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Phenolic Glycosides from Sugar Maple (Acer saccharum) Bark

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Abstract

Four new phenolic glycosides, saccharumosides A-D (1-4), along with eight known phenolic glycosides, were isolated from the bark of sugar maple (Acer saccharum). The structures of 1-4 were elucidated on the basis of spectroscopic data analysis. All compounds isolated were evaluated for cytotoxicity effects against human colon tumorigenic (HCT-116 and Caco-2) and nontumorigenic (CCD-18Co) cell lines.

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... 9−12 In particular, sugar maple bark contains unique phenolic glycosides among a few identified molecules. 13 A recent study by our team highlighted the great interest of sugar maple bark hot-water extract (SBkE) as a safe food additive due to its high antioxidant content (ORAC value, 3722 μmol Trolox eq/g), its diversity of mineral nutrients, and nontoxic effect reported on human neutrophil-like cells. 14 The SBkE production process has also been studied at the pilot-lab scale, confirming satisfactory recovery of antioxidant phenolic compounds (ORAC value, 3152 μmol Trolox eq/g). ...
... The other common simple phenolics, vanilloloside (bk26/bd22) was previously reported in sugar maple bark. 13 Exhibiting maximal UV absorbance at 276 nm, it was characterized by an intense MS fragment at m/z 137 [M + H − 162 − 18] + related to successive HL and H 2 O loss. ...
... Based on its UV spectrum (λ max = 265, 338−339 nm) and MS peaks at m/z 193 [M + H − 162] + (loss of the glucosyl) and 178 [scopoletin + H − 15] + (further loss of a methyl radical CH 3 • ), bk48/bd47 was elucidated as scopolin (scopoletin-7-O-β-D-glucopyranoside). 13,53,55 We report a total of nine coumarins including two glycosides in SBkE ( Figure 3B). Already found in Acer, 9 55 Four known coumarinolignans previously found in sugar maple ( Figure 3C) were identified based on their UV (λ max = 257−259 and 321−324 nm) and MS spectra. ...
Article
Recent studies about hot-water extracts from sugar maple (Acer saccharum Marsh.) bark and buds demonstrated their potentials as antioxidant food additives. However, the phenolic structures responsible for the properties of these maple-derived extracts have yet to be determined. By performing HPLC–DAD–HRMS(/MS)-based dereplication, we were able to spike and classify almost 100 metabolites in each hot-water extract. Sugar maple bark hot-water extract is rich in simple phenolic compounds and phenylpropanoid derivatives while bud extract contains predominantly flavonoids, benzoic acids and their complex derivatives (condensed and hydrolysable tannins). Among those chemical structures, we tentatively identified 69 phenolic compounds that are potentially new to the genus Acer. Considering the growing commercial demand in natural products, the phenolic fingerprints of sugar maple bark and bud hot-water extracts will help promoting these two maple-derived products as new sources of bioactive compounds for food, nutraceutical and cosmetic industries.
... Maple bark extracts, mainly those from red maple, reportedly showed in vitro radical scavenging ability, hence a potent antioxidant [8]. In addition, phenolicrich bark extracts from sugar maple and red maple were demonstrated to have glucidase inhibitory and anticancer activities [6,9]. These abovementioned health beneficial activities of maple bark extracts were mainly credited to phenolic compounds found in them. ...
... Total Phytochemicals Maple bark is reported to contain a wide range of extractable phenolic compounds including gallic acid derivatives and flavonoids such as quercetin glycosides, rutin and kaempferol [6,9,27]. These aforementioned compounds are of increasing interest due to their ability to scavenge free radicals. ...
... This increase of viability is suggestive of a stimulation/activation of neutrophils at this concentration of extracts, as described by McCracken et al. [35]. This could be possible as the fingerprint of phenolic compound in maple bark and bud are somehow similar [6,9,19]. In the case of early apoptosis (Fig. 1b-2), no significant difference was found between the control and cells treated with bark extracts (P = 0.228). ...
Article
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Sugar maple (Acer saccharum M.) and red maple (Acer rubrum L.) barks were treated with hot water to extract nutrients in order to explore, for the first time, its potential as safe dietary antioxidants. The organic and inorganic nutrients of these extracts, as well as their safety on human PLB-985 cells differentiated into neutrophils-like cells, were determined. Proximate analysis showed that both bark extracts were low in moisture and fat. Sugar maple bark extract (SM-BX) showed crude protein and ash content higher than those found in red maple bark extract (RM-BX). In addition, SM-BX had total sugars higher than those evaluated in RM-BX, while complex sugars (oligo- and/or poly-saccharides) were similarly abundant in both bark extracts. Furthermore, SM-BX demonstrated a wide array of vital minerals (K, Ca, Mg, P, Na, Fe and Cu) in quantity larger than that evaluated in RM-BX, whereas RM-BX have Zn and Mn levels higher than those found in SM-BX. Phytochemical analyses showed that RM-BX exhibited total phenolic and flavonoid contents higher than those measured in SM-BX. Consequently, RM-BX presented an antioxidant activity higher than that of SM-BX: 2.85-fold ABTS radical cation scavenging capacity and 1.9-fold oxygen radical absorbance capacity. Finally, RM-BX and SM-BX were greatly safe since, at concentration up to 100 μg/ml, they did not modify the viability of neutrophils as determined by flow-cytometry assay using Annexin V-FITC/Propidum Iodide as markers. In conclusion, our in vitro studies indicate that both red and sugar maple bark extracts have a real potential as food additives.
... Phenolic glycoside esters (PG) are some of the most abundant secondary metabolites in plants with novel bioactivities 16 . Several PG have been isolated from the plants of the different families and reported to possess various bioactivities including anticancer activity [17][18][19] . Previously, Tao et al. 19 isolated four new PG esters including saccharumoside B from the bark of Acer saccharum (sugar maple tree) and reported cytotoxic activity of saccharumoside B on human colon cancer cell line. ...
... Several PG have been isolated from the plants of the different families and reported to possess various bioactivities including anticancer activity [17][18][19] . Previously, Tao et al. 19 isolated four new PG esters including saccharumoside B from the bark of Acer saccharum (sugar maple tree) and reported cytotoxic activity of saccharumoside B on human colon cancer cell line. Mechanism of action of cytotoxic saccharumoside B in cancers remains to be elusive. ...
... Finally, the synthesis of naturally occurring phenolic glycoside ester, saccharumoside-B (10) (Fig. 3) was done by the debenzylation of compound 9a using Pd/CaCO 3 and TEA under H 2 atmosphere. Spectral data of synthetic sacharramoside-B was found to be identical to those of reported isolated product ( Supplementary Figures 1-28) 19 . ...
Article
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A new series of phenolic glycoside esters, saccharumoside-B and its analogs (9b-9n, 10) have been synthesized by the Koenigs-Knorr reaction. Antiproliferative activities of the compounds (9b-9n, 10) were evaluated on various cancer cell lines including, MCF-7 breast, HL-60 leukemia, MIA PaCa-2 pancreatic, DU145 prostate, HeLa cervical and CaCo-2 colon, as well as normal human MCF10A mammary epithelial and human peripheral blood mononuclear cells (PBMC) by MTT assay. Compounds (9b-9n, 10) exhibited considerable antiproliferative effects against cancer cells with IC50 range of 4.43 ± 0.35 to 49.63 ± 3.59 μM, but they are less cytotoxic on normal cells (IC50 > 100 μM). Among all the compounds, 9f showed substantial antiproliferative activity against MCF-7 and HL-60 cells with IC50 of 6.13 ± 0.64 and 4.43 ± 0.35, respectively. Further mechanistic studies of 9f were carried out on MCF-7 and HL-60 cell lines. 9f caused arrest of cell cycle of MCF-7 and HL-60 cells at G0/G1 phase. Apoptotic population elevation, mitochondrial membrane potential loss, increase of cytosolic cytochrome c and Bax levels, decrease of Bcl-2 levels and enhanced caspases-9 and -3 activities were observed in 9f-treated MCF-7 and HL-60 cells. These results demonstrate anticancer and apoptosis-inducing potentials of 9f in MCF-7 and HL-60 cells via intrinsic pathway.
... From the review of literature, the compound vanilloloside (compound 4) was selected by virtue of having reported MIC values of [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] μg/mL against the Gram-negative bacteria Escherichia coli, Klebsiella pneumoniae, Salmonella typhimurium and Pseudomonas aeruginosa [15]. Moreover, vanilloloside was previously isolated from honeybee venom and several plant species, whereby it was associated with wound healing, neuroprotection, anti-inflammatory, antibacterial, antimutagenic, and anticancer activities, among others [16][17][18][19][20][21][22]. ...
... From the review of literature, the compound vanilloloside (compound 4) was selected by virtue of having reported MIC values of [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] μg/mL against the Gram-negative bacteria Escherichia coli, Klebsiella pneumoniae, Salmonella typhimurium and Pseudomonas aeruginosa [15]. Moreover, vanilloloside was previously isolated from honeybee venom and several plant species, whereby it was associated with wound healing, neuroprotection, anti-inflammatory, antibacterial, antimutagenic, and anticancer activities, among others [16][17][18][19][20][21][22]. ...
Article
The ongoing threat of Antimicrobial Resistance (AMR) complicated by the rise of Multidrug-Resistant (MDR) pathogens calls for increased efforts in the search for novel treatment options. While deriving inspiration from antibacterial natural compounds, this study aimed at using synthetic approaches to generate a series of glucovanillin derivatives and explore their antibacterial potentials. Among the synthesized derivatives, optimum antibacterial activities were exhibited by those containing 2,4- and 3,5-dichlorophenylamino group coupled to a glucovanillin moiety (compounds 6 h and 8d respectively). In those compounds, the Minimum Inhibitory Concentrations (MIC) of 128-256 μg/mL were observed against reference and MDR strains of Klebsiella pneumoniae, Methicillin-resistant Staphylococcus aureus (MRSA) and vancomycin-resistant Enterococcus faecium (VRE). Moreover, these findings emphasize the claims from previous reports on the essence of smaller molecular size, the presence of protonatable amino groups and halogens in potential antibacterial agents. The observed moderate and broad-spectrum activities of the stated derivatives point to their suitability as potential leads towards further efforts to improve their antibacterial activities.
... The same approach can be used to develop structurally modi ed analogs of saccharumoside B (Fig. 1A). This phenolic glycoside from sugar maple (Acer saccharum) bark is of great interest to medicinal chemists because of its unique biological properties [7], including promising anti-tumor activity [7][8]. For example, saccharumoside-B and its derivatives (Fig. 1B) showed high antiproliferative activity against various tumor cell lines (MCF-7, HL-60, MIA PaCa-2, DU145, HeLa, CaCo-2, MCF10A) with IC 50 values ranged from 4.4 ± 0.4 to 49.6 ± 3.6 µM, and low cytotoxicity to normal cells (IC 50 > 100 µM). ...
... The same approach can be used to develop structurally modi ed analogs of saccharumoside B (Fig. 1A). This phenolic glycoside from sugar maple (Acer saccharum) bark is of great interest to medicinal chemists because of its unique biological properties [7], including promising anti-tumor activity [7][8]. For example, saccharumoside-B and its derivatives (Fig. 1B) showed high antiproliferative activity against various tumor cell lines (MCF-7, HL-60, MIA PaCa-2, DU145, HeLa, CaCo-2, MCF10A) with IC 50 values ranged from 4.4 ± 0.4 to 49.6 ± 3.6 µM, and low cytotoxicity to normal cells (IC 50 > 100 µM). ...
Preprint
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In this work, a series of novel pyridine- and pyridoxine-based saccharumoside-B derivatives were synthesized, and their antitumor activity on nine human tumor cell lines (MCF-7, MDA-MB-231, A-498, SNB-19, M-14, NCI-H322M, HCT-115, HCT-116, PC-3) and cytotoxicity on three conditionally normal cell lines (HEK-293, Chang Liver, MSC) were studied in comparison with camptothecin, doxorubicin and saccharumoside-B. Structure-activity patterns, and in particular the contribution to antitumor activity of the peripheral fragments of the studied pharmacophore were analyzed. Our synthetic explorations also allowed us to propose a new efficient approach to the synthesis of saccharumoside B, which was used as a reference drug.
... Studies on bark, leaves, and buds of red maple (Acer rubrum L.) and sugar maple (Acer saccharum Marsh.) provided information regarding highly potent phenolic glycosides including galloyl derivatives specific to the genus Acer and their biological properties (Yuan et al. 2011;Ma et al. 2016;Park et al. 2017;Meda et al. 2017). Based on the traditional use of bark infusions in Aboriginal Canadian folk medicine and these recent achievements, the extraction of antioxidants from red and sugar maple bark using hot water has been optimised at lab scale (Geoffroy et al. 2017a). ...
... Considering all this, additional investigations of the structures and possible immunostimulating activities of the oligo/polysaccharides present in SMBE seem relevant to provide information about their potential for prebiotic applications. Being of less interest for a specific application, the low content in phenolic compounds in SMBE associated to a large variety of structures found in sugar maple bark (Yuan et al. 2011) could still present interest as a food additive if used as a totum. ...
Article
The growing customer demand in safer food additives leads the food industry to investigate new sources of bioactive compounds. In addition, the need for “greener” production processes makes aqueous extractions of by-products from plant or wood processing increasingly attractive. Based on recent studies demonstrating the biological properties of the constituents from maple bark, this paper investigates sustainable ways of efficiently producing red and sugar maple bark extracts (RMBE and SMBE) as antioxidant food additives. Several ways to obtain dried extracts were investigated considering the final quality of the extracts (antioxidant capacity, total phenolic, sugar, and protein contents), the extract recovery, and energy consumption of the process. Optimising the concentration and drying steps using principal component analysis provided two optimal variants of the process. Reverse osmosis/freeze-drying appeared to maximise extract quality, while reverse osmosis/spray-drying allowed the lowest power consumption for a sufficient quality. Optimal extracts from both species provided moderate-to-high ORAC and EC50 DPPH· values compared to recognised natural food additives confirming their interest for antioxidant enrichment. Considering the favourable repeatability between pilot-scale production processes for RMBE and SMBE despite their distinct chemical profiles, this study could provide a decent basis to investigate the optimal processing of other water-extractable materials.
... Our group is interested in isolating bioactive compounds from edible and medicinal plant species. As part of this research program, we recently investigated maple syrup (Li & Seeram, 2010) and extended those studies to non-consumed parts of the maple species used for its production (Yuan, Wan, Liu, & Seeram, 2012;Yuan et al., 2011;Wan et al., 2012). Our discovery of new bioactive compounds from the stems and bark of these maple species (Wan et al., 2012;Yuan et al., 2011Yuan et al., , 2012) encouraged us to initiate similar studies on other food plants. ...
... As part of this research program, we recently investigated maple syrup (Li & Seeram, 2010) and extended those studies to non-consumed parts of the maple species used for its production (Yuan, Wan, Liu, & Seeram, 2012;Yuan et al., 2011;Wan et al., 2012). Our discovery of new bioactive compounds from the stems and bark of these maple species (Wan et al., 2012;Yuan et al., 2011Yuan et al., , 2012) encouraged us to initiate similar studies on other food plants. Based on our ongoing and future planned studies, this report is being included under this overarching theme. ...
... The extractable polyphenols from sugar maple bark have been intensively studied by our team in recent years [9,10]. Previous investigations have reported that the sugar maple bark contains unique phenolic glycosides, among which are a few identified molecules such as gallotannins, lignans, coumarins, and coumarinolignans [10,11]. These compounds and their extracts have been reported to exhibit a broad spectrum of in vitro and in vivo biological activities, including antioxidant, antitumor, antimicrobial, anti-inflammatory, antidiabetic, and hepatoprotective activities, in addition to promoting osteoblast differentiation [9,12]. ...
... In addition to being ornamental, sugar maple is basically best known for the production of maple syrup, a widely consumed high antioxidant-rich product produced from the sap of the sugar maple tree [7,8]. Despite the availability of scientific documentation on the identification of several antioxidant PCs from sugar maple syrup, sap, bark, and wood [9][10][11][12][13], sugar maple leaves (SML) biomass is yet underexploited and considered as natural waste biomass which is why in urban and peri-urban areas, maple leaves are either ground to make compost or burnt directly. As a consequence, serious economic (disposal/handling of biomass represents a cost to the local government) and environmental problems (such as greenhouse gas emissions, air pollution, loss of soil moisture, and loss of balance in ecosystem) have been evolved [14][15][16]. ...
Article
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A maceration process was optimized using a full factorial design coupled to a response surface model for the extraction of phenolic compounds (PCs) from sugar maple leaves (SML). As part of the extraction process, high-speed homogenization (HSH) as a pre-treatment condition was investigated to promote the efficiency of maceration. Finally, characterization of SML was performed using colorimeter, SEM, FTIR spectroscopy, and LC-ESI-Q-TOF-MS/MS. The antioxidant activity of the extract was investigated as well using standard methods. Results showed that ethanol concentration and solid-to-solvent ratio had significant effects (p < 0.05) on the extraction of PCs and HSH can be considered as an effective pre-treatment towards maximizing phenolic compounds recovery from SML. Under the optimal conditions (ethanol concentration of 61.63% at a solid-to-solvent ratio of 1:38.22 g/mL), the experimental %total yield (28.57%), total phenolics (110.87 mg GAE/g DM), and total flavonoids (18.95 mg CTE/g DM) were in close agreement with the predicted values. A total of 81 PCs were tentatively identified including mostly phenolic acids and flavonoids and their derivatives from SML using LC-ESI-Q-TOF-MS/MS. What is more, a gallotannins pathway existing in SML from gallic acid to tetragalloyl-D-glucopyranose was proposed. The study suggested SML as a promising source of PCs which can be effectively extracted through maceration and be further used as natural antioxidants in the formulation of functional food systems.
... Maple bark is a rich source of phenolics compounds and has glucidase inhibitory and anticancer activities (Yuan et al., 2011(Yuan et al., , 2012. Several plant parts and their extracts have been used o characterization the content of total phenolics. ...
Chapter
Plant extracts contain a varied range of chemicals such as terpenoids, phenolic compounds, alkaloids, glucosinolates, and various organic acids. These chemicals are responsible for their unique nature and perceived biological activity of plant extracts. Owing to the wide acclaimed biological activities of plant extracts, they have been used as natural ingredients and have received significant renewed interest recently. Several plant extracts have been used as commercial preservatives in food because of their green image. The current chapter discusses various chemicals present in plant extracts and emphasizes the structure activity relationship of these chemicals.
... Maple bark is a rich source of phenolics compounds and has glucidase inhibitory and anticancer activities (Yuan et al., 2011(Yuan et al., , 2012. Several plant parts and their extracts have been used o characterization the content of total phenolics. ...
Chapter
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In recent years, great interest has been focused on using natural extracts of plant origin because of the possible adverse effects associated with the consumption of synthetic products being manufactured in the markets. A variety of plant extracts are known to have rich source of vitamins, minerals, phenolic compounds, antioxidants, alkaloids, and many other secondary metabolites. The interest in these natural components is not only due to their biological value but also to their economic impact. These secondary metabolites have the potential to cure various chronic diseases. Being an integral part of traditional medicine, these extracts need to be explored for various phytochemcial characterization, isolation, and their mechanism.
... A wide number of glycosides described in previous studies showed promising antitumor activity [8][9][10][11][12][13][14][15][16][17][18][19]. Saccharumoside-B (Fig. 1A), a phenolic glycoside isolated from Sugar Maple (Acer saccharum) bark, also demonstrated promising antitumor effects [20]. In particular, saccharumoside-B and its derivatives (Fig. 1B) showed high antiproliferative activity against various tumor cell lines (MCF-7, HL-60, MIA PaCa-2, DU145, HeLa, CaCo-2, and MCF10A) with IC 50 values ranged from 4.43 ± 0.35 to 49.63 ± 3.59 μM, and low cytotoxicity to normal cells (IC 50 > 100 μM) [21]. ...
Article
Full-text available
A series of 11 new pyridoxine-based structural analogs of saccharumoside-B were obtained using original synthetic approach. Antitumor activity of these compounds against nine human tumor cell lines (MCF-7, MDA-MB-231, A-498, SNB-19, M-14, NCI-H322M, HCT-115, HCT-116, and PC-3) was studied, and cytotoxic activity to three normal (HEK-293, Chang Liver, and MSC) cell lines was evaluated. Among the synthesized compounds, 12d, 12e, 13b, 13d, 13e, and 14 exhibited the highest antitumor activity, comparable to that of camptothecin and doxorubicin, but with significantly increased selectivity toward tumor cells.
... Over 300 compounds have been identified from maple species, and the majority of these compounds are phenolics including tannins, flavonoids, lignans, phenylpropanoids, and phenolic acids [1]. Our laboratory had initiated a research program to identify the phytochemical constituents of various maple species found in North America including Acer rubrum L. (red maple) [10], Acer saccharum Marsh (sugar maple) [11], Acer saccharinum L. (silver maple) [12], and Acer pseudoplatanus L. (sycamore maple) [13]. During the course of these studies, we found that an n-butanol fraction of Acer platanoides L. (Norway maple) stem bark, which has not been previously chemically investigated, showed cytotoxicity against a panel of human cancer cells. ...
Article
Four new barringtogenol C-type triterpenoid saponins, namely acerplatanosides A – D (1–4), along with 22 known compounds (5–26), were isolated from the stem bark of Norway maple (Acer platanoides). Their structures were elucidated on the basis of comprehensive spectroscopic analyses and chemical hydrolysis. This is the first report of triterpenoid saponins isolated from Norway maple. Compounds 1, 3, and 4 showed cytotoxicity against 4 human cancer cell lines with IC50 values ranging from 9.4 to 39.5 µM.
... These phenolic glycosides have been isolated from bark of sugar maple. [35] Acertannin isolated from A. saccharum has shown antihyperglyce- mic effects on rats. [36] A mixture of phenolic extractives with antioxidant activities have been reported from sugar maple bark through catalytic organosolv pulping, [37] or optimized hot water extraction. ...
Article
The bark of trees is an abundant material for chemical by-products. The combination effects of different concentrations of Acer saccharum var. saccharum inner (IB) and outer (OB) bark acetone extracts with citric acid (CA) applied to Leucaena leucocephala wood were evaluated against the growth of three common molds (Trichoderma viride, Fusarium subglutinans, and Aspergillus niger). IB, OB, and CA solutions were prepared at 0.25% and 0.5% and their combinations were formulated in equal amounts. Acetone extracts of IB and OB were analyzed for their chemicals composition and phenolic compounds using GC/MS and PHLC, respectively. The IB acetone extract contained 4-hydroxy-4-methyl-2-pentanone (31.67%), palmitic acid (15.52%), and linoleic acid (11.14%), while the OB acetone extract contained 1,2-benzenedicarboxylic acid, bis(2-ethylhexyl) ester (9.34%), (Z,E)-9,12-tetradecadien-1-ol (8.86%), and cis-tetrahydro-6-methoxy-2H-pyran-3-ol (5.72%). The HPLC analysis indicated the presence of 14 phenolic compounds in IB extract with major constituents caffeine (362.88 µg/g extract), and p-hydroxy benzoic acid (358.06 µg/g extract), while OB contained 12 compounds with major constituents p-hydroxy benzoic acid (8950.5 µg/g extract), gallic acid (5261 µg/g extract) and salicylic acid (572.38 µg/g extract). High total phenolic content in OB (292.67 mg GAE/g) was associated with high antioxidant activity with an IC50 values of 1.77 and 4.14 μg/mL, as measured by DPPH and β-Carotene-linoleic acid, respectively. The combination treatment of IB0.25%+ OB0.25%+CA0.25% produced the highest antifungal effects against growth of T. viride with an inhibition percentage (IP) of 10.37%, IB0.5%+CA0.5% (IP 16.66%) with F. subglutinans, while CA0.5% and OB0.25%, showed IP of 27.77% and 23.70% with A. niger, respectively. The combination effects of IB, OB and CA could be used as biocide agents for preventing mold growth on wood.
... Our group has reported on the isolation and structure elucidation (by NMR and HREISMS) of over 70 phytochemicals, from the sugar, red, and sycamore (A. pseudoplatanus) maples [3][4][5][6][7]. Among these species, only the red maple yielded glucitol-core containing gallotannins (GCGs) [3,4,6]. ...
Article
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In the course of our group's investigation of members of the maple (Acer) genus, a series of glucitol-core containing gallotannins (GCGs) were isolated and identified (by NMR and HREISMS). Among higher plants, only certain maple species are known to produce GCGs, compounds with potential nutraceutical and cosmetic applications due to their reported antioxidant, antidiabetic, anti-α-glucosidase, anti-glycation, anticancer, and skin health promoting effects. Herein, we sought to investigate whether the previously un-investigated silver maple (Acer saccharinum) species was also a source of GCGs. Nine phenolic compounds, including six GCGs, were identified (by HPLC-DAD analyses using previously isolated standards) as ginnalins A-C (1-3), maplexins B, D, and F (4-6), methyl syringate (7), methyl gallate (8), and 3-methoxy-4-hydroxyphenol-1-β-D-(6-galloyl)-glucopyranoside (9). In addition, one sesquiterpenoid, namely, pubineroid A (10), was isolated and identified (by NMR).
... Traditional and anecdotal medicinal claims for other parts of these plants in Amerindian medicine have also incited the interest to study different maple tissues. Previous phytochemical studies have reported gallotannins, procyanidins, lignans, coumarins, and flavonoids in leaves, bark and wood of the red maple and sugar maple species [8][9][10][11]. ...
Article
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We are reporting here the results of the first study on phenolic constituents of hot water and aqueous ethanol extracts of sugar (Acer saccharum Marsh) and red maple (Acer rubrum L.) buds. The bud extracts were compared for their phenolic fingerprints using Thin Layer Chromatography (TLC) supported by chemometric tools. The NP/PEG (Natural Products/Polyethylene Glycol) derivatized TLC plate was photographed using a digital camera. The image of each plate was subsequently processed using the Image J program (1.50a version). The global analysis of TLC tracks showed major differences in colours, intensities, and positions of spots on the phenolic fingerprint of the extracts of buds from red and sugar maple. The chemometric approach revealed that phenolic compounds with lower Retention factor (Rf) were revealed for sugar maple extracts, while those exhibiting bright intensity spots at Rf between 0.3 and 0.8 were observed for red maple extracts, thus indicating the differences between their phenolic fingerprints. The solvent used for extraction seems also to have an effect on the phenolic compounds extracted from maple buds. The results of the principal component analysis suggest that there are significant differences in the phenolic fingerprints between the bud extracts of sugar and red maple which are related to both the species and the solvent applied for extraction. The obtained results demonstrate the interest to apply TLC as an efficient method in screening of phytochemicals, especially in combination with new informatics and statistical tools.
... Pakdel et al (2002) studied the extraction of betulin, a triterpenoid compound with antitumor activity, from white birch bark by a vacuum pyrolysis method. Yuan et al (2011) identified the chemical structures of four phenolic glycosides from sugar maple bark. Ross et al (1996) analyzed the chemical composition of the bark oil of balsam fir. ...
Article
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In this study, the major components in barks from five Canadian tree species and their chemical and biological properties were characterized. The extractives soluble in hexane, ethanol, and 1% NaOH solution were measured through successive extractions. Total phenolic content was determined by the Folin-Ciocalteu method, antioxidant activity was evaluated by 1,1-diphenyl-2-picrylhydrazyl-free radical scavenging assay, and the characteristics of functional groups were analyzed by Fourier transform IR spectroscopy. The formaldehyde-condensable polyphenols were estimated with the Stiasny method. Lignin and holocellulose contents were determined by gravimetric method. Results showed that the amounts of extractives soluble in the three solvents varied significantly with bark species. Lodgepole pine bark contained the highest content of hexane-soluble extractives (15.0%), and aspen bark contained a very high content of ethanol solubles (22.3%). The 1% NaOH solubles ranged from 20.5 to 35.5% of the original bark. Except balsam fir, the total phenolic contents of ethanol solubles were between 200 and 300 mg equivalent catechin per gram of extract. The ethanol-soluble extractives from lodgepole pine bark and sugar maple bark had considerably high antioxidant potential; their IC50 values were about 11 mg/mL. The barks of softwood species contained a higher amount of formaldehyde-condensable polyphenols than those of hardwood species included in this study.
... By repeated silica gel column chromatography, ODS column chromatography, and preparative HPLC, we achieved: (2E)-oct-2-enoate-2-O-β-D-glucopyranosyl-β-D-glucopyranoside (1); (2E)-2,6- dimethyl -6-hydroxyl-oct-2,7-dienoate-2-O-β-D-glucopyranosyl-β-D-glucopyranoside (2); saccharumoside C(3) [16] ; O-β-D-apiofuranosyl-(1→6)-O-β-D-glucopyranosides of 3-methyl-2- butenol (4) [17]; 3-methyl-but-2-en-1-yl β-D-gluco-pyranosyl (1→6)-β-D-glucopyranoside(5) [18]; benzyl-glucopyranoside(6) [19]; Hexyl-O-β-D-glucopyranoside (7) [20]; and caproic acid(8). The structures of all compounds are showed in ...
Article
Two new saccharide fatty acid esters (1) and (2), and six other compounds were isolated from the fruit of Morinda citrifolia L. (Rubiaceae) The structures were established as (2E)-oct-2-enoate-2-0-β-D-glucopyranosyl-β-D-glucopyranoside(l), (2E)-2,6-dimethyl-6-hydroxyl-oct-2,7-dienoate-2-0-β-D-glucopyranosyl-β-D-glucopyranoside(2), saccharumoside C(3), C-β-D-apiofuranosyl-(l-→6)-0-β-D-glucopyranosides of 3-methyl-2-butenol(4), 3-methyl-but-2-en-l-yl β-D-glucopyranosyl (1-→6)-β-D-glucopyranoside(5), benzyl-glucopyranoside(6), Hexyl-C-β-D-glucopyranoside(7), and caproic acid(8). Compound 1 and 2 showed moderate activity against ABTS (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonate)) radical in concentration of 0.1-3.2 mg/mL.
... The 13 C NMR and HSQC spectra revealed the presence of 21 carbon resonances, comprising one methoxy, two oxymethylenes, twelve methines (seven sp 2 and five sp 3 ), and six quaternary carbons, of which one was an ester carbonyl. The 1 H and 13 C NMR (Table 1) spectra were similar to those of phenolic glycosides, and indicated the presence of a vanillyl alcohol, a glucose, and a 4-hydroxybenzoyl moiety (Yuan et al., 2011). Analyses of the 1D and 2D NMR including HSQC and HMBC data allowed for the establishment of the structure of 1. ...
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Four new phenolic compounds, vitexnegheteroins A-D (1-4), were isolated from the seeds of Vitex negundo var. heterophylla, together with eight known compounds. Their structures were established on the basis of extensive 1D and 2D NMR experiments, as well as their mass spectroscopic data. The absolute configuration of compound 4 was determined by comparing its experimental CD spectrum with that calculated by the time-dependent density functional theory (TDDFT) method. The antioxidant and anti-inflammatory activities of these phenolics were also evaluated. Most of the compounds showed strong ABTS radical scavenging activities and all the tested isolates exhibited inhibitory effects on lipopolysaccharide-induced NO production in murine microglial BV-2 cells. The bioactive studies supported the traditional use of this edible aromatic plant and disclosed the potency of it to be developed as new antioxidant and anti-inflammatory functional food.
... contorta (Higuchi et al. 1977), only their 1 H NMR data have been reported. In contrast, large amounts of data have been published for native lignan glycosides (Sugiyama et al. 1993; Jin et al. 1999; Kamel 2003; Machida et al. 2009; Yuan et al. 2011b), although differences in the conditions under which the NMR measurements were collected have diminished the overall usefulness of these data, and they are consequently not suitable for the analysis of phenyl glyoside-type LCCs. The systematic collection of fundamental data for the correlations between the 1 H and 13 C signals from the 2D HSQC spectra of phenyl glycoside type LCC model compounds is therefore strongly desired. ...
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Twelve monolignol (coniferyl alcohol, sinapyl alcohol and p-coumaryl alcohol) beta-glycosides (beta-glucosides, beta-galactosides, beta-xylosides and beta-mannosides) were synthesised to obtain fundamental NMR data for the analysis of phenyl glycoside type lignin-carbohydrate complexes (LCCs). That is, the 1,2-trans glycosides (the beta-glucosides, beta-galactosides and beta-xylosides) and the 1,2-cis glycosides (the beta-mannosides) were synthesized by means of Koenig-Knorr glycosylation and beta-selective Mitsunobu glycosylation strategies, respectively. In addition, dihydromonolignol and p-hydroxybenzaldehyde derivative beta-glycosides were also prepared from the corresponding monolignol glycosides and their intermediates, respectively. The correlation observed for the C-1 beta-H-1 beta bonds of the sugar moieties in the HSQC spectra of the all beta-glycosides varied and were in the range of delta(C)/alpha(H) 96-104/ 4.7-5.4 ppm. Especially, it was found that the correlations derived from the C-1 beta-H-1 beta bonds of the guaiacyl and p-hydroxyphenyl beta-mannosides were close to those derived from the C-1 alpha-H-1 alpha bonds of the 4-O-methyl-alpha-D-glucuronic acid moieties described in the literature.
... The moiety of 6 has been detected previously in different compounds like glehlinosides from Glehnia littoralis (Euphorbiaceae) [27], 6 -O-vanilloylsucrose from Saccharum officinarum (Poaceae) [28], 6 -O-vanilloyicariside B 5 from Baccaurea ramiflora (Euphorbiaceae) [29], amburoside G from Amburana cearensis (Fabaceae) [30], saccharumosides from Acer saccharum (Aceraceae) [31], and 1 -O-galloyl-6 -O-vanilloyl--d-glucopyranose from Alchornea trewioides (Euphorbiaceae) [32]. This is the first case where 6 has been isolated as a separate compound. ...
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An ethanolic extract and its ethyl acetate-soluble fraction from leaves of Calendula officinalis L. (Asteraceae) were found to show an inhibitory effect on amylase. From the crude extract fractions, one new phenolic acid glucoside, 6'-O-vanilloyl- β -D-glucopyranose, was isolated, together with twenty-four known compounds including five phenolic acid glucosides, five phenylpropanoids, five coumarins, and nine flavonoids. Their structures were elucidated based on chemical and spectral data. The main components, isoquercitrin, isorhamnetin-3-O- β -D-glucopyranoside, 3,5-di-O-caffeoylquinic acid, and quercetin-3-O-(6''-acetyl)- β -D-glucopyranoside, exhibited potent inhibitory effects on amylase.
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Objectives: The present study reports antioxidant potential, the in-vitro antiproliferative activity of saccharumoside-B, and molecular docking studies on the binding affinity of saccharumoside-B towards various proteins involved in breast cancer pathogenesis. Methods: The in-vitro antioxidant activity of saccharumoside-B was determined by DPPH, superoxide and nitric oxide free radical scavenging assays. The antiproliferative activity was evaluated in-vitro by MTT assay. The binding affinity of saccharumoside-B towards the HSP90, HER2, human estrogen receptor and tyrosine-protein kinase C-SRC were determined by the molecular docking studies. Results: Saccharumoside-B showed a significant dose-dependent antioxidant activity and potent dose-dependent antiproliferative effect on the MCF-7 breast cancer cell line (IC50 = 22.57±0.39µM) among all other cell lines studied. Tamoxifen was used as a positive control for MCF-7 cell line (IC50 = 27.97±1.07µM). The IC50 of saccharumoside-B on normal MCF-10A cell line (IC50>1000µM) showed a promising safety profile, whereas tamoxifen’s IC50 on MCF-10A normal cell line was found to be 29.6 ± 0.84 µM. The molecular docking analysis revealed that saccharumoside-B was inserted into the active site pockets of all the tested proteins involved in the breast cancer pathogenesis with varying binding affinities. Conclusion: The antioxidant studies revealed the potential antioxidant effect of saccharumoside-B. The in-vitro and in-silico studies are indicating the safe and multiple target protein inhibitory potential of saccharumoside-B against breast cancer. This study suggests that saccharumoside-B can be developed into a new class of anticancer drugs with a high safety profile in the future.
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We synthesized a number of new derivatives of phenolic glycoside saccharumoside-B based on pyridoxine and 3-hydroxy-2-methylpyridine and studied their cytotoxicity in vitro against three normal (HEK-293, Chang Liver, MSC) and nine tumor (MCF-7, MDA-MB-231, A-498, SNB-19, M-14, NCI-H322M, HCT-115, HCT-116, PC-3) human cell lines compared with camptothecin, doxorubicin, and saccharumoside-B. The effect of the peripheral fragments of phenolic glycoside on the target activity was studied and the structure—antitumor activity relationship was established. A new efficient approach to the synthesis of saccharumoside-B was proposed.
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Background Saccharumoside-B and its analogs were found to have anticancer potential in-vitro. The present study reports acute toxicity, molecular docking, ADMET profile analysis, and in-vitro and in-vivo anti-inflammatory activity of saccharumoside-B for the first time. Methods The in-vitro enzyme inhibitory activity of saccharumoside-B on PLA2, COX-1, COX-2, and 5-LOX enzymes were evaluated by the cell-free method, its effect on TNF-α, IL-1β, and IL-6 secretion levels in LPS stimulated THP-1 human monocytes was determined by ELISA based methods. The anti-inflammatory activity was evaluated in-vivo by carrageenan-induced rat paw edema model. To test its binding affinity at the active site pockets of PLA2 enzymes and assess drug-like properties, docking experiments and ADMET studies were performed. Results Saccharumoside-B showed selective inhibition of sPLA2 enzyme (IC50 = 7.53 ± 0.232 µM), thioetheramide-PC was used as a positive control. It showed significant inhibition (P ≤ 0.05) of TNF-α, IL-1β, and IL-6 cytokines compared to the positive control dexamethasone. Saccharumoside-B showed a dose-dependent inhibition of carrageenan-induced rat paw edema, with a maximum inhibition (76.09 ± 0.75) observed at 3 hours after the phlogistic agent injection. Saccharumoside-B potentially binds to the active site pocket of sPLA2 crystal protein (binding energy - 7.6 Kcal/Mol). It complies with Lipinski’s Rule of Five, showed a promising safety profile, and the bioactivity scores suggested it as a better enzyme inhibitor. Conclusion Saccharumoside-B showed significant PLA2 inhibition. It can become a potential lead molecule in synthesizing a new class of selective PLA2 inhibitors with a high safety profile in the future.
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Rhododendron micranthum is used traditionally as a remedy for the treatment of chronic bronchitis in China. To clarify the chemical basis and provide a reference for the rational use of this medicinal plant, a phytochemical study was carried out on the twigs and leaves of R. micranthum, which afforded eight new compounds (1–8) and eight known compounds (9–16). Their structures were rigorously determined by comprehensive HRESIMS, NMR and electronic circular dichroism (ECD) analyses. The anti-inflammatory activities of these compounds were evaluated. Compounds 3, 13, and 14 suppressed the transcription of the NF-κB-dependent reporter gene in LPS-induced 293T/NF-κB-luc cells at 10 μM, while no effect on cell viability was observed.
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Descaudatine A (1), an undescribed phenolic glycoside, along with a known analogue (2) and ten flavonoids (3-12), were isolated from the whole plant of Desmodium caudatum. Compounds 1 and 4 exhibited potent antioxidant activities with the IC50 of 58.59 μM and 31.31 μM, respectively, which were approached to that of the positive control Vitamin C (IC50 = 46.32 μM). Meanwhile, 12 showed moderate antioxidant activity with the IC50 of 173.9 μM. Besides, compounds 3 and 6 inhibited the proliferation of HeLa cells with IC50 values of 56.14 μM and 69.04 μM, respectively. Further studies indicated that 3 and 6 could dose-dependently induce PARP cleavage and might trigger caspase-3, 8, 9 activation to induce apoptosis. RXRα is an ideal anticancer target of nuclear receptor. The reporter gene assay of RXRα indicated that 3 and 6 could inhibited the 9-cis-RA induced RXRα transcription in a concentration-dependent manner.
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The red maple and sugar maple (Acer rubrum and A. saccharum, respectively) contain acertannins (ginnalins and maplexins), galloylated derivatives of 1,5-anhydro-D-glucitol (1,5-AG, 1). These compounds have a variety of potential medicinal properties and we have shown that some of them promote the expression of ceramide synthase 3. We now report on the beneficial effects of ginnalin B, (6-O-galloyl-1,5-AG, 5), leading to acceleration of skin metabolism and reduction of the turnover time. Ginnalin B dose-dependently increased the relative amount of keratin 10, keratin 1, and filaggrin gene, with maximal increase of 1.7-, 2.9, and 5.2-fold at 100 μM, respectively. The validation study showed that it had superior capacity to induce multiple stages of keratinocyte differentiation and significantly elevated the immunostaining site of keratin 10 and filaggrin in a 3-dimensional cultured human skin model, by 1.2 and 2.8-fold, respectively. Furthermore, ginnalin B caused the arrest of proliferation at the G 0 /G 1 phase but it did not induce apoptotic cell death in normal human keratinocytes. Molecular studies revealed that ginnalin B up-regulated the levels of NOTCH1 and a concomitant increase p21 expression. Ginnalin B, therefore, represents a new class of promising functional and medical cosmetic compound and it could contribute to the maintenance of homeostasis of the epidermis.
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Sapium baccatum has been traditionally used as therapeutic remedies. To support its medicinal benefits, our current phytochemical investigation attempted to further discover novel bioactive compounds from S. baccatum. Eight new phenolic compounds, namely, seven coumarins (1–7) and one monoterpene galloylglycoside (8), together with 23 (9–31) known compounds were isolated. Their structures were determined by extensive spectroscopic methods and comparison with literatures. The three pairs of enantiomers of 1, 2 and 7 were confirmed on the basis of HPLC chiral analysis, electronic circular dichroism data and optical rotations. Two coumarins (1–2) were proven to be artifacts through HPLC analysis. The inhibitory effects on TNF-α secretion were examined biologically in LPS-induced BV2 microglia cells and all of the tested compounds exhibited significant inhibitory activity, especially new compound 1 possessed stronger inhibitory effects compared to the positive control quercetin. In addition, compounds 14 and 15 showed weak antifungal activity against Candida albicans SC5314 with MIC values both at 64 μg/mL. The results laid a solid foundation for additional research on S.baccatum related to its anti-inflammatory and antifungal medicinal value.
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In the forest industry, bark is an abundant residue, predominantly converted into calorific energy. As the antioxidant potential of phenolic compounds from sugar maple (Acer saccharum Marsh.) and red maple (Acer rubrum L.) bark has previously been established, the present study focused on the hot-water extraction optimization of these barks. Several process parameters (maple species, temperature, duration, ratio bark/water, particle size) were thus studied and large disparities were found between the two species. Extraction yield, phenolic content, and antioxidant capacity of red maple extracts were several times higher than those of sugar maple extracts. Principal component analysis, applied to the selected best extraction conditions, identified 3–4 clusters depending on the maple species. These groups were sorted from the highest extraction yield and energy consumption combined with the lowest phenolic content and antioxidant capacity, to moderate extraction yield and energy consumption with the highest phenolic content and antioxidant capacity.
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Scope: Maple syrup contains various polyphenols and we investigated the effects of a polyphenol-rich maple syrup extract (MSXH) on the physiology of mice fed a high-fat diet (HFD). Methods and results: The mice fed a low-fat diet (LFD), an HFD, or an HFD supplemented with 0.02% (002MSXH) or 0.05% MSXH (005MSXH) for 4 weeks. Global gene expression analysis of the liver was performed, and the differentially expressed genes were classified into three expression patterns; pattern A (LFD < HFD > 002MSXH = 005MSXH, LFD > HFD < 002MSXH = 005MSXH), pattern B (LFD < HFD = 002MSXH > 005MSXH, LFD > HFD = 002MSXH < 005MSXH), and pattern C (LFD < HFD > 002MSXH < 005MSXH, LFD > HFD < 002MSXH > 005MSXH). Pattern A was enriched in glycolysis, fatty acid metabolism, and folate metabolism. Pattern B was enriched in tricarboxylic acid cycle while pattern C was enriched in gluconeogenesis, cholesterol metabolism, amino acid metabolism, and endoplasmic reticulum stress-related event. Conclusion: Our study suggested that the effects of MSXH ingestion showed (1) dose-dependent pattern involved in energy metabolisms and (2) reversely pattern involved in stress responses. This article is protected by copyright. All rights reserved.
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Covering: 2009 to 2015Lignans and neolignans are a large group of natural products derived from the oxidative coupling of two C6-C3 units. Owing to their biological activities ranging from antioxidant, antitumor, anti-inflammatory to antiviral properties, they have been used for a long time both in ethnic as well as in conventional medicine. This review describes 564 of the latest examples of naturally occurring lignans and neolignans, and their glycosides in some cases, which have been isolated between 2009 and 2015. It comprises the data reported in more than 200 peer-reviewed articles and covers their source, isolation, structure elucidation and bioactivities (where available), and highlights the biosynthesis and total synthesis of some important ones.
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Ethnopharmacological relevance: The genus Acer (Aceraceae), commonly known as maple, comprises approximately 129 species that primarily grow in the northern hemisphere, especially in the temperate regions of East Asia, eastern North America, and Europe. These plants have been traditionally used to treat a wide range of diseases in East Asia and North America. Moreover, clinical studies have shown that medicinal plants belonging to Acer are highly effective in the treatment of rheumatism, bruises, hepatic disorders, eye disease, and pain, and in detoxification. This review provides a systematic and constructive overview of the traditional uses, chemical constituents, and pharmacological activities of plants of the genus Acer. Material and methods: This review is based on a literature study of scientific journals and books from libraries and electronic sources such as SciFinder, ScienceDirect, Springer, PubMed, CNKI, Google Scholar, Baidu Scholar, and Web of Science. The literature in this review related to chemical constituents and pharmacological activities dates from 1922 to the end of October 2015. Furthermore, ethnopharmacological information on this genus was obtained from libraries and herbaria in China and USA. Results: In traditional medicine, 40 species, 11 subspecies, and one varieta of the genus Acer are known to exhibit a broad spectrum of biological activities. To date, 331 compounds have been identified from 34 species of the genus Acer, including flavonoids, tannins, phenylpropanoids, diarylheptanoids, terpenoids, benzoic acid derivatives, and several other types of compounds, such as phenylethanoid glycosides and alkaloids. Preliminary pharmacological studies have shown that the extracts and compounds isolated from this genus exhibit a broad spectrum of biological activities such as antioxidant, antitumor, anti-inflammatory, antidiabetic, hepatoprotective, and antiobesity activities, as well as promoting osteoblast differentiation. To date, reports on the toxicity of Acer species to humans are very limited, and the major safety concern of these plants is in the veterinary field. Conclusions: Based on our systematic review, Acer species can be used to treat rheumatism, hepatic disorders, eye disease, pain, etc. effectively. Some indications from ethnomedicine have been validated by pharmacological activities, such as the anti-inflammatory and hepatoprotective activities of the species. The available literature showed that most of the activities of these species can be attributed to flavonoids and tannins. To ensure the safety and efficacy in clinical practice in the future, studies identifying active molecules and clarifying their pharmacological mechanisms as well as toxicity are needed.
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Glucitol-core containing gallotannins (GCGs) are polyphenols containing galloyl groups attached to a 1,5-anhydro-D-glucitol core, which is uncommon among naturally occurring plant gallotannins. GCGs have only been isolated from maple (Acer) species, including the red maple (Acer rubrum), a medicinal plant which along with the sugar maple (Acer saccharum), are the major sources of the natural sweetener, maple syrup. GCGs are reported to show antioxidant, α-glucosidase inhibitory, and antidiabetic effects, but their antiglycating potential is unknown. Herein, the inhibitory effects of five GCGs (containing 1-4 galloyls) on the formation of advanced glycation end-products (AGEs) were evaluated by MALD-TOF mass spectroscopy, and the BSA-fructose, and G.K. peptide-ribose assays. The GCGs showed superior activities compared to the synthetic antiglycating agent, aminoguanidine (IC50 15.8-151.3 vs. > 300 µM) at the early, middle, and late stages of glycation. Circular dichroism data revealed that the GCGs were able to protect the secondary structure of BSA protein from glycation. The GCGs did not inhibit AGEs formation by the trapping of reactive carbonyl species, namely, methylglyoxal, but showed free radical scavenging activities in the DPPH assay. The free radical quenching properties of the GCGs was further confirmed by electron paramagnetic resonance spectroscopy using ginnalin A (contains 2 galloyls) as a representative GCG. In addition, this GCG chelated ferrous iron, an oxidative catalyst of AGEs formation, supporting a potential antioxidant mechanism of antiglycating activity for these polyphenols. Therefore, GCGs should be further investigated for their antidiabetic potential given their antioxidant, α-glucosidase inhibitory, and antiglycating properties.
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Forsythoneosides A-D (1-4), four unusual adducts of a flavonoid unit fused to a phenylethanoid glycoside through a pyran ring or carbon-carbon bond, and four new phenylethanoid glycosides (5-8) were isolated from the fruits of Forsythia suspensa, together with nine known compounds. The structures of 1-8, including their absolute configurations, were elucidated by spectroscopic data as well as experimental and calculated electronic circular dichroism analysis. Compounds 2 and 4 inhibited PC12 cell damage induced by rotenone, and increased cell viability from 53.9 ± 7.1% to 70.1 ± 4.0% and 67.9 ± 5.2% at 0.1 μM, respectively.
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Thirteen new limonoids, dysoxylumosins A-M (1-13), along with six known analogues (14-19) were isolated from the twigs of Dysoxylum mollissimum. Their structures were established on the basis of spectroscopic data analysis. Compounds 1-6, 8, and 12 exhibited significant inhibitory activities against human and/or mouse 11β-hydroxysteroid dehydrogenase type 1 (11β-HSD1). Dysoxylumosin F (6), the most potent substance isolated, showed an IC50 value of 9.6 ± 0.90 nM against human 11β-HSD1. (Chemical Equation Presented). © 2015 The American Chemical Society and American Society of Pharmacognosy.
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Stauntonia brachyanthera Hand-Mazz., known as zhuyaozi or north banana by Dong Ethnicity in the southwest of China, is widely accepted as a delicious fruit with high economic value because of the presence of health-promoting components and the delivery of new tastes. In search for antioxidant compounds, the activity-guided fractionation and purification processes were performed on the stems and roots of S. brachyanthera, which resulted in the isolation of six new compounds, brachyanin A–F (1–6), and seven known compounds (7–13). Their structures were elucidated by 1D and 2D NMR, and HR-ESI-MS. Brachyanin A (1) exhibited significant cytotoxicity against HepG2 and K562 cell lines with IC50 values of 6.93 and 7.89 µM, respectively, and possessed antioxidant activity. Six compounds presented stronger antioxidant activities than those of vitamin C and quercetin in three tests (DPPH, ABTS, and FRAP). Among them, calceolarioside B (9) exhibited strongest activity and was present in higher amounts in the plant, which could be designated as characteristic component for the pharmacognostic identification and the quality control of S. brachyanthera. These findings laid solid theoretical references for the exploration of traditional usage of S. brachyanthera.
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In this study the chemical constituents of the higher polar sustances from Desmodium caudatum were investigated.The compounds were isolated by using column chromatographies over silicagel, polyamide, ODS, Sephadex LH-20, and preparative HPLC. The structures of these compounds were identified on the basis of NMR and MS spectra. Thirteen compounds were obtained and their structures were identified as vanillin(1), loliolide(2), indole-3-carboxaldehyde(3), salicylic acid(4), swertisin(5), saccharumoside C(6), isosinensin (7), kaempferol 3-O-β-D-glucopyranoside-7-O-α-L-rhamnopyranoside (8), isovitexin (9), vitexin (10), nothofagin(11), resveratroloside (12), and 2"-α-rhamnopyranosyl-7-O-methylvitexin (13). Except for compound 5, the remaining compounds were isolated from D. caudatum for the first time. Compounds 2, 3, 6-8, 11-13 were separated from the genus Desmodium for the first time.
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A Co-O-Si complex oxide containing 34 wt% Co was prepared by coprecipitation of Na2SiO3 and Co(NO3)2. It had a high surface area (562 m2/g), with highly dispersed Co and Si. After sulfidation, the catalyst (CS10) exhibited high activity in hydrodesulfurization (HDS) of thiophene (99.4%) and skeletal isomerization of 1-hexene (35%) at 573 K. It could therefore be used for the skeletal isomerization of linear olefins during deep HDS of gasoline, to reduce octane number loss caused by saturation of olefins.
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Maple syrup has nutraceutical potential given the macronutrients (carbohydrates, primarily sucrose), micronutrients (minerals and vitamins) and phytochemicals (primarily, phenolics) found in this natural sweetener. Here we conducted compositional (ash, fiber, carbohydrates, minerals, amino acids, organic acids, vitamins, phytochemicals), in vitro biological, and in vivo safety (animal toxicity) studies on maple syrup extracts (MSX-1 and MSX-2) derived from two declassified maple syrup samples. Along with macronutrient and micronutrient quantification, thirty-three phytochemicals were identified (by HPLC-DAD) and nine phytochemicals, including two new compounds, were isolated and identified (by NMR) from MSX. At doses of up to 1000 mg/Kg/day, MSX was well tolerated with no signs of overt toxicity in rats. MSX showed antioxidant (DPPH assay) and anti-inflammatory (in RAW 264.7 macrophages) effects and inhibited glucose consumption (by HepG2 cells) in vitro. Thus, MSX should be further investigated for potential nutraceutical applications given its similar chemical composition with pure maple syrup.
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The methanol extract of Melochia odorata yielded three 4-quinolone alkaloids including waltherione A (1) and two new alkaloids, waltherione C (2) and waltherione D (3). Waltheriones A and C showed significant activities in an in vitro anti-HIV cytoprotection assay at concentrations of 56.2 and 0.84 μM and inhibition of HIV P24 formation of more than 50% at 1.7 and 0.95 μM, respectively. The structures of the alkaloids were established by spectroscopic data interpretation. © 2014 The American Chemical Society and American Society of Pharmacognosy.
Article
Maple sap has been consumed for centuries as a tonic by the indigenous peoples of eastern North America but is primarily utilized in this region to produce maple syrup. The natural watery form of maple sap makes its application as a functional beverage appealing but due to microbial growth, sterilization or pasteurization would be necessary before sap could be consumed. This study was designed to investigate the chemical composition (sugars, amino acids, organic acids, minerals, and phenolics) and antioxidant effects of maple sap after undergoing pasteurization and sterilization. After both processes, sugars, amino acids, organic acids, and minerals were preserved in the sap samples and they had similar phenolic contents (0.25–0.27 mg/100 g gallic acid equivalents) and antioxidant activities (IC50 ca. 550 μg/mL by DPPH assay). HPLC-DAD analyses revealed over 25 constituents in the sap samples of which 15 were identified using phenolic standards. In addition, one compound, 3′,5′-dimethoxy-4′-hydroxy-(2-hydroxy)acetophenone, not previously reported from maple syrup, was isolated and identified (by NMR) for the first time from maple sap. Therefore, the preservation of chemical constituents and antioxidant activity in maple sap after pasteurization and sterilization warrants its application as a functional beverage beyond its primary use for maple syrup production alone.
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Two new coumarin glycosides, namely nitensosides A-B (1-2), together with six known compounds, scopolin (3), 5,6,7-trimethoxycoumarin (4), d-calycanthine (5), calycanthoside (6), xeroboside (7), and scopoletin (8), were isolated from Chimonanthus nitens. The structures of the new compounds were elucidated by comprehensive analysis of IR, MS, and NMR spectroscopic data. Compounds 3, 4, 7, and 8 showed moderate inhibitory activity against Micrococcus luteus.
Article
Maplexins A-I are a series of structurally related gallotannins recently isolated from the red maple (Acer rubrum) species. They differ in number and location of galloyl derivatives attached to 1,5-anhydro-glucitol. Here, maplexins A-I were evaluated for anticancer effects against human tumorigenic (colon, HCT-116; breast, MCF-7) and non-tumorigenic (colon, CCD-18Co) cell lines. The maplexins which contained two (maplexins C-D) or three (maplexins E-I) galloyl derivatives each, inhibited cancer cell growth while those with only one galloyl group (maplexins A-B) did not. Moreover, maplexins C-D showed greater antiproliferative effects than maplexins E-I (IC(50)=59.8-67.9 and 95.5-108.5 μM vs. 73.7-165.2 and 115.5-182.5 μM against HCT-116 and MCF-7 cells, respectively). Notably, the cancer cells were up to 2.5-fold more sensitive to the maplexins than the normal cells. In further mechanistic studies, maplexins C-D (at 75 μM concentrations) induced apoptosis and arrested cell cycle (in the S-phase) of the cancer cells. These results suggest that the number of galloyl groups attached to the 1,5-anhydro-glucitol moiety in these gallotannins are important for antiproliferative activity. Also, this is the first in vitro anticancer study of maplexins.
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Chemoselective NIS/ cat. TfOH-mediated glycosylation of ethyl2,3,4-tri-O-benzoyl-1-thio-β-d-glucopyranoside (13) with ethyl2,3-di-O-acetyl-5-O-benzyl-1-thio-αβ-d-erythro-apiofuranoside (4a) gave dimer14 in an excellent yield. BF3•Et2O-catalysed condensation of the α-trichloroacetimidate31, accessible in two steps from14, with 3,4,5-trimethoxyphenol gave β-linked derivative32 followed by deprotection gave Kelampayoside A. Protecting group manipulations of32 and subsequent caffeoylation of resulting36 followed by deprotection gave Kelampayoside B.
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A new tetrazolium analog of 3-(4,5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide (MTT) was evaluated as a substitute for MTT in the microculture screening assay for in vitro cell growth. This new tetrazolium compound, 3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2- (4-sulfophenyl)-2H-tetrazolium, inner salt (MTS), in the presence of phenazine methosulfate (PMS), gave a water-soluble formazan product that had an absorbance maximum at 490-500 nm in phosphate-buffered saline. The amount of colored product formed was proportional to the number of cells and the time of incubation of the cells with MTS/PMS. MTS/PMS was reactive in all the cell lines tested which included mouse leukemia L1210 cells, mouse Ehrlich tumor cells, mouse 3T3 fibroblasts, and human colon tumor cells (HT-29). HT-29 and 3T3 fibroblasts reduced MTS/PMS more efficiently than they reduced MTT. Comparable to the amount of product formed from MTT, MTS/PMS gave excellent product formation. The IC50 value for pyrazoloimidazole obtained using MTS/PMS was 200 microM; for 5-fluoro-2'-deoxyuridine, the IC50 value was 0.9 nM. These values compared very favorably with the IC50 values obtained by direct cell counts. Further, the same IC50 values were obtained when the absorbances of the formazan product in the 96-well plates were determined after different times of incubation.
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Three new lignan glycosides were isolated from the bark of Eucommia ulmoides OLIV. (Eucommiaceae). Their structures were established as (-)-olivil 4', 4"-di-O-β-D-glucopyranoside (1), (+)-1-hydroxypinoresinol 4', 4"-di-O-β-D-glucopyranoside (2) and (+)-medioresinol 4'-O-β-D-glucopyranoside (named eucommin A) (3), based on chemical evidence and spectroscopic studies. A known lignan glycoside, (+)-syringaresinol O-β-D-glucopyranoside (4) was also isolated.
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Coumarin glucosides, esculin (1) and scopolin (2), were isolated from the bark of Olea africana MILL. (O. europaea L. subsp. africana (MILL.) GREEN) while isoscopoletin-β-D-glucoside (magnolioside) (3) was isolated from the bark of Olea capensis L. The secoiridoid glucoside oleuropein (4) was also isolated from both species.
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From the water-soluble portion of the methanol extract of the herbal medicine fennel, the fruit of Foeniculum vulgare Miller (Umbelliferae), four new phenylpropanoid glycosides, three new benzyl alcohol derivative glycosides, one new phenylethanoid and its glycoside were obtained. They were characterized by spectral investigation.
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The province of Quebec in Canada leads the world’s production of maple syrup, a natural sweetener obtained by thermal evaporation of sap collected from maple (Acer) species. As part of our laboratory’s detailed chemical investigation of Canadian maple syrup, a novel phenolic compound, 2,3,3-tri-(3-methoxy-4-hydroxyphenyl)-1-propanol, assigned the common name of quebecol, was obtained. Quebecol was isolated using a combination of chromatographic methods and identified by detailed 1D and 2D nuclear magnetic resonance (NMR) and mass spectral (MS) analyses. Liquid chromatography mass spectral (LC-MS) analyses revealed that quebecol is not originally present in maple sap. This observation, as well as the lack of a feasible biosynthetic pathway to explain its origin, suggests that quebecol is formed during the processing and/or extraction of maple syrup. Thus, the identification and biological evaluation of non-natural, process-derived compounds in maple syrup are warranted since such molecules may contribute towards the biological activities reported for this natural sweetener.
Article
The novel natural products joannesialactone, (−)-α-barbatenal, 4-hydroxy-10-epirotundone, and the E- and Z-isomers of 2-(4-hydroxyphenyl)ethenyl-α-l-rhamnopyranoside and the 3-O-rhamnosides of the dimeric proanthocyanidins afzelechin-(4α → 8)-epiafzelechin-3-O-vanillate, afzelechin-(4α → 8)-epicatechin-3-O-vanillate, afzelechin-(4α → 8)-epiafzelechin-3-O-syringate and afzelechin-(4α → 8)-epicatechin-3-O-syringate have been isolated from the root bark of Joannesia princeps, along with the antibiotic principle cyperenal, the colouring matter assufulvenal, curcusones C and D and 16 further known compounds. Structure determination was achieved manily by spectroscopic studies and/or by comparison with authentic substances.
Article
From the aerial parts of Epimedium diphyllum, a new ionone derivative glucoside, icariside B8, two new lignan glycosides, icarisides E4 and E5 and a new phenylethanoid glucoside, icariside D2, have been isolated together with 20 known compounds. The structures of four new compounds were established by spectral and chemical evidence.
Article
Cinnacassides A–E (1–5), five novel glycosides with a unique geranylphenylacetate carbon skeleton, were isolated from the stem bark of Cinnamomum cassia. Each of the cinnacassides A–D (1–4) possesses one of the four stereoisomers in the aglycone. Their structures were established by extensive spectroscopic analysis and chemical and chiroptical methods. A plausible biosynthetic route to 1–5 was also proposed.Graphical abstract
Article
The anti-hyperglycemic effects of the leaves of sugar maple, Acer saccharum and purification and identification of the active compound were investigated. Extracts of the leaves showed a potent inhibitory effect on α-glucosidase in both in vivo and in vitro experiments. In vitro enzyme-inhibitory assay-guided fractionation of the crude extract gave active compound, acertannin (2,6-di-O-galloyl-1,5-anhydro-d-glucitol) by spectroscopic analysis. This is the first report that acertannin from A. saccharum may be used in diabetes care.
Article
Using a hydroxyl radical scavenging assay, bioactivity-guided fractionation of a methanol-soluble extract of the fruits of Euterpe oleracea (acai) led to the isolation of 22 compounds of previously known structure. Altogether, 14 of these isolates were found to be active in an in vitro hydroxyl radical scavenging assay and seven of these isolates in a 1,1-diphenyl-2-picrylhydrazyl radical scavenging assay. Dihydroconiferyl alcohol, (+)-lariciresinol, (+)-pinoresinol, (+)-syringaresinol, and protocatechuic acid methyl ester exhibited cytoprotective activity in cultured MCF-7 cells stressed by H2O2. Lignans have not been previously reported as constituents of this species and were found to be representative of the aryltetrahydronaphthalene, dihydrobenzofuran, furofuran, 8-O-4'-neolignan, and tetrahydrofuran structural types.
Article
Maple syrup is made by boiling the sap collected from certain maple ( Acer ) species. During this process, phytochemicals naturally present in tree sap are concentrated in maple syrup. Twenty-three phytochemicals from a butanol extract of Canadian maple syrup (MS-BuOH) had previously been reported; this paper reports the isolation and identification of 30 additional compounds (1-30) from its ethyl acetate extract (MS-EtOAc) not previously reported from MS-BuOH. Of these, 4 compounds are new (1-3, 18) and 20 compounds (4-7, 10-12, 14-17, 19, 20, 22-24, 26, and 28-30) are being reported from maple syrup for the first time. The new compounds include 3 lignans and 1 phenylpropanoid: 5-(3″,4″-dimethoxyphenyl)-3-hydroxy-3-(4'-hydroxy-3'-methoxybenzyl)-4-(hydroxymethyl)dihydrofuran-2-one (1), (erythro,erythro)-1-[4-[2-hydroxy-2-(4-hydroxy-3-methoxyphenyl)-1-(hydroxymethyl)ethoxy]-3,5-dimethoxyphenyl]-1,2,3-propanetriol (2), (erythro,threo)-1-[4-[2-hydroxy-2-(4-hydroxy-3-methoxyphenyl)-1-(hydroxymethyl)ethoxy]-3,5-dimethoxyphenyl]-1,2,3-propanetriol (3), and 2,3-dihydroxy-1-(3,4- dihydroxyphenyl)-1-propanone (18), respectively. In addition, 25 other phenolic compounds were isolated including (threo,erythro)-1-[4-[(2-hydroxy-2-(4-hydroxy-3-methoxyphenyl)-1-(hydroxymethyl)ethoxy]-3-methoxyphenyl]-1,2,3-propanetriol (4), (threo,threo)-1-[4-[(2-hydroxy-2-(4-hydroxy-3-methoxyphenyl)-1-(hydroxymethyl)ethoxy]-3-methoxyphenyl]-1,2,3-propanetriol (5), threo-guaiacylglycerol-β-O-4'-dihydroconiferyl alcohol (6), erythro-1-(4-hydroxy-3-methoxyphenyl)-2-[4-(3-hydroxypropyl)-2,6-dimethoxyphenoxy]-1,3-propanediol (7), 2-[4-[2,3-dihydro-3-(hydroxymethyl)-5-(3-hydroxypropyl)-7-methoxy-2-benzofuranyl]-2,6-dimethoxyphenoxy]-1-(4-hydroxy-3-methoxyphenyl)-1,3-propanediol (8), acernikol (9), leptolepisol D (10), buddlenol E (11), (1S,2R)-2-[2,6-dimethoxy-4-[(1S,3aR,4S,6aR)-tetrahydro-4-(4-hydroxy-3,5-dimethoxyphenyl)-1H,3H-furo[3,4-c]furan-1-yl]phenoxy]-1-(4-hydroxy-3-methoxyphenyl)-1,3-propanediol (12), syringaresinol (13), isolariciresinol (14), icariside E4 (15), sakuraresinol (16), 1,2-diguaiacyl-1,3-propanediol (17), 2,3-dihydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-1-propanone (19), 3-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)propan-1-one (20), dihydroconiferyl alcohol (21), 4-acetylcatechol (22), 3',4',5'-trihydroxyacetophenone (23), 3,4-dihydroxy-2-methylbenzaldehyde (24), protocatechuic acid (25), 4-(dimethoxymethyl)pyrocatechol (26), tyrosol (27), isofraxidin (28), and 4-hydroxycatechol (29). One sesquiterpene, phaseic acid (30), which is a known metabolite of the phytohormone abscisic acid, was also isolated from MS-EtOAc. The antioxidant activities of MS-EtOAc (IC(50) = 75.5 μg/mL) and the pure isolates (IC(50) ca. 68-3000 μM) were comparable to that of vitamin C (IC(50) = 40 μM) and the synthetic commercial antioxidant butylated hydroxytoluene (IC(50) = 3000 μM), in the diphenylpicrylhydrazyl radical scavenging assay. The current study advances scientific knowledge of maple syrup constituents and suggests that these diverse phytochemicals may impart potential health benefits to this natural sweetener.
Article
Twenty-three phenolic compounds were isolated from a butanol extract of Canadian maple syrup (MS-BuOH) using chromatographic methods. The compounds were identified from their nuclear magnetic resonance and mass spectral data as 7 lignans [lyoniresinol (1), secoisolariciresinol (2), dehydroconiferyl alcohol (3), 5'-methoxy-dehydroconiferyl alcohol (4), erythro-guaiacylglycerol-β-O-4'-coniferyl alcohol (5), erythro-guaiacylglycerol-β-O-4'-dihydroconiferyl alcohol (6), and [3-[4-[(6-deoxy-α-l-mannopyranosyl)oxy]-3-methoxyphenyl]methyl]-5-(3,4-dimethoxyphenyl)dihydro-3-hydroxy-4-(hydroxymethyl)-2(3H)-furanone (7)], 2 coumarins [scopoletin (8) and fraxetin (9)], a stilbene [(E)-3,3'-dimethoxy-4,4'-dihydroxystilbene (10)], and 13 phenolic derivatives [2-hydroxy-3',4'-dihydroxyacetophenone (11), 1-(2,3,4-trihydroxy-5-methylphenyl)ethanone (12), 2,4,5-trihydroxyacetophenone (13), catechaldehyde (14), vanillin (15), syringaldehyde (16), gallic acid (17), trimethyl gallic acid methyl ester (18), syringic acid (19), syringenin (20), (E)-coniferol (21), C-veratroylglycol (22), and catechol (23)]. The antioxidant activities of MS-BuOH (IC50>1000 μg/mL), pure compounds, vitamin C (IC50=58 μM), and a synthetic commercial antioxidant, butylated hydroxytoluene (IC50=2651 μM), were evaluated in the diphenylpicrylhydrazyl (DPPH) radical scavenging assay. Among the isolates, the phenolic derivatives and coumarins showed superior antioxidant activity (IC50<100 μM) compared to the lignans and stilbene (IC50>100 μM). Also, this is the first report of 16 of these 23 phenolics, that is, compounds 1, 2, 4-14, 18, 20, and 22, in maple syrup.
Article
Two new neolignans (1 and 2) were isolated from the root bark of Illicium henryi, along with four known neolignans and seven known flavonoids (3-13). Their structures were elucidated on the basis of spectroscopic and chemical methods. The absolute configurations of compounds 1 and 2 were determined by the CD spectrum.
Article
A new lignan glycoside, 5-(3″,4″-dimethoxy-phenyl)-3-hydroxy-3-(4'-hydroxy-3'-methoxybenzyl)-4-hydroxymethyl-dihydrofuran-2-one 4'-O-α-L: -rhamnopyranoside (1), with seven known compounds, compound 2, koaburside, icariside E(4), cleomiscosin C, cleomiscosin D, scopoletin, and 5'-demethylaquillochin, were isolated from the EtOH extract of the wood of Acer saccharum (Aceraceae). Their structures were determined by 1D and 2D nuclear magnetic resonance (NMR) and mass spectroscopy analysis. All of the isolated compounds, 1-8, were tested for their antioxidant activity in superoxide dismutase (SOD)-like assay.
Article
Seven sesquiterpene glycosides with copacamphane, picrotoxane, and alloaromadendrane sesquiterpene aglyons along with three phenolic glycosides have been isolated from the stems of Dendrobium moniliforme. Among them, dendromonilisides A-D (1-4) were characterized as new compounds, and their structures were determined on the basis of spectral and chemical methods and by X-ray diffraction analysis. The six known compounds were identified as dendrosides A, C, and F, dendromoniliside E, vanilloloside, and acanthoside B. In a preliminary biological test procedure, compounds 1, 3, and vanilloloside were found to stimulate the proliferation of B cells and inhibit the proliferation of T cells in vitro.
Article
Further study on the constituents from the bark of Tabebuia impetiginosa (Mart. ex DC) Standley afforded twelve compounds, consisting of four iridoid glycosides, one phenylethanoid glycoside, five phenolic glycosides, and one lignan glycoside, along with seven known compounds. The structures of these compounds were determined based on the interpretation of their NMR and MS measurements and by chemical evidence.
Article
Six new sesquiterpene glycosides, compounds 1-6, with eudesmanolide, elemanolide, lindenane, and germacranolide sesquiterpene aglycons, along with one known compound, chloranoside A (7), have been isolated from the whole plant of Sarcandra glabra. The structures of 1-6 were elucidated by chemical and spectroscopic methods including (1)H-(1)H COSY, HMQC, HMBC, and NOESY NMR experiments. In addition, compounds 1-7 showed pronounced hepatoprotective activities against D-galactosamine-induced toxicity in WB-F344 rat hepatic epithelial stem-like cells.
  • K Yoshikawa
  • Y Kawahara
  • S Arihara
  • T Hashimoto
Yoshikawa, K.; Kawahara, Y.; Arihara, S.; Hashimoto, T. J. Nat. Med. 2011, 65, 191−193.
  • L Li
  • N P Seeram
  • L Li
  • N P Seeram
Li, L.; Seeram, N. P. J. Agric. Food Chem. 2011, 59, 7708−7716. (6) Li, L.; Seeram, N. P. J. Funct. Foods 2011, 3, 125−128.
colorless, amorphous powder MeOH); UV (MeOH) λ max (log ε) 299 (3.56), 265 (3.78), 220 (3.99) nm; IR ν max 3415, 2935, 1699, 1598, 1500, 1064 cm −1 ; 1 H NMR and 13 C NMR data, see Table 1
  • B Saccharumoside
Saccharumoside B (2): colorless, amorphous powder; [α] 20 D +75 (c 0.2, MeOH); UV (MeOH) λ max (log ε) 299 (3.56), 265 (3.78), 220 (3.99) nm; IR ν max 3415, 2935, 1699, 1598, 1500, 1064 cm −1 ; 1 H NMR and 13 C NMR data, see Table 1; HRESIMS m/z 465.1395
  • C S Zhao
  • Q F Liu
  • F Halaweish
  • B P Shao
  • Y Q Ye
  • W M Zhao
  • H Tsukamoto
  • S Hisada
  • S Nishibe
Zhao, C. S.; Liu, Q. F.; Halaweish, F.; Shao, B. P.; Ye, Y. Q.; Zhao, W. M. J. Nat. Prod. 2003, 66, 1140−1143. (19) Tsukamoto, H.; Hisada, S.; Nishibe, S. Chem. Pharm. Bull. 1985, 33, 396−399. (20) Cory, A. H.; Owen, T. C.; Barltrop, J. A.; Cory, J. G. Cancer Commun. 1991, 3, 207−212.
  • T Deyama
  • T Ikawa
  • S Nishibe
Deyama, T.; Ikawa, T.; Nishibe, S. Chem. Pharm. Bull. 1985, 33, 3651−3657.
  • Y W Chin
  • H B Chai
  • W J Keller
  • A D Kinghorn
Chin, Y. W.; Chai, H. B.; Keller, W. J.; Kinghorn, A. D. J. Agric. Food Chem. 2008, 56, 7759−7764.
  • J Kitajima
  • T Ishikawa
  • Y Tanaka
  • M Ono
  • Y Ito
  • T Nohara
Kitajima, J.; Ishikawa, T.; Tanaka, Y.; Ono, M.; Ito, Y.; Nohara, T. Chem. Pharm. Bull. 1998, 46, 1587−1590. (17) Achenbach, H.; Benirschke, G. Phytochemistry 1997, 45, 149− 157.
colorless, amorphous solid MeOH); UV (MeOH) λ max (log ε) 321 (3.69), 236 (3.87) nm; IR ν max 3430, 1698, 1603, 1495 cm −1 ; 1 H NMR and 13 C NMR data, see Table 2
  • D Saccharumoside
Saccharumoside D (4): colorless, amorphous solid; [α] 20 D −13 (c 0.4, MeOH); UV (MeOH) λ max (log ε) 321 (3.69), 236 (3.87) nm; IR ν max 3430, 1698, 1603, 1495 cm −1 ; 1 H NMR and 13 C NMR data, see Table 2; HRESIMS m/z 507.1352 [M + HCOO] − (calcd for C 20 H 27 O 15, 507.1350).
  • Y Li
  • D M Zhang
  • J B Li
  • S S Yu
  • Y M Luo
Li, Y.; Zhang, D. M.; Li, J. B.; Yu, S. S.; Luo, Y. M. J. Nat. Prod. 2006, 69, 616−620. (12) Duynstee, H. I.; Koning, M. C.; Marel, G. A.; Boom, J. H. Tetrahedron 1999, 55, 9881−9891.
883−887. (9) Molecular rotation where MW is the molecular weight and [α] D is the specific rotation; thus, [M] D(aglycone) was calculated as a negative value on the basis of the formula
  • G Yuan
  • T Zhang
  • C Yang
  • S P Wu
  • Y Yue
G.; Yuan, T.; Zhang, C.; Yang, S. P.; Wu, Y.; Yue, J. M. Tetrahedron 2009, 65, 883−887. (9) Molecular rotation [M] D = MW × [α] D /100, where MW is the molecular weight and [α] D is the specific rotation; thus, [M] D(aglycone) was calculated as a negative value on the basis of the formula [M] D(glycoside) = [M] D(aglycone) + [M] D(sugar).
  • T Warashina
  • Y Nagatani
  • T Noro
(13) Warashina, T.; Nagatani, Y.; Noro, T. Phytochemistry 2005, 66, 589−597. (14) Miyase, T.; Ueno, A.; Takizawa, N.; Kobayashi, H.; Oguchi, H. Phytochemistry 1989, 28, 3483−3485.
colorless, amorphous solid MeOH); UV (MeOH) λ max (log ε) 293 (3.45), 267 (3.73), 223 (3.91) nm; IR ν max 3344, 2968, 1691, 1608, 1496, 1043 cm −1 ; 1 H NMR and 13 C NMR data, see Table 1
  • A Saccharumoside
Saccharumoside A (1): colorless, amorphous solid; [α] 20 D −31 (c 0.5, MeOH); UV (MeOH) λ max (log ε) 293 (3.45), 267 (3.73), 223 (3.91) nm; IR ν max 3344, 2968, 1691, 1608, 1496, 1043 cm −1 ; 1 H NMR and 13 C NMR data, see Table 1; HRESIMS m/z 671.2314
  • W J Xiang
  • L Ma
  • L H Hu
  • S Liao
Xiang, W. J.; Ma, L.; Hu, L. H. Fitoterapia 2010, 81, 1228−1231. (8) (a) Hudson, C. S. J. Am. Chem. Soc. 1909, 31, 66−86. (b) Liao, S.
colorless, amorphous solid; [α] 20 D −86 (c 0.5, MeOH); UV (MeOH) λ max (log ε)92) nm
  • C Saccharumoside
Saccharumoside C (3): colorless, amorphous solid; [α] 20 D −86 (c 0.5, MeOH); UV (MeOH) λ max (log ε) 320 (3.69), 234 (3.92) nm;
colorless, amorphous solid; [α] 20 D −13 (c 087) nm
  • D Saccharumoside
Saccharumoside D (4): colorless, amorphous solid; [α] 20 D −13 (c 0.4, MeOH); UV (MeOH) λ max (log ε) 321 (3.69), 236 (3.87) nm;
colorless, amorphous powder MeOH) UV (MeOH) λ max (log ε) 299 (3.56)99) nm; IR ν max 3415
  • B Saccharumoside
Saccharumoside B (2): colorless, amorphous powder; [α] 20 D +75 (c 0.2, MeOH); UV (MeOH) λ max (log ε) 299 (3.56), 265 (3.78), 220 (3.99) nm; IR ν max 3415, 2935, 1699, 1598, 1500, 1064 cm −1 ; 1 H NMR and 13 C NMR data, see Table 1; HRESIMS m/z 465.1395
colorless, amorphous solid92) nm
  • C Saccharumoside
Saccharumoside C (3): colorless, amorphous solid; [α] 20 D −86 (c 0.5, MeOH); UV (MeOH) λ max (log ε) 320 (3.69), 234 (3.92) nm;
  • W M Zhao
  • H Tsukamoto
  • S Hisada
  • S Nishibe
Zhao, W. M. J. Nat. Prod. 2003, 66, 1140−1143. (19) Tsukamoto, H.; Hisada, S.; Nishibe, S. Chem. Pharm. Bull. 1985, 33, 396−399. (20) Cory, A. H.; Owen, T. C.; Barltrop, J. A.; Cory, J. G. Cancer Commun. 1991, 3, 207−212.
colorless, amorphous solid MeOH) UV (MeOH) λ max (log ε) 293 (3.45)91) nm; IR ν max 3344
  • A Saccharumoside
Saccharumoside A (1): colorless, amorphous solid; [α] 20 D −31 (c 0.5, MeOH); UV (MeOH) λ max (log ε) 293 (3.45), 267 (3.73), 223 (3.91) nm; IR ν max 3344, 2968, 1691, 1608, 1496, 1043 cm −1 ; 1 H NMR and 13 C NMR data, see Table 1; HRESIMS m/z 671.2314
Molecular rotation where MW is the molecular weight and [α] D is the specific rotation; thus, [M] D(aglycone) was calculated as a negative value on the basis of the formula(sugar) (10)
  • G Yuan
  • T Zhang
  • C Yang
  • S P Wu
  • Y Yue
  • J M Chin
  • Y W Chai
  • H B Keller
  • W J Kinghorn
  • A D Li
  • Y Zhang
  • D M Li
  • J B Yu
  • S S Luo
  • Y M Duynstee
  • H I Koning
  • M C Marel
  • G A Boom
  • J H Deyama
  • T Ikawa
  • T Nishibe
  • S Kitajima
  • J Zhao
  • C S Liu
  • Q F Halaweish
  • F Shao
G.; Yuan, T.; Zhang, C.; Yang, S. P.; Wu, Y.; Yue, J. M. Tetrahedron 2009, 65, 883−887. (9) Molecular rotation [M] D = MW × [α] D /100, where MW is the molecular weight and [α] D is the specific rotation; thus, [M] D(aglycone) was calculated as a negative value on the basis of the formula [M] D(glycoside) = [M] D(aglycone) + [M] D(sugar). (10) Chin, Y. W.; Chai, H. B.; Keller, W. J.; Kinghorn, A. D. J. Agric. Food Chem. 2008, 56, 7759−7764. (11) Li, Y.; Zhang, D. M.; Li, J. B.; Yu, S. S.; Luo, Y. M. J. Nat. Prod. 2006, 69, 616−620. (12) Duynstee, H. I.; Koning, M. C.; Marel, G. A.; Boom, J. H. Tetrahedron 1999, 55, 9881−9891. (13) Warashina, T.; Nagatani, Y.; Noro, T. Phytochemistry 2005, 66, 589−597. (14) Miyase, T.; Ueno, A.; Takizawa, N.; Kobayashi, H.; Oguchi, H. Phytochemistry 1989, 28, 3483−3485. (15) Deyama, T.; Ikawa, T.; Nishibe, S. Chem. Pharm. Bull. 1985, 33, 3651−3657. (16) Kitajima, J.; Ishikawa, T.; Tanaka, Y.; Ono, M.; Ito, Y.; Nohara, T. Chem. Pharm. Bull. 1998, 46, 1587−1590. (17) Achenbach, H.; Benirschke, G. Phytochemistry 1997, 45, 149− 157. (18) Zhao, C. S.; Liu, Q. F.; Halaweish, F.; Shao, B. P.; Ye, Y. Q.;
Fraction 2C1d was separated using semipreparative HPLC (MeOH−H 2 O, 10:90 to 50:50 in 18 min, 3 mL/min) and yielded 3 (8 mg) and 4 (4 mg). Fraction 2C1e was purified by semipreparative HPLC (MeOH−H 2 O
  • O-Β-D-Glucopyranoside
-O-β-D-glucopyranoside (10 mg). Fraction 2C1d was separated using semipreparative HPLC (MeOH−H 2 O, 10:90 to 50:50 in 18 min, 3 mL/min) and yielded 3 (8 mg) and 4 (4 mg). Fraction 2C1e was purified by semipreparative HPLC (MeOH−H 2 O, 10:90 to 40:60 in 12 min, 3 mL/min) to yield vanilloloside (8 mg).
): colorless, amorphous powder
  • B Saccharumoside
Saccharumoside B (2): colorless, amorphous powder; [α] 20 D +75 (c 0.2, MeOH);
): colorless, amorphous solid
  • C Saccharumoside
Saccharumoside C (3): colorless, amorphous solid; [α] 20
  • L Li
  • N P Seeram
Li, L.; Seeram, N. P. J. Agric. Food Chem. 2010, 58, 11673− 11679.
  • L Li
  • N P Seeram
Li, L.; Seeram, N. P. J. Agric. Food Chem. 2011, 59, 7708−7716.
  • L Li
  • N P Seeram
Li, L.; Seeram, N. P. J. Funct. Foods 2011, 3, 125−128.
  • Y Li
  • D M Zhang
  • J B Li
  • S S Yu
  • Y M Luo
Li, Y.; Zhang, D. M.; Li, J. B.; Yu, S. S.; Luo, Y. M. J. Nat. Prod. 2006, 69, 616−620.
  • H I Duynstee
  • M C Koning
  • G A Marel
  • J H Boom
Duynstee, H. I.; Koning, M. C.; Marel, G. A.; Boom, J. H. Tetrahedron 1999, 55, 9881−9891.
  • C S Zhao
  • Q F Liu
  • F Halaweish
  • B P Shao
  • Y Q Ye
  • W M Zhao
Zhao, C. S.; Liu, Q. F.; Halaweish, F.; Shao, B. P.; Ye, Y. Q.; Zhao, W. M. J. Nat. Prod. 2003, 66, 1140−1143.