricated PEG-array spots on a glass slide. The sensor chip was then evaluated for the detection of morphine in plasma. We demonstrated that this proof-of-concept platform can be used to develop fluorescence-based sensors against morphine. More importantly, this technology can also be applied to the discovery of other novel illuminating peptidic sensors for the detection of illicit drugs and cancer biomarkers in body fluids. Full article
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