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Tracing dynamic changes of heterogeneous cell wall components during xylem differentiation is essential for understanding the intricate architecture of wood cell walls at the individual secondary cell wall layer level. Here we employ histochemical- and immunological approaches to visualize the deposition of cellular polymers during xylem differentiation in Pinus bungeana. In axial tracheids, deposition of crystalline cellulose and glucomannan preceded xylan and lignin. Lignification was initiated in primary cell wall corners during development of the S 1 layer and intensified with cell wall thickening. Immunofluorescence labeling showed an earlier deposition of glucomannan than xylan with strong presence in S 1 layer corner regions at early stages of differentiation. Quantification of immunogold-labeled xylan and glucomannan showed distinct increasing trends during thickening of tracheid wall layers with xylan labeling of the S 1 and S 2 layers at the S 3 stage greater than the S 2 stage. Differential cell wall polymer deposition was evident in mature tracheid areas with glucomannan absent in warty layers. Pectins were highly concentrated in unlignified primary cell walls but decreased with axial tracheid wall differentiation. The sequence of polymer deposition in ray cells was similar but lagged behind axial tracheids with ray parenchyma remaining unlignified with thinner cell walls than ray tracheids., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Research on ancient adhesives from the South African Stone Age is expanding, driven by excellent preservation conditions of adhesives and the potential to address diverse archaeological questions. These adhesives are primarily characterized through microscopic and chemical analysis. Despite geographic variability, a consistently identified component is Podocarpus resin or tar. We challenge these identifications, considering another Podocarpaceae genus, Afrocarpus, and the Cupressaceae genus Widdringtonia. Gas Chromatography-Mass Spectrometry was employed to analyze molecular signatures of modern wood, tar, resin, and seed cones from these genera. The results form an extensive reference database and reveal challenges in distinguishing these genera based on the diterpenoid signature. While Podocarpus is frequently cited, we advocate for a broader classification as Podocarpaceae when phenolic diterpenoids are found in high abundances and pimaranes and abietanes in lower abundances, and Widdringtonia when the opposite is true. The study differentiates materials used in adhesive production, including leaves and wood, highlighting the significance of α,ω-dicarboxylic acids, hydroxy acids, n-alkanes, and alcohols. Tars produced from leaves are characterized by odd-numbered n-alkanes, while tars produced from twigs and branches are characterized by long-chain α,ω-dicarboxylic acids, hydroxy acids, and alcohols. Because the differences between these adhesives in terms of raw material procurement and production are great, a more nuanced and cautious approach that acknowledges the challenges in differentiating tree species on a molecular level and considers archaeological and environmental context is required., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Chasan et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

Objective: To investigate the effects of Araucaria sp. brown propolis (ABP) against trinitrobenzenesulfonic acid (TNBS)-induced colitis in rats., Methods: Animals received vehicle (1% DMSO, 1 ml/kg) or hydroalcoholic extract of ABP (hydroalcoholic extract of Araucaria sp. brown propolis (HEABP), 30, 100, and 300 mg/kg) orally, or dexamethasone (25 mg/kg, s.c.) for 5 days. On day 4, the animals received intracolonic TNBS (150 mg/kg), on day 6 they were euthanized. The weight of the animals, the macroscopic and microscopic colonic damage, reduced glutathione (GSH) and malondialdehyde (MDA) levels, and the activity of glutathione S-transferase (GST), catalase (CAT), superoxide dismutase (SOD), and myeloperoxidase (MPO) were measured in colon homogenate. The action of HEABP and two isolated compounds in neutrophil migration was recorded., Key Findings: HEABP (100 and 300 mg/kg), but not dexamethasone, decreased colonic lesion, and increased colonic mucin staining. In parallel, HEABP decreased MDA and restored GSH levels and the activity of SOD, CAT, and GST in the colon. A dose-dependent inhibition of MPO activity was observed (LogIC50 = 1.9). Moreover, HEBPA and the junicedric and abietic acids inhibited the neutrophil chemotaxis in vitro and HEBPA reduced neutrophil migration in vivo., Conclusion: HEABP may be promising in the therapies for inflammatory bowel diseases, reducing oxidative and inflammatory damage, especially mediated by neutrophils., (© The Author(s) 2024. Published by Oxford University Press on behalf of the Royal Pharmaceutical Society. All rights reserved. For commercial re-use, please contact reprints@oup.com for reprints and translation rights for reprints. All other permissions can be obtained through our RightsLink service via the Permissions link on the article page on our site—for further information please contact journals.permissions@oup.com.)

Due to integrated pollution prevention and control measures and the reduced burning of coal, air concentrations of mercury (Hg 0 ) are currently levelling off. In the future, however, evasion from land surfaces will probably reverse this trend. Reasons are the rising temperatures and the loss of forest cover caused by calamities, droughts, storms and wildfires. Plant leaves constitute an important matrix for the accumulation of gaseous mercury and uptake and re-volatilisation by plants depends on the species, the vitality and the age and morphology of leaf organs. It has been shown that older conifer needles show higher concentrations than young needles and Hg accumulation is increasing throughout the season. In present study, we collected branches from Norway Spruce (Picea abies) in a former cinnabar mining region in Northern Palatinate, where artisanal and small-scale mining left innumerable waste dumps. While mining, smelting and processing of the ores were terminated during WWII, high total mercury concentrations remained in the top soils locally, with presumably only small fractions being plant available. In the lab, up to seven needle age classes were analysed. 1000 needle weights increased with age and as expected, also the Hg concentrations were elevated in the older needles. Needle concentrations were higher than those reported from other national biomonitoring programs confirming the regional imprint from legacy mercury. To complement our biomonitoring study, we collected edible mushrooms in former mining areas. Hg concentrations in most samples exceeded the EU maximum residue levels (MRL), while only a few broke the existing cadmium and lead limits. Tolerable weekly intake (TWI) for inorganic mercury would be surpassed with the consumption of a small portion of mushrooms. Further studies should be performed on the outgassing of Hg from mine wastes and the incorporation of Hg in the local food web, including its methylation and biomagnification., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

4-aminophenol (AP), an aromatic phenolic compound, is commonly found in commercial products that eventually enter and pollute environmental water sources. The precise detection and quantification of AP in environmental samples are critical for comprehensively assessing contamination levels, safeguarding public health, and formulating effective remediation strategies. In the shed of light, this work proposes an electrochemical sensing platform for detecting and quantifying AP using Araucaria heterophylla biomass-derived activated carbon (AH-AC) prepared via the SC-CO 2 pathway. To evaluate the significance of SC-CO 2 -mediated chemical activation (SC-AHAC), a comparative study with conventional activation methods (C-AHAC) was also conducted. The physical characterizations such as structural, morphological, optical, and elemental analysis demonstrate the greater I D /I G value and enhanced surface functionalities of SC-AHAC than C-AHAC. The obtained lower empirical factor (R) value of 1.89 for SC-AHAC suggests increased disorder and a higher presence of single-layer amorphous carbon compared to C-AHAC (2.03). In the electrochemical analysis, the active surface area of the SC-AHAC modified electrode (0.069 cm 2 ) is higher than that of the C-AHAC modified electrode (0.061 cm 2 ), demonstrating the significance of SC-CO 2 activation. Further, the quantitative analysis on SC-AHAC@SPCE resulted in a sensitivity of 3.225 μA μM -1  cm -2 with the detection limit and quantification limit of 2.13 and 7.11 nM L -1 , respectively, in the linear range of 0.01-582.5 μM L -1  at the oxidation potential of 0.13V. This suggests that the prepared SC-AHAC could be a promising electrocatalyst for AP detection in the environmental and healthcare sectors., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Rosin, a natural resin obtained from conifer trees, has a long history of use in traditional folk medicine for treating abscesses, wounds, carbuncles, and burns, etc. It has been employed in ancient Egypt, China, Nordic countries, and Turkey as a therapeutic remedy. This comprehensive review examines the traditional uses, phytochemistry, and pharmacology of rosin, and it provides a critical update on current knowledge of rosin and identifies potential therapeutic opportunities. The chemical composition of rosin is known to vary depending on factors such as botanical sources, geographical locations, and processing methods. Rosin acids, which account for over 90% of its primary chemical constituents, have been identified as the predominant compounds in rosin. Researchers have isolated approximately 50 compounds from rosin, with terpenoid rosin acids being the most prevalent. Furthermore, the review highlights the potential pharmacological activities of rosin and its constituents. Crude extracts and isolated rosin acids have demonstrated promising properties, including antimicrobial, anti-inflammatory, anti-tumor, insecticidal, wound healing, and anti-obesity effects. However, the review emphasizes that further research is needed, as existing studies are predominantly preliminary. Many of the reported bioactivities require further verification, and the underlying mechanisms of action remain largely unexplored. In conclusion, rosin has been extensively used in traditional medicine across different cultures, and its chemical composition has been confirmed to a significant extent. The pharmacological activities observed in crude extracts and isolated rosin acids support its traditional uses. Nevertheless, additional research is necessary to deepen our understanding of the pharmacological mechanisms underlying its effects., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

The foragers of the southern African Middle Stone Age were among the first humans to adapt their environment and its resources to their needs. They heat-treated stone to alter its mechanical properties, transformed yellow colorants into red pigments and produced moldable adhesive substances from plants. Until now, only Podocarpus conifers have been identified as the botanical origin of Middle Stone Age adhesives. This is curious as these conifers do not produce sticky exudations that could be recognized as potential adhesives. To obtain an adhesive, tar must be made with a technical process based on fire. However, the nature of these technical processes has remained unknown, hampering our understanding of the meaning of this adhesive technology for the cultural evolution of early Homo sapiens. Here, we present the first evidence of a technique used for tar making in the Middle Stone Age. We created an experimental reference collection containing naturally available adhesives along manufactured tars from plants available in the Middle Stone Age and compared these to artifacts using gas chromatography-mass spectrometry and infrared spectroscopy. We found that, in the Howiesons Poort at Sibhudu Cave, tar was made by condensation, an efficient above-ground process. Even more surprisingly, the condensation method was not restricted to Podocarpus. The inhabitants of Sibhudu also produced tar from the leaves of other plants. These tars were then used, either without further transformation or were processed into ochre-based compound adhesives, suggesting that people needed different moldable substances with distinct mechanical properties. This has important implications for our understanding of Middle Stone Age H. sapiens, portraying them as skilled engineers who used and transformed their resources in a knowledgeable way., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The leaves of Araucaria cunninghamii are known to be nonedible and toxic. Previous studies have identified biflavones in various Araucaria species. This study aimed to investigate the in vitro cytotoxicity of the isolated compounds from Araucaria cunninghamii after metabolomics and network pharmacological analysis. Methanol extract of Araucaria cunninghamii leaves was subjected to bioassay-guided fractionation. The active fraction was analyzed using LC-HRMS, through strategic database mining, by comparing the data to the Dictionary of Natural Products to identify 12 biflavones, along with abietic acid, beta-sitosterol, and phthalate. Eight compounds were screened for network pharmacology study, where in silico ADME analysis, prediction of gene targets, compound-gene-pathway network and hierarchical network analysis, protein-protein interaction, KEGG pathway, and Gene Ontology analyses were done, that showed PI3KR1, EGFR, GSK3B, and ABCB1 as the common targets for all the compounds that may act in the gastric cancer pathway. Simultaneously, four biflavones were isolated via chromatography and identified through NMR as dimeric apigenin with varying methoxy substitutions. Cytotoxicity study against the AGS cell line for gastric cancer showed that AC1 biflavone (IC 50 90.58 μM) exhibits the highest cytotoxicity and monomeric apigenin (IC 50 174.5 μM) the lowest. Besides, the biflavones were docked to the previously identified targets to analyze their binding affinities, and all the ligands were found to bind with energy ≤-7 Kcal/mol., (© 2024 John Wiley & Sons Ltd.)

Background: Lung cancer, a chronic and heterogeneous disease, is the leading cause of cancer-related death on a global scale. Presently, despite a variety of available treatments, their effectiveness is limited, often resulting in considerable toxicity and adverse effects. Additionally, the development of chemoresistance in cancer cells poses a challenge. Trilobolide-6-O-isobutyrate (TBB), a natural sesquiterpene lactone extracted from Sphagneticola trilobata, has exhibited antitumor effects. Its pharmacological properties in NSCLC lung cancer, however, have not been explored., Purpose: This study evaluated the impact of TBB on the A549 and NCI-H460 tumor cell lines in vitro, examining its antiproliferative properties and initial mechanisms of cell death., Methods: TBB, obtained at 98 % purity from S. trilobata leaves, was characterized using chromatographic techniques. Subsequently, its impact on inhibiting tumor cell proliferation in vitro, TBB-induced cytotoxicity in LLC-MK2, THP-1, AMJ2-C11 cells, as well as its effects on sheep erythrocytes, and the underlying mechanisms of cell death, were assessed., Results: In silico predictions have shown promising drug-likeness potential for TBB, indicating high oral bioavailability and intestinal absorption. Treatment of A549 and NCI-H460 human tumor cells with TBB demonstrated a direct impact, inducing significant morphological and structural alterations. TBB also reduced migratory capacity without causing toxicity at lower concentrations to LLC-MK2, THP-1 and AMJ2-C11 cell lines. This antiproliferative effect correlated with elevated oxidative stress, characterized by increased levels of ROS, superoxide anion radicals and NO, accompanied by a decrease in antioxidant markers: SOD and GSH. TBB-stress-induced led to changes in cell metabolism, fostering the accumulation of lipid droplets and autophagic vacuoles. Stress also resulted in compromised mitochondrial integrity, a crucial aspect of cellular function. Additionally, TBB prompted apoptosis-like cell death through activation of caspase 3/7 stressors., Conclusion: These findings underscore the potential of TBB as a promising candidate for future studies and suggest its viability as an additional component in the development of novel anticancer drugs prototypes., Competing Interests: Declaration of competing interest The authors declare that they have no competing interests., (Copyright © 2024. Published by Elsevier GmbH.)

The natural abundance of stable carbon and nitrogen isotopes (δ 13 C and δ 15 N) in leaves can provide comprehensive information on the physiological and ecological processes of plants and has been widely used in ecological research. However, recent studies on leaf δ 13 C and δ 15 N have focused mainly on woody species, few studies have been conducted on herbs in different vegetation types, and their differences and driving factors are still unclear. In this study, we focused on the herbs in subalpine coniferous forests, alpine shrublands, and alpine mea-dows on the eastern Qinghai-Tibet Plateau, and investigated the differences in leaf δ 13 C and δ 15 N of herbs and the driving factors. The results showed that there were significant differences in leaf δ 13 C and δ 15 N values of herbs among different vegetation types, with the highest δ 13 C and δ 15 N values in alpine meadows, followed by alpine shrublands, and the lowest in subalpine coniferous forests. Using variation partitioning analysis, we revealed that differences in leaf δ 13 C and δ 15 N of herbs among various vegetation types were driven by both leaf functional traits and climate factors, with the contribution of leaf functional traits being relatively higher than that of climate factors. Hierarchical partitioning results indicated that mean annual temperature (MAT), chlorophyll content index, leaf nitrogen content per unit area (N area ), and leaf mass per area were the main drivers of leaf δ 13 C variations of herbs across different vegetation types, while the relative importance of N area and MAT for variation in leaf δ 15 N of herbs was much higher than those other variables. There was a strong coupling relationship between leaf δ 13 C and δ 15 N as indicated by the result of the ordinary least squares regression. Our findings could provide new insights into understanding the key drivers of leaf δ 13 C and δ 15 N variations in herbs across different vegetation types.

The ability of the ancient Egyptians to preserve the human body through embalming has not only fascinated people since antiquity, but also has always raised the question of how this outstanding chemical and ritual process was practically achieved. Here we integrate archaeological, philological and organic residue analyses, shedding new light on the practice and economy of embalming in ancient Egypt. We analysed the organic contents of 31 ceramic vessels recovered from a 26th Dynasty embalming workshop at Saqqara 1,2 . These vessels were labelled according to their content and/or use, enabling us to correlate organic substances with their Egyptian names and specific embalming practices. We identified specific mixtures of fragrant or antiseptic oils, tars and resins that were used to embalm the head and treat the wrappings using gas chromatography-mass spectrometry analyses. Our study of the Saqqara workshop extends interpretations from a micro-level analysis highlighting the socio-economic status of a tomb owner 3-7 to macro-level interpretations of the society. The identification of non-local organic substances enables the reconstruction of trade networks that provided ancient Egyptian embalmers with the substances required for mummification. This extensive demand for foreign products promoted trade both within the Mediterranean 8-10 (for example, Pistacia and conifer by-products) and with tropical forest regions (for example, dammar and elemi). Additionally, we show that at Saqqara, antiu and sefet-well known from ancient texts and usually translated as 'myrrh' or 'incense' 11-13 and 'a sacred oil' 13,14 -refer to a coniferous oils-or-tars-based mixture and an unguent with plant additives, respectively., (© 2023. The Author(s).)

Castanopsis is diffusely spread in tropical and subtropical regions and is an important nectar source plant in China. The Castanopsis honey (CH) is characterized by its bitter taste. However, its composition and functions remain unclear. In this study, the physicochemical parameters, chemical composition, and antioxidant capacity of CH were comprehensively investigated, with the anti-inflammatory effects of the Castanopsis honey extract (CHE) evaluated based on the RAW 264.7 cell inflammatory model. The results revealed a high level of quality in CH based on the quality standards. Among a total of 84 compounds identified in CH, 5 high response compounds and 29 phenols were further quantified by UPLC-Q/TOF-MS. The high content of phenylethylamine (117.58 ± 64.81 mg kg -1 ) was identified as a potential marker of CH. Furthermore, the CH showed evident antioxidant activities, and the anti-inflammatory activities of CHE were observed to inhibit the release of nitric oxide (NO) and reduce the content of tumor necrosis factor alpha (TNF-α) and improve the content of interleukin-10 (IL-10) by regulating the NF-κB pathway. Our study indicates that CH has sound physicochemical properties and biological activities with a high level of quality, providing strong experimental evidence to support the further economic and agricultural development and application of CH.

The current study was intended to explore the phytochemical profiling and therapeutic activities of Putranjiva roxburghii Wall. Crude extracts of different plant parts were subjected to the determination of antioxidant, antimicrobial, antidiabetic, cytotoxic, and protein kinase inhibitory potential by using solvents of varying polarity ranges. Maximum phenolic content was notified in distilled water extracts of the stem (DW-S) and leaf (DW-L) while the highest flavonoid content was obtained in ethyl acetate leaf (EA-L) extract. HPLC-DAD analysis confirmed the presence of various polyphenols, quantified in the range of 0.02 ± 0.36 to 2.05 ± 0.18 μg/mg extract. Maximum DPPH scavenging activity was expressed by methanolic extract of the stem (MeOH-S). The highest antioxidant capacity and reducing power was shown by MeOH-S and leaf methanolic extract (MeOH-L), respectively. Proficient antibacterial activity was shown by EA-L extract against Bacillus subtilis and Escherichia coli . Remarkable α-amylase and α-glucosidase inhibition potential was expressed by ethyl acetate fruit (EA-F) and n-Hexane leaf (nH-L) extracts, respectively. In case of brine shrimp lethality assay, 41.67% of the extracts (LC 50 < 50 µg/mL) were considered as extremely cytotoxic. The test extracts also showed mild antifungal and protein kinase inhibition activities. The present study explores the therapeutic potential of P . roxburghii and calls for subsequent studies to isolate new bioactive leads through bioactivity-guided isolation.

Urease plays a significant role in the pathogenesis of urolithiasis pyelonephritis, urinary catheter encrustation, hepatic coma, hepatic encephalopathy, and peptic acid duodenal ulcers. Salvinia molesta was explored to identify new bioactive compounds with particular emphasis on urease inhibitors. The aqueous methanol extract was fractionated using solvents of increasing polarity. A series of column chromatography and later HPLC were performed on butanol extract. The structures of the resulting pure compounds were resolved using NMR (1D and 2D), infrared, and mass spectroscopy. The novel isolate was evaluated for antioxidant activity (using DPPH, superoxide anion radical scavenging, oxidative burst, and Fe +2 chelation assays), anti-glycation behavior, anticancer activity, carbonic anhydrase inhibition, phosphodiesterase inhibition, and urease inhibition. One new glucopyranose derivative 6'-O-(3,4-dihydroxybenzoyl)-4'-O-(4-hydroxybenzoyl)-α/β-D-glucopyranoside (1) and four known glycosides were identified. Glycoside 1 demonstrated promising antioxidant potential with IC 50 values of 48.2 ± 0.3, 60.3 ± 0.6, and 42.1 ± 1.8 μM against DPPH, superoxide radical, and oxidative burst, respectively. Its IC 50 in the Jack bean urease inhibition assay was 99.1 ± 0.8 μM. The mechanism-based kinetic studies presented that compound 1 is a mixed-type inhibitor of urease with a K i value of 91.8 ± 0.1 μM. Finally, molecular dynamic simulations exploring the binding mode of compound 1 with urease provided quantitative agreement between estimated binding free energies and the experimental results. The studies corroborate the use of compound 1 as a lead for QSAR studies as an antioxidant and urease inhibitor. Moreover, it needs to be further evaluated through the animal model, that is, in vivo or tissue culture-based ex-vivo studies, to establish their therapeutic potential against oxidative stress phosphodiesterase-II and urease-induced pathologies., (© 2021 Wiley Periodicals LLC.)

The class of plant exudates that contain the phenol functionality, termed phenolics , is defined, surveyed, and characterized by solid-state 13 C NMR spectroscopy and by solution-state 1 H NMR spectroscopy. Materials in this group are identified by the phenolic 13 C resonance (from the ipso carbon of ArOH) at δ 145-160 (δ 160-167 for ArOR). The resonance patterns define several subclasses based on the collective similarity of their 13 C spectra, specifically, aloetics from the genus Aloe , guaiacs from the genus Guaiacum and other eurosid and conifer genera, xanthics from the genus Garcinia , and kinos from the genus Eucalyptus and many other genera. Phenolic exudates often are mixed with terpenoid materials (the building block of exudates known as resins ) and carbohydrates (the building block of exudates known as gums ) to form hybrid subgroups such as guaiac gums, guaiac resins, and kino resins. There are numerous phenolic exudates not affiliated with any of these groups, both as pure phenolics and as hybrids (phenolic resins, phenolic gum resins, and phenolic waxes).

To elucidate the chemical linkages between lignin and carbohydrates in ginkgo cell walls, 13 C- 2 H-enriched cell wall-dehydrogenation polymers (CW-DHP) were selectively prepared with cambial tissue from Ginkgo biloba L. by feeding D-glucose-[6- 2 H 2 ], coniferin-[α- 13 C], and phenylalanine ammonia-lyase (PAL) inhibitor. The abundant detection of 13 C and 2 H confirmed that D-glucose-[6- 2 H 2 ] and coniferin-[α- 13 C] were involved in the normal metabolism of ginkgo cambial cells that had been effectively labelled with dual isotopes. In the ginkgo CW-DHP, ketal and ether linkages were formed between the C-α of lignin side chains and carbohydrates, as revealed by solid state CP/MAS 13 C-NMR differential spectroscopy. Furthermore, the DMSO/TBAH ionic liquids system was used to fractionate the ball-milled CW-DHP into three lignin-carbohydrate complex (LCC) fractions: glucan-lignin complex (GL), glucomannan-lignin complex (GML), and xylan-lignin complex (XL). The XRD determination indicated that the cellulose type I of the GL was converted into cellulose type II during the separation process. The molecular weight was in the order of Ac-GL > Ac-GML > XL. The 13 C-NMR and 1 H-NMR differential spectroscopy of 13 C- 2 H-enriched GL fraction indicated that lignin was linked with cellulose C-6 by benzyl ether linkages. It was also found that there were benzyl ether linkages between the lignin side chain C-α and glucomannan C-6 in the 13 C- 2 H-enriched GML fraction. The formation of ketal linkages between the C-α of lignin and xylan was confirmed in the 13 C- 2 H-enriched XL fraction.

The number of colon cancer patients is increasing, and new alternatives for treatment are important. We focused on the sesquiterpene lactone onoseriolide from Hedyosmum racemosum , which is widely used in traditional medicine. This compound was evaluated to determine its cytotoxic effect and the mechanism of cell death that is induced in the human colon cancer cell line RKO. A dose-dependent decrease in cell viability was observed. p53 expression increased followed by an increase in p21 expression, which is involved in cell cycle arrest in the G 2 /M phase. Caspase-3 activation and PARP-1 cleavage, which are apoptotic markers, were also monitored. Autophagy markers were also studied, and Beclin 1 was downregulated, while LC-3II increased in a dose-dependent manner. There were no changes in SQSTM1/p62 regulation. Onoseriolide exerts cytotoxic and cytostatic effects, activating the autophagy pathway as a protective mechanism and apoptosis as the cell death pathway.

Species of Podocarpus are used traditionally in their native areas for the treatment of fevers, asthma, coughs, cholera, chest pain, arthritis, rheumatism, and sexually transmitted diseases. To identify natural products having efficacy against inflammatory bowel disease (IBD), we identified a new, 16-hydroxy-4β-carboxy- O -β-D-glucopyranosyl-19-nor-totarol ( 4 ) together with three known diterpenoids from P. macrophyllus . Furthermore, all the extracts, fractions, and isolates 1 - 4 were investigated for their anti-inflammatory effects by assessing the expression on nitric oxide (NO) production and proinflammatory cytokines in lipopolysaccharide (LPS)-stimulated RAW 264.7 and HT-29 cells. Among them, nagilactone B ( 2 ) exhibited a potent anti-inflammatory effect against NO production on RAW 264.7 cells; therefore, nagilactone B was further assessed for anti-inflammatory activity. Western blot analysis revealed that nagilactone B significantly decreased the expression of LPS-stimulated protein, inducible nitric oxide synthase (iNOS), cyclooxygenase (COX)-2, and phosphorylated extracellular regulated kinase (pERK)1/2. In addition, nagilactone B downregulated tumor necrosis factor (TNF)-α, interleukin (IL)-6, and IL-8 levels in LPS-induced macrophages and colonic epithelial cells. To our best knowledge, this is the first report on the inhibitory effect of nagilactone B (pure state) and rakanmakilactone G against NO production in LPS-stimulated RAW 264.7 cells. Thus, diterpenoids isolated from P . macrophyllus could be employed as potential therapeutic phytochemicals for IBD.

Conifers have long been recognized for their therapeutic potential in different disorders. Alkaloids, terpenes and polyphenols are the most abundant naturally occurring phytochemicals in these plants. Here, we provide an overview of the phytochemistry and related commercial products obtained from conifers. The pharmacological actions of different phytochemicals present in conifers against bacterial and fungal infections, cancer, diabetes and cardiovascular diseases are also reviewed. Data obtained from experimental and clinical studies performed to date clearly underline that such compounds exert promising antioxidant effects, being able to inhibit cell damage, cancer growth, inflammation and the onset of neurodegenerative diseases. Therefore, an attempt has been made with the intent to highlight the importance of conifer-derived extracts for pharmacological purposes, with the support of relevant in vitro and in vivo experimental data. In short, this review comprehends the information published to date related to conifers' phytochemicals and illustrates their potential role as drugs.

Chromatographic purification of the alcoholic extract from the aerial parts of the Saudi plant Nuxia oppositifolia (Hochst.), Benth., resulted in five isolated phenolic compounds. Two flavones, hispidulin ( 1 ) and jaceosidin ( 2 ), and the phenylethanoid glycosides, verbascoside ( 3 ), isoverbascoside ( 4 ), and conandroside ( 5 ), were identified and their chemical structures were determined by spectroscopic analyses. The insecticidal activity of compounds 1 and 2, in addition to 11 compounds isolated in a previous research ( 6 - 16 ), was evaluated against the Yellow Fever mosquito, Aedes aegypti . Four compounds displayed adulticidal activity with LD 50 values of 2-2.3 μg/mosquito. Free radical scavenging properties of the plant extracts and compounds ( 1 - 5 ) were evaluated by measuring the 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) and 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonate radical cation (ABTS •+ ) scavenging activity. All compounds exhibited notable activity, compared with the positive control, l-Ascorbic acid. This study suggests that N. oppositifolia could be a promising source of secondary metabolites, some with lethal adulticidal effect against Ae. aegypti .

Bark beetles (family: Curculionidae; subfamily: Scolytinae) in the Dendroctonus and Ips genera are the most destructive forest pests in the Northern hemisphere. They use cytochromes P450 (P450s) to detoxify tree-produced terpenes to produce pheromones, in de novo pheromone production and to oxidize odorants on antennae. Many Dendroctonus spp. use trans-verbenol as an aggregation pheromone, and it is formed from host-tree produced α-pinene hydroxylated by CYP6DE1 during larval stages, stored as verbenyl ester of fatty acids, and then released when the female begins feeding on a new host tree. Ips spp. hydroxylate de novo produced myrcene to form ipsdienol. Subsequent steps form the appropriate enantiomeric composition of ipsdienol and convert ipsdienol to ipsenol. In this article we review recent progress in elucidating the functions of P450s in Ips and Dendroctonus species and in doing so provide insights into the role of these enzymes in host phytochemical detoxification and pheromone production., (Crown Copyright © 2021. Published by Elsevier Inc. All rights reserved.)

Introduction: Water-soluble, but not lipid-soluble, extract of Dicranopteris linearis leaves has been proven to possess hepatoprotective activity. The present study aimed to validate the hepatoprotective and antioxidant activities, and phytoconstituents of lipid-soluble (chloroform) extract of D. linearis leaves., Methods: The extract of D. linearis leaves (CEDL; 50, 250 and 500 mg/kg) was orally administered to rats for 7 consecutive days followed by the oral administration of 3 g/kg PCM to induce liver injury. Blood was collected for liver function analysis while the liver was obtained for histopathological examination and endogenous antioxidant activity determination. The extract was also subjected to antioxidant evaluation and phytochemicals determination via phytochemical screening, HPLC and UPLC-HRMS analyses., Results: CEDL exerted significant (p < 0.05) hepatoprotective activity at 250 and 500 mg/kg and significantly (p < 0.05) reversed the PCM-induced decrease in rat's liver endogenous antioxidant (catalase and superoxide dismutase) level. CEDL possessed a high antioxidant capacity when measured using the ORAC assay, but a low total phenolic content value and radical scavenging activity as confirmed via several radical scavenging assays, which might be attributed particularly to the presence of triterpenes. Phytochemicals screening demonstrated the presence of triterpenes and flavonoids, while UPLC-HRMS analysis showed the presence of polyphenols belonging to the hydroxybenzoic acids, hydroxycinammates and flavonoid groups., Discussion and Conclusion: Lipid-soluble bioactive compounds of CEDL demonstrated hepatoprotective effect against PCM intoxication partly via the modulation of the endogenous antioxidant defense system, and exerted high antioxidant capacity. Further investigation is warranted to identify the potential hepatoprotective leads from CEDL for future drug development.

Ugonins are unique flavonoids with cyclohexyl motif from Helminthostachys zeylanica. Ugonins (1-6) from the target plant displayed significant inhibitions against both PTP1B (IC 50 s = 0.6-7.3 μM) and α-glucosidase (IC 50 s = 3.9-32.9 μM), which are crucial enzymes associated with diabetes. A cyclohexyl motif was proved to be the key functionality for PTP1B and α-glucosidase. For example, 1 was 26-fold effective to PTP1B and 15-fold to α-glucosidase than its mother compound, luteolin. This tendency was well elucidated with distinctive differences of binding affinities (K SV ) between ugonins and mother compounds to PTP1B enzyme. Inhibitory mechanisms to PTP1B and α-glucosidase were fully characterized to be competitive, non-competitive and mixed type I according to the position of cyclohexyl functionality. In particular, the ugonin J (1) has a cyclohexyl on the B ring was estimated as a reversible, competitive and a slow binding inhibitor with parameters: K i app  = 0.1234 μM, k 3  = 0.5713 μM -1  min -1 , and k 4  = 0.0705 min -1 . In-depth molecular docking experiments disclosed the specific binding sites and residues of competitive inhibitor (1) and non-competitive inhibitor (4) to PTP1B enzymes. As well, all six ugonins (1-6) also inhibited α-glucosidase effectively, in which cyclohexyl motif was also the key functionality of inhibitions., Competing Interests: Declaration of competing interest The authors declare no conflicts of interest., (Copyright © 2020. Published by Elsevier B.V.)

We characterized a new cycloartane glycoside, herein known as aspleniumside F (1), along with five known compounds as kaempferol-3-O-[(6-O-(E)-feruloyl)-β-D-glucopyranosyl]-(1→2)-β-D-galacopyranoside (2), quercetin-3-O-[(6-O-(E)-feruloyl)-β-D-glucopyranosyl]-(1→2)-β-D-glucopyranoside (3), kaempferol-3-O-[(6-O-(E)-caffeoyl)-β-D-glucopyranosyl]-(1→2)-β-D-glucopyranoside (4), kaempferol-3-O-[(6-O-(E)-caffeoyl)-β-D-glucopyranosyl]-(1→2)-β-D-glucopyranosyl-7-O-β-D-glucopyranoside (5), and kaempferol-3-O-[(6-O-p-coumaroyl)-β-D-glucopyranosyl]-(1→2)-β-D-glucopyranosyl-7-O-β-D-glucopyranoside (6), from Asplenium ruprechtii Sa. Kurata, a folk medicine widely used to treat Thromboangiitis obliterans in China, Japan, and Korea. Based on spectroscopic, mainly 1D-, 2D-NMR and (+)-HR-ESI-MS, analyses as well as through comparisons with previous reports, its chemical structure was determined as 3β,24,30-tri-β-D-glucopyranosyl-23,25-dihydroxycycloartane (= (23R,24R)-3β,24-bis-(β-D-glucopyranosyloxy)-23,25-dihydroxy-9β-9,19-cyclolanostan-29-yl β-D-glucopyranoside). According to the 1 H coupling constant of anomeric protons and co-TLC of the acid hydrolysate with D-glucose, all three glycoside groups in 1 were revealed as β-D-glucopyranosyl. Furthermore, SOD-like antioxidant activity evaluation via IC 50 of 12.43, 6.78, 9.12, 6.94 and 4.85 μM revealed that compounds 2-6 had bioactivity., (© 2020 Wiley-VHCA AG, Zurich, Switzerland.)

The continued development of folk medicine to potentially treat infectious diseases has resulted in an increase in natural sources of antimicrobial agents, particularly the use of plant essential oils containing volatile products from secondary metabolism. The objectives of this investigation were to (i) analyze the chemical components of essential oils using GC/MS and (ii) to examine their in vitro antimicrobial activities against four strains of bacteria (Staphylococcus aureus, Bacillus subtilis, Escherichia coli and Shigella flexneri) and one fungus (Candida albicans) by determining minimum inhibitory concentrations (MICs) and minimum bactericidal concentrations (MBCs) in liquid and solid media, respectively, from different Pyrrosia petiolosa locations. Eighty-eight evaporable compounds were confirmed in their essential oils; the major components in the oils were 2,4-pentadienal (12.5 %), phytol (10.5 %) and nonanal (8.6 %). Based on hierarchical cluster analysis, Pyrrosia samples were categorized into four groups, indicating significant essential oil diversity from different Pyrrosia locations. Results also indicated that essential oils had a broad spectrum of antibacterial activities, particularly against Shigella flexneri and Staphylococcus aureus with MICs of 5 μL/mL. Results from this investigation are the first to record the chemical component and antimicrobial potential of essential oils from different P. Petiolosa locations., (© 2020 Wiley-VHCA AG, Zurich, Switzerland.)

The use of metallic nanoparticles in engineering and biomedicine disciplines has gained considerable attention. Scientists are exploring new synthesis protocols of these substances considering their small size and lucrative antimicrobial potential. Among the most economical techniques of synthesis of metallic nanoparticles via chemical routes, which includes the use of chemicals as metal reducing agents, is considered to generate nanoparticles possessing toxicity and biological risk. This limitation of chemically synthesized nanoparticles has engendered the exploration for the ecofriendly synthesis process. Biological or green synthesis approaches have emerged as an effective solution to address the limitations of conventionally synthesized nanoparticles. Nanoparticles synthesized via biological entities obtained from plant extracts exhibit superior effect in comparison to chemical methods. Recently, conifer extracts have been found to be effective in synthesizing metallic nanoparticles through a highly regulated process. The current review highlights the importance of conifers and its extracts in synthesis of metallic nanoparticles. It also discusses the different applications of the conifer extract mediated metallic nanoparticles.

Breynia retusa (Dennst.) Alston (also known as Cup Saucer plant) is a food plant with wide applications in traditional medicine, particularly in Ayurveda. Extracts obtained with four solvents (dichloromethane, methanol, ethyl acetate and water), from three plant parts, (fruit, leaf and bark) were obtained. Extracts were tested for total phenolic, flavonoid content and antioxidant activities using a battery of assays including 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), ferric reducing antioxidant power (FRAP), cupric reducing antioxidant capacity (CUPRAC), total antioxidant capacity (TAC) (phosphomolybdenum) and metal chelating. Enzyme inhibitory effects were investigated using acetylcholinesterase (AChE), butyrylcholinesterase (BChE), tyrosinase, α-amylase and α-glucosidase as target enzymes. Results showed that the methanolic bark extract exhibited significant radical scavenging activity (DPPH: 202.09 ± 0.15; ABTS: 490.12 ± 0.18 mg Trolox equivalent (TE)/g), reducing potential (FRAP: 325.86 ± 4.36: CUPRAC: 661.82 ± 0.40 mg TE/g) and possessed the highest TAC (3.33 ± 0.13 mmol TE/g). The methanolic extracts were subjected to LC-DAD-MS n and NMR analysis. A two-column LC method was developed to separate constituents, allowing to identify and quantify forty-four and fifteen constituents in bark and fruits, respectively. Main compound in bark was epicatechin-3- O -sulphate and isolation of compound was performed to confirm its identity. Bark extract contained catechins, procyanidins, gallic acid derivatives and the sulfur containing spiroketal named breynins. Aerial parts mostly contained flavonoid glycosides. Considering the bioassays, the methanolic bark extract resulted a potent tyrosinase (152.79 ± 0.27 mg kojic acid equivalent/g), α-amylase (0.99 ± 0.01 mmol acarbose equivalent ACAE/g) and α-glucosidase (2.16 ± 0.01 mmol ACAE/g) inhibitor. In conclusion, methanol is able to extract the efficiently the phytoconstituents of B. retusa and the bark is the most valuable source of compounds.

Essential oils (EOs) are regarded as alternative therapeutic agents for many diseases. In phytotherapy research areas, it is now well reported that conifers are the rich source of EOs. This review aims to update information on the biological sources and the best extraction processes of the significant constituents along with the traditional and therapeutic properties of the EOs from selected conifers of Himachal Pradesh, Northwestern Himalaya. In the present review, ten conifer species of high values have been selected. Results from several studies suggest that the conifers contain monoterpenes, sesquiterpenes, diterpenes, ketones, alcohols, and esters, which are used in medicines, food products, and cosmetics as well as other commercial and industrial products. Traditionally, the EOs from the conifers have been reported to be used against fever, cough, bronchitis, skin diseases, gastrointestinal disorders, and asthma. The pharmacological studies suggest that these EOs can be used as antirheumatic, antiseptic, antispasmodic, anticancer, anti-inflammatory, antitoxic, aphrodisiac, and astringent agents. It is, therefore, concluded that the EOs from the conifers might be one of the promising tools for the treatment of various diseases. Extensive research is required to ascertain the efficacy of the EOs from unstudied conifers., (© 2020 John Wiley & Sons, Ltd.)

Stratiotes aloides L. is common water plant in central Poland. Due to its expansive character, S. aloides L. can strongly affect the functioning of aquatic ecosystems. S. aloides L. was an important famine plant in central Poland. This plant was commonly collected and cooked until the turn of the 20th century. It has also been used to heal wounds, especially when these are made by an iron implement. The objective of the present work was to study the phenolic profile in the leaves and roots of S. aloides as well as their antioxidant potential and ability to inhibit lipoxygenase (LOX) in the light of their potential bioaccessibility. The dominant compound in its leaves was luteolin-7-O-hexoside-glucuronide (5.84 mg/g DW), whereas the dominant root component was chrysoeriol-7-O-hexoside-glucuronide (0.83 mg/g DW). Infusions from leaves, roots, and their 1:1 ( v / v ) mixture contained potentially bioaccessible antiradical compounds. S. aloides is a good source of water-extractable reductive compounds. Especially valuable are the leaves of this plant. The roots of S. aloides contained very active hydrophilic compounds able to chelate metal ions. However, their potential bioaccessibility was relatively low. The hydrophilic compounds from the leaves were the most effective XO inhibitors (EC 50 = 9.91 mg DW/mL). The water-extractable compounds derived from the leaves and roots acted as uncompetitive LOX inhibitors.

Hair loss is becoming increasingly prevalent as dietary and living habits change. The search for natural products to limit hair loss has led to tapping into traditional cosmetic knowledge. We studied three plants of the Polynesian cosmetopoeia, Bidens pilosa , Calophyllum inophyllum and Fagraea berteroana , to determine their ability to promote hair growth. Their chemical content was characterized by liquid chromatography coupled to mass spectrometry (LC-MS). Their proliferative activity on dermal papilla cells (DPCs) was assessed via MTT assay and molecular targets were evaluated by RT-qPCR analysis of seven factors involved in the modulation of the hair cycle, CCND1 , LEF1 , DKK1 , WNT5A PPARD , TGFΒ1 , PPARD and RSPO2 . Our results show that our extracts significantly increased proliferation of dermal papilla cells. Furthermore, LC-MS/MS analysis revealed a diversity of molecules, flavonoids, iridoids and organic acids, some known for hair-inducing properties. Finally, specific extracts and fractions of all three plants either upregulated CCND1 , LEF1 and PPARD involved in stimulating hair follicle proliferation and/or lowered the gene expression levels of hair growth inhibiting factors, DKK1 and TGFB1 . Our findings suggest that extracts from B. pilosa, C. inophyllum and F. berteroana are interesting candidates to stimulate hair growth.

An ethanol extract of the powdered twigs of Podocarpus imbricatus afforded 14 new diterpenoids ( 1 - 14 ), which all share an aromatized C ring. These isolates belong to five diterpenoid types that include abietanes ( 1 - 3 ), semperviranes ( 4 - 9 ), totaranes ( 10 - 12 ), a C-17 norabietane ( 13 ), and an icetexane ( 14 ). Their structures were assigned mainly by analysis of the spectroscopic data, and the absolute configuration of 1 was determined by X-ray crystallography. A biosynthetic pathway for five of the biogenetically related types of diterpenoids was proposed. Compound 7 showed moderate inhibitory activity against Zika virus with an IC 50 value of 2.5 μM.

Currently, coniferous shoots are almost absent as a food ingredient despite their wide availability in many parts of the world. The aim of the study was to assess and compare the composition of selected plant metabolites, evaluate the antioxidant and antimicrobial properties of selected shoots collected in 2019 from the arboretum in Zielonka (Poland), including individual samples from Picea abies L. (PA), Larix decidua Mill (LD), Pinus sylvestris L. (PS), Pseudotsuga menziesii (PM) and Juniperus communis L. (JC). The present work has shown that aqueous extracts obtained from tested shoots are a rich source of phenols such as caffeic acid, ferulic acid, chlorogenic acid, 4-hydroxybenzoic acid and many others. Obtained extracts exhibit antioxidant and antimicrobial properties in vitro. The highest sum of the studied phenolic compounds was found in the PA sample (13,947.80 µg/g dw), while the lowest in PS (6123.57 µg/g dw). The samples were particularly rich in ferulic acid, chlorogenic acid and 4-hydroxybenzoic acid. The highest values regarding the Folin-Ciocâlteu reagent (FCR) and ferric reducing ability of plasma (FRAP) reducing ability tests, as well as the total flavonoid content assay, were obtained for the LD sample, although the LD (14.83 mg GAE/g dw) and PM (14.53 mg GAE/g dw) samples did not differ statistically in the FCR assay. With respect to free radical quenching measurements (DPPH), the PA (404.18-μM Trolox/g dw) and JC (384.30-μM Trolox/g dw) samples had the highest radical quenching ability and did not differ statistically. Generally, extracts obtained from PA and PS showed the highest antimicrobial activity against tested Gram-negative bacteria, Gram-positive bacteria and fungi.

Glioblastoma (GBM) is the most malignant central nervous system tumor, with poor prognosis. Temozolomide (TMZ) has been used as a first-line drug for the treatment of GBM for over a decade, but its treatment benefits are limited by acquired resistance. Polysaccharides from Cibotium barometz (CBPs) are polysaccharides purified from the root of Cibotium barometz (L.) J. Sm., possessing sensitizing activity. The purpose of this study was to investigate the anti-cancer effect of CBP from different processing methods on U87 cells using a 1 H NMR-based metabolic approach, complemented with qRT-PCR and flow cytometry, to identify potential markers and discover the targets to explore the underlying mechanism. Cibotium barometz is usually processed under sand heating in clinical applications. Polysaccharides from both the processed (PCBP) and raw (RCBP) C. barometz were prepared, and the effect on enhancing the sensitivity to TMZ was investigated in vitro. CBP can significantly increase the toxicity of TMZ to the U87 cell line, promote apoptosis, enhance cell cycle changes, and arrest cells in S phase, and RCBP demonstrated better activity. Multivariate statistical analyses, such as principal component analysis (PCA) and orthogonal projection to latent structure with discriminant analysis (OPLS-DA), were used to identify metabolic biomarkers, and 12 metabolites in the cell extract samples were clearly identified as altered after RCBP exposure. NMR-based cell metabolomics provided a holistic method for the identification of CBP's apoptosis-enhancing mechanisms and the exploration of its potential applications in preclinical and clinical studies., Competing Interests: Declaration of competing Interest These authors declare no conflicts of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Glandular trichomes (GTs) are defensive structures that produce and accumulate specialized metabolites and protect plants against herbivores, pathogens, and abiotic stress. GTs have been extensively studied in angiosperms for their roles in defense and biosynthesis of high-value metabolites. In contrast, trichomes of gymnosperms have been described in fossilized samples, but have not been studied in living plants. Here, we describe the characterization of GTs on young stems of a hybrid white spruce. Metabolite and histological analysis of spruce GTs support a glandular function with accumulation of a diverse array of mono-, sesqui- and diterpenes including diterpene methylesters. Methylated diterpenes have previously been associated with insect resistance in white spruce. Headspeace analysis of spruce GTs showed a profile of volatiles dominated by monoterpenes and a highly diverse array of sesquiterpenes. Spruce GTs appear early during shoot growth, prior to the development of a lignified bark and prior to accumulation of terpenes in needles. Spruce GTs may provide an early, terpene-based chemical defense system at a developmental stage when young shoots are particularly vulnerable to foliage and shoot feeding insects, and before the resin duct system characteristic of conifers has fully developed.

Foodborne pathogens are a real public health concern in an escalating antimicrobial resistance scenario. Natural products represent a promising source of bioactive molecules, and essential oils have attracted much attention due to their myriad of biological properties, including antibacterial activities. In this context, essential oils obtained from the leaves of Chromolaena squalida , Campomanesia sessiliflora, Myrsine guianensis, Matayba guianensis, Siparuna guianensis, Ocotea minarum and Endlicheria paniculata -species from the Cerrado biome of Midwest Brazil-were extracted and evaluated for their antibacterial activity against a panel of four standard and three clinical multidrug-resistant bacterial strains. All tested oils showed moderate to good activity against at least four bacterial strains, including Salmonella Typhi and oxacillin-resistant Staphylococcus. The essential oils from C. squalida , C. sessiliflora , My. guianensis and Ma. guianensis showed strong inhibition of clinical Staphylococcus strains, which cause bovine mastitis and are related to milk-borne diseases. Their chemical profiles were investigated by gas chromatography coupled to mass spectrometry (GC/MS), which revealed a predominance of mono- and sesquiterpene hydrocarbons, some of which with well-known antimicrobial properties. The essential oil from Cerrado plants proved active against resistant Gram-positive and Gram-negative bacteria, revealing their potentialities for the development of new alternative agents to prevent the spreading of resistant bacterial contamination.

The paper presents experimental results concerning the ultrasonically-assisted extraction of bioactive compounds from Erodium glaucophyllum roots. A comparison with conventional methodology is presented, and thereby the phytochemical composition and the antioxidant and anti-inflammatory activities of extracts are evaluated. The phenolic profile of Erodium extracts was analyzed by TOF-LC-MS-MS. The identification of phenolic compounds revealed that the major component was (+)-gallocatechin in the aqueous extracts obtained for the different extraction methodologies. The highest quantity of phenolic compounds and antioxidant capacity was found in the hydroethanolic extract obtained by conventional extraction (29.22-25.50 mg GAE/g DM; 21.174 mM Trolox equivalent). The highest content of carotenoids, varying from 0.035 to 0.114 mg/g dry matter, was reached by ultrasonic-assisted extraction. Furthermore, Erodium extracts showed a potent inhibition of the inflammatory reaction by means of the inhibition of tumor necrosis factor-alpha (TNF-α). The extracts obtained when ultrasound extraction was combined with ethanol:water (50:50, v/v) presented the greatest inhibition (92%).

Thirty-three compounds ( 1 - 33 ) were isolated from the rhizomes of Osmunda japonica . Their structures were elucidated on the basis of spectral analysis and identified as ent -kaurene terpenoids (1-3), anthraquinones (4-8), flavonoids (9-12), steroids (13-15), and other compounds ( 16 - 33 ). Compound 1 - 14 , 19 - 27 were isolated from the genus osmunda for the first time. Compound 28-29 were isolated from the plant for the first time. Cytotoxicities of all compounds against Hela, HepG2 and A549 cell lines were measured by MTT assay, and their antioxidant activities were determined by DPPH and ABTS radical scavenging assays. Compound 2 exhibited potent cytotoxicity against Hela, HepG2 cell lines with IC 50 values of 9.31 and 9.66 μM, respectively. Compound 9 showed good antioxidant activity. The Trolox-equivalent antioxidant capacity (TEAC) value was 0.95 mM in ABTS assay, and the IC 50 value was 18.63 μM in DPPH assay.

Murraya paniculata (L.) is a traditional Chinese medicine (TCM) wildly grown in southeast China, and used for abortion in folk. Murrayone, a coumarin-containing compound extracted from M. paniculata, is the most bioactive substance in this species and is being developed as a novel cancer metastasis chemopreventive agent based on its unique pharmacological properties. In the present study, a novel rapid and sensitive method for quantitative analysis of murrayone in rat plasma and for determining its pharmacokinetics in rats was developed and validated using UPLC/MS/MS. Plasma samples were subjected to protein precipitation and then directly analyzed by UPLC/MS/MS. Both murrayone and coumarin as an internal standard (I.S.) were carried on a C 18 column with a gradient mobile phase consisting of acetonitrile and water at a flow rate of 0.3 mL/min. Several gradient elution procedures were evaluated to achieve effective chromatography resolution and a sensitive response to murrayone and the I.S.. Mass spectrometry was carried out using a triple-quadrupole system via positive electrospray ionization and multiple reaction monitoring (MRM). Good linearity (r 2  = 0.9987) was achieved over a linear range of 4.0-1600 ng/mL with a lower limit of quantitation (LLOQ) of 4.0 ng/mL for murrayone. The inter- and intraday accuracy and precision ranged from 90.0 to 99.7% and 1.1 to 12.3% at four quality control concentrations, respectively. The average absolute recoveries of murrayone and the I.S. were determined to be 85.9-92.4% and 86.5-90.7%, respectively, at 10.0, 80.0, and 800 ng/mL. Murrayone was stable under a variety of storage and processing conditions that may be routinely encountered in laboratories based on all the stability tests. This newly developed method was successfully applied to the pharmacokinetic study of murrayone in rats for the first time, and the current assay methodology could provide important insights into potential therapeutics and facilitate further pharmacodynamic explorations of murrayone., Competing Interests: Declaration of Competing Interest None., (Copyright © 2019. Published by Elsevier B.V.)

Six spirobiflavonoid stereoisomers including two new ones, spiropensilisols A (1) and B (2), were isolated from a mass-limited trunk barks of Glyptostrobus pensilis, an endangered conifer endemic to China. The new structures featuring a benzofuran-containing spirolactone and their absolute configurations were determined by extensive spectroscopic methods. All the isolates showed significant inhibitory activities against the human protein tyrosine phosphatase 1B (PTP1B) enzyme, a potential therapeutic target for diabetes and obesity, with IC 50 values ranging from 3.3 to 17.1 µM. A preliminary SAR analysis with assistance of the molecular modeling approach was performed for the most potent compound (i.e., 1), to understand the nature of interactions governing the binding mode of spirobiflavonids within the active site of the PTP1B enzyme., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Dicranopteris linearis leaf has been reported to exert antinociceptive activity. The present study elucidates the possible mechanisms of antinociception modulated by the methanol extract of D. linearis leaves (MEDL) using various mouse models. The extract (25, 150, and 300 mg/kg) was administered orally to mice for 30 min priot to subjection to the acetic acid-induced writhing-, hot plate- or formalin-test to establish the antinociceptive profile of MEDL. The most effective dose was then used in the elucidation of possible mechanisms of action stage. The extract was also subjected to the phytochemical analyses. The results confirmed that MEDL exerted significant ( p < 0.05) antinociceptive activity in those pain models as well as the capsaicin-, glutamate-, bradykinin- and phorbol 12-myristate 13-acetate (PMA)-induced paw licking model. Pretreatment with naloxone (a non-selective opioid antagonist) significantly ( p < 0.05) reversed MEDL effect on thermal nociception. Only l-arginine (a nitric oxide (NO) donor) but not N(ω)-nitro-l-arginine methyl ester (l-NAME; a NO inhibitor) or 1 H -[1,2,4]oxadiazolo[4,3-a]quinoxalin-1-one (ODQ; a specific soluble guanylyl cyclase inhibitor) significantly ( p < 0.05) modified MEDL effect on the writhing test. Several polyphenolics and volatile antinociceptive compounds were detected in MEDL. In conclusion, MEDL exerted the opioid/NO-mediated antinociceptive activity, thus, justify D. linearis as a potential source for new analgesic agents development.

Bark of Norway spruce and Scots pine trees contain large amounts of condensed tannins. Tannins extracted with hot water could be used in different applications as they possess antioxidative and antimicrobial activities. The use of bark tannins as e.g., food preservatives calls for increases in our knowledge of their antioxidative activities when applied in foodstuffs. To assess the ability of bark tannins to prevent lipid oxidation, hot water extracts were evaluated in a liposome model. Isolated tannins were also applied in dry-cured, salty meat snacks either as liquid extracts or in dry-powder form. Consumer acceptance of the snacks was tested by a sensory evaluation panel where outlook, odor, taste, and structure of the snacks were evaluated and compared to a commercial product without tannin ingredients. Our results show that conifer bark tannin-rich extracts have high capacity to prevent lipid oxidation in the liposome model. The efficacies of pine and spruce bark extracts were ten to hundred folds higher, respectively, than those of phenolic berry extracts. The bark extracts did not significantly influence the odor or taste of the meat snacks. The findings indicate that bark extracts may be used as sustainable food ingredients. However, more research is needed to verify their safety.

Nuxia oppositifolia is traditionally used in diabetes treatment in many Arabian countries; however, scientific evidence is lacking. Hence, the present study explored the antidiabetic and antioxidant activities of the plant extracts and their purified compounds. The methanolic crude extract of N. oppositifolia was partitioned using a two-solvent system. The n -hexane fraction was purified by silica gel column chromatography to yield several compounds including katononic acid and 3-oxolupenal. Antidiabetic activities were assessed by α-amylase and α-glucosidase enzyme inhibition. Antioxidant capacities were examined by 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) scavenging assays. Further, the interaction between enzymes (α-amylase and α-glucosidase) and ligands (3-oxolupenal and katononic acid) was followed by fluorescence quenching and molecular docking studies. 3-oxolupenal and katononic acid showed IC 50 values of 46.2 μg/mL (101.6 µM) and 52.4 μg/mL (119.3 µM), respectively against the amylase inhibition. 3-oxolupenal (62.3 µg/mL or 141.9 μM) exhibited more potent inhibition against α-glucosidases compared to katononic acid (88.6 µg/mL or 194.8 μM). In terms of antioxidant activity, the relatively polar crude extract and n -butanol fraction showed the greatest DPPH and ABTS scavenging activity. However, the antioxidant activities of the purified compounds were in the low to moderate range. Molecular docking studies confirmed that 3-oxolupenal and katononic acid interacted strongly with the active site residues of both α-amylase and α-glucosidase. Fluorescence quenching results also suggest that 3-oxolupenal and katononic acid have a good affinity towards both α-amylase and α-glucosidase enzymes. This study provides preliminary data for the plant's use in the treatment of type 2 diabetes mellitus.

Invisible to the naked eye lies a tremendous diversity of organic molecules and organisms that make major contributions to important biogeochemical cycles. However, how the diversity and composition of these two communities are interlinked remains poorly characterized in fresh waters, despite the potential for chemical and microbial diversity to promote one another. Here we exploited gradients in chemodiversity within a common microbial pool to test how chemical and biological diversity covary and characterized the implications for ecosystem functioning. We found that both chemodiversity and genes associated with organic matter decomposition increased as more plant litterfall accumulated in experimental lake sediments, consistent with scenarios of future environmental change. Chemical and microbial diversity were also positively correlated, with dissolved organic matter having stronger effects on microbes than vice versa. Under our experimental scenarios that increased sediment organic matter from 5 to 25% or darkened overlying waters by 2.5 times, the resulting increases in chemodiversity could increase greenhouse gas concentrations in lake sediments by an average of 1.5 to 2.7 times, when all of the other effects of litterfall and water color were considered. Our results open a major new avenue for research in aquatic ecosystems by exposing connections between chemical and microbial diversity and their implications for the global carbon cycle in greater detail than ever before., Competing Interests: The authors declare no competing interest.

A new diterpene, cassipouryl hexadecanoate ( 2 ), in addition to the cassipourol ( 1 ) and four terpenes ( 3-6 ) were isolated from the twigs and leaves of Dacrycarpus imbricatus (Blume) de Laub. The structures of the two monocyclic diterpenes ( 1 , 2 ), were elucidated on the basic of 1D and 2D NMR spectroscopic data and compared with the literature. These two monocyclic diterpenes ( 1 , 2 ) were tested for their anti-proliferative activity on acute myeloid leukemia (OCI-AML) cells. The results showed that 1 had significantly anti-proliferative activity whereas 2 was weakly active.

Conifers have evolved complex oleoresin terpene defenses against herbivores and pathogens. In co-evolved bark beetles, conifer terpenes also serve chemo-ecological functions as pheromone precursors, chemical barcodes for host identification, or nutrients for insect-associated microbiomes. We highlight the genomic, molecular and biochemical underpinnings of the large chemical space of conifer oleoresin terpenes and volatiles. Conifer terpenes are predominantly the products of the conifer terpene synthase (TPS) gene family. Terpene diversity is increased by cytochromes P450 of the CYP720B class. Many conifer TPS are multiproduct enzymes. Multisubstrate CYP720B enzymes catalyse multistep oxidations. We summarise known terpenoid gene functions in various different conifer species with reference to the annotated terpenoid gene space in a spruce genome. Overall, biosynthesis of terpene diversity in conifers is achieved through a system of biochemical radiation and metabolic grids. Expression of TPS and CYP720B genes can be specific to individual cell types of constitutive or traumatic resin duct systems. Induced terpenoid transcriptomes in resin duct cells lead to dynamic changes of terpene composition and quantity to fend off herbivores and pathogens. While terpenoid defenses have contributed much to the evolutionary success of conifers, under new conditions of climate change, these defences may become inconsequential against range-expanding forest pests., (© 2019 The Authors. New Phytologist © 2019 New Phytologist Trust.)

The present study aims to evaluate phytochemical and pharmacological potential of total protoflavones from Macrothelypteris viridifrons . In the phytochemical study, an HPLC analysis method was established, and the optimal extraction and purification conditions were analyzed. The extractive condition was optimized as follows: the backflow extraction with 20 folds of 70% ethanol at 80◦C for 1 h twice. Moreover, by combining the alkali-extraction and acid-precipitation method with the macroporous resin purification technology, the final purity rate of total protoflavones was no less than 54.85%. In the pharmacological study, the total protoflavones from M. viridifrons showed a significant tumor-inhibitory effect in the H22 hepatoma cells transplantation model with a higher inhibitory rate of 55.76% in high dosage (100mg/kg) treatment group compared with the positive control group (20 mg/kg cyclophosphamide). Taken of all, these results support that protoflavones are the material basis of M. viridifrons as an anticancer folk medicine.

Background: Rapid emergence of multidrug resistant (MDR) organisms in hospital and community settings often result into treatment failure, thus leading the clinicians with fewer treatment options. Cyathea gigantea, an ethnomedicinally important fern used in cuts and wound infections. So, if this medicinal plant is used in treating the MDR infections then it might bring certain relief in future treatment options., Methods: Antibacterial activity of C. gigantea against MDR bacteria was assed using well diffusion and broth microdilution methods to determine the diameters of growth inhibition zones, minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC). Synergistic activity was also determined with the conventional antibiotics by disc diffusion method followed by FIC index of each of the tested antibiotic was calculated. The active extract was then subjected to fractionation by column chromatography and antibacterial activity was done with each of the collected fractions., Results: Crude extract of C. gigantea was found to be active against all the tested organisms. The MIC was 200 μg/ml against Gram-positive i.e., Staphylococcus aureus ATCC 25923 and 400 μg/ml against Gram-negative i.e., Escherichia coli ATCC 25922 and Pseudomonas aeruginosa PAO1, while the MBC was 400 μg/ml in case of Gram-positive and 800 μg/ml for Gram-negative. The synergistic activity revealed that the plant extract increased the antibacterial property of the studied antibiotics and the FIC index showed that significant synergistic activity was shown by ciprofloxacin followed by tetracycline, ampicillin and oxacillin. Antibacterial activity with the fractionated extract showed that the FR II, FR III and FR IV were active against both Gram-positive and Gram-negative bacteria, whereas FR I, FR V and FR VI did not show antibacterial property against any of the tested bacteria., Conclusions: Extracts of C. gigantea was found active against both selected Gram-positive and Gram-negative organisms and thus offers the scientific basis for the traditional use of the fern. The present study also provides the basis for future study to validate the possible use against multidrug resistant organisms.

The lindenane-type sesquiterpenoid chlojaponilactone B ( 1 ), isolated from Chloranthus japonicus , has been reported to possess anti-inflammatory properties. The present study aimed to further explore the molecular mechanisms underlying the anti-inflammatory activity of 1 . RNA-seq analyses revealed the significant changes in the expression levels of genes related to multiple inflammatory pathways upon treatment of lipopolysaccharide (LPS)-induced RAW 264.7 murine macrophages with 1 . Real time PCR (RT-PCR) and Western blotting were used to confirm the modulations in the expression of essential molecules related to inflammatory responses. Compound 1 inhibited toll like receptor 4 (TLR4) and myeloid differentiation factor 88 (MyD88) activation upon LPS stimulation, influencing the expression of NF-κB and pro-inflammatory mediators. Molecular docking studies showed that 1 bound to TLR4 in a manner similar to that of TAK-242, a TLR4 inhibitor. Moreover, our results showed that 1 suppressed inflammatory responses by inhibiting TLR4 and subsequently decreasing reactive oxygen species (ROS) generation, downregulating the NF-κB, thus reducing the expression of the pro-inflammatory cytokines iNOS, NO, COX-2, IL-6 and TNF-α; these effects were similar to those of TAK-242. We proposed that 1 should be considered as a potential anti-inflammatory compound in future research.

The remotion of hexavalent chromium in the form of chromate in aqueous solution was done using the aquatic plant Salvinia sp as biosorbent. The chemical modification of the Salvinia surface was performed by organosolv adapted method. The untreated Salvinia and the modified were characterized by infrared spectroscopy, Boehm titration, scanning electron microscopy, energy dispersive system, point of zero charge, surface area analysis, and porosity. Batch adsorption experiments were performed to observe the effects of pH, contact time, initial concentration, and temperature on the metal removal process. The characterization results show the chemistry modifically changed the modified Salvinia structure compared with untreated Salvinia. The adsorption test results showed the maximum adsorption capacity of 26.03 mg g -1 . The kinetic equilibrium was reached in about 3 h, and the better temperature and pH were 298 K and 7, respectively. The adsorption and kinetic models were Freundlich and pseud-second order, respectively. This study showed the Salvinia sp after the chemical treatment can be used with biosorbent for hexavalent chromate in the form of chromate, being a natural material with low cost and plentiful in the environment.

In the current study, the green synthesis of zinc oxide nanoparticles (ZnONPs) using the leaf extract of Cyanometra ramiflora and zinc acetate precursor is presented. The phyto-components of the extract aided the reduction and the formation of nanoparticles. The purified ZnONPs were characterized by UV-Vis spectroscopy, SEM, EDS, XRD, BET, and FTIR techniques. A sharp absorption maximum at 360 nm in the UV-Vis data affirmed the formation of ZnONPs. SEM image revealed the nanoflower morphology and EDS showed strong signals for zinc and oxygen elements. XRD spectrum confirmed the hexagonal wurtzite crystalline structure of size 13.33 nm. A significant large surface area of 16.27 m 2 /g with mesopores, was affirmed using BET analysis. FTIR substantiated the existence of the characteristic zinc and oxygen bonding vibrations at 557 cm -1 , 511 cm -1 and 433 cm -1 . The photocatalytic activity of the ZnONPs was examined using the pollutant dye, Rhodamine B. A remarkable degradation efficiency of 98% within 200 min was achieved under sunlight irradiation and a degradation constant of 0.017 min -1 was obtained. Therefore, ZnONPs synthesized using a cheap and abundant source - the leaf extract of C.ramiflora possibly will play a promising part in the degradation of toxic dyes present in the wastewater., (Copyright © 2019 Elsevier B.V. All rights reserved.)