Liriogerphines E-U, further unique sesquiterpene-alkaloid hybrids from the rare Chinese tulip tree.

Seventeen undescribed sesquiterpene-alkaloid hybrids (liriogerphines E-U, 1-17) were isolated and identified during a further phytochemical investigation on the branches and leaves of Chinese tulip tree (Liriodendron chinense), a rare medicinal and ornamental plant endemic to China. These unique heterodimers are conjugates of germacranolide-type sesquiterpenoids with structurally diverse alkaloids [i.e., aporphine- (1-15), proaporphine- (16), and benzyltetrahydroisoquinoline-type (17)] via the formation of a C-N bond. The previously undescribed structures were elucidated by comprehensive spectroscopic data analyses and electronic circular dichroism calculations. Such a class of sesquiterpene-alkaloid hybrids presumably biosynthesized via an aza-Michael addition is quite rare from terrestrial plants. In particular, the sesquiterpene-benzyltetrahydroisoquinoline hybrid skeleton has never been reported until the present study. All the isolates were evaluated for their cytotoxic effects against a small panel of leukemia cell lines (Raji, Jeko-1, Daudi, Jurkat, MV-4-11 and HL-60), and some of them exhibited considerable activities.

Structural characterization of the lignin-carbohydrate complex in biomass pretreated with Fenton oxidation and hydrothermal treatment and consequences on enzymatic hydrolysis efficiency.

In this study, lignin-carbohydrate complexes (LCCs) were isolated from biomass (raw and pretreated) to investigate the structural changes in biomass pretreated by Fenton oxidation and hydrothermal treatment, and their effect on enzymatic hydrolysis. The composition and structure of the LCCs fractions were investigated via carbohydrate analysis, XRD, FT-IR, and 2D HSQC NMR. The biomass degradation rate of yellow poplar and larch during Fenton oxidation and hydrothermal treatment was approximately 30%. Most of the hemicellulose was degraded during pretreatment, while xylan remained in the yellow poplar, and galactan, mannan, and xylan remained in the larch. The fractional yield of glucan-rich LCC (LCC1) in the yellow poplar (raw and pretreated biomass) was high, while that of glucomannan-rich LCC (LCC3) in larch was higher than the yield yellow poplar. Phenyl glycoside, γ-ester, and benzyl ether linkages were observed in the LCCs of yellow poplar, while phenyl glycoside and γ-ester were detected in those of larch. Following pretreatment, the frequencies of ß-ß', ß-5, and γ-ester in the LCCs of larch were found to be higher than in those of yellow poplar. The efficiencies of enzymatic hydrolysis for the pretreated yellow poplar and larch were 93.53% and 26.23%, respectively. These finding indicated that the ß-ß', ß-5, and γ-ester linkages included in the pretreated biomass affected the efficiency of enzymatic hydrolysis.

Tulipiferamide A, an Alkamide from Liriodendron tulipifera, Exhibits an Anti-Inflammatory Effect via Targeting IKKß Phosphorylation.

Three new alkamides, tulipiferamides A-C (1-3, respectively), and 30 known compounds (4-33) were obtained from the roots of Liriodendron tulipifera (Magnoliaceae). Dehydrotemisin (4), an elemane sesquiterpene lactone, was isolated for the first time from nature. The structures were deduced by the interpretation of NMR spectroscopic and MS spectral data. The geometries of the double bonds in tulipiferamides A-C (1-3, respectively) were determined on the basis of 1H-1H coupling constants and 13C chemical shifts. The presence of the alkamide type in this plant is reported for the first time. An analysis of the inflammatory response revealed that seven compounds (1, 4, 7, 9, 14, 23, and 27) suppressed the nitric oxide production induced by LPS in RAW264.7 macrophages. Furthermore, tulipiferamide A (1) inhibits NF-κB activation by selectively targeting IKKß, an upstream kinase of NF-κB, resulting in the suppression of inflammatory mediators, including iNOS, COX-2, IL-1ß, TNFα, and IL-6. Our results provide a rationale for the further development of tulipiferamide A as a selective IKKß inhibitor to modulate inflammatory diseases.

High porosity with tiny pore constrictions and unbending pathways characterize the 3D structure of intervessel pit membranes in angiosperm xylem.

Pit membranes between xylem vessels play a major role in angiosperm water transport. Yet, their three-dimensional (3D) structure as fibrous porous media remains unknown, largely due to technical challenges and sample preparation artefacts. Here, we applied a modelling approach based on thickness measurements of fresh and fully shrunken pit membranes of seven species. Pore constrictions were also investigated visually by perfusing fresh material with colloidal gold particles of known sizes. Based on a shrinkage model, fresh pit membranes showed tiny pore constrictions of ca. 20 nm, but a very high porosity (i.e. pore volume fraction) of on average 0.81. Perfusion experiments showed similar pore constrictions in fresh samples, well below 50 nm based on transmission electron microscopy. Drying caused a 50% shrinkage of pit membranes, resulting in much smaller pore constrictions. These findings suggest that pit membranes represent a mesoporous medium, with the pore space characterized by multiple constrictions. Constrictions are much smaller than previously assumed, but the pore volume is large and highly interconnected. Pores do not form highly tortuous, bent, or zigzagging pathways. These insights provide a novel view on pit membranes, which is essential to develop a mechanistic, 3D understanding of air-seeding through this porous medium.

Exploring new applications of tulip tree (Liriodendron tulipifera L.): leaf essential oil as apoptotic agent for human glioblastoma.

Liriodendron tulipifera L. (Magnoliaceae), also known as "tulip tree," is a hardwood plant native to North America, cultivated all over the world and used on an industrial level, especially for its fine wood and to make honey. It has also been traditionally exploited for its antimalarial properties. However, our knowledge about the bioactivity of its essential oil remains patchy. In this research, we focused on the biological evaluation of the volatile fractions obtained from different parts of the plant which are normally discharged by industry, including leaves, flowers, and fruits. For the purpose, the essential oils were obtained by hydrodistillation and analyzed by gas chromatography-mass spectrometry (GC-MS). Then, they were evaluated as radical scavenging, antioxidant, antimicrobial, and antiproliferative agents by using DPPH, ABTS, FRAP, disk diffusion, and MTT methods, respectively. The significant toxicity exhibited on human tumor cells, namely A375 malignant melanoma, HCT116 colon carcinoma, MDA-MB 231 breast adenocarcinoma, and T98G glioblastoma multiforme cell lines, prompted us to study the mechanism of action by acridine orange/ethidium bromide double staining and caspase 3 assays. Our findings shed light on the potential applications of tulip tree derivatives as anticancer drugs.

American Civil War plant medicines inhibit growth, biofilm formation, and quorum sensing by multidrug-resistant bacteria.

A shortage of conventional medicine during the American Civil War (1861-1865) spurred Confederate physicians to use preparations of native plants as medicines. In 1863, botanist Francis Porcher compiled a book of medicinal plants native to the southern United States, including plants used in Native American traditional medicine. In this study, we consulted Porcher's book and collected samples from three species that were indicated for the formulation of antiseptics: Liriodendron tulipifera, Aralia spinosa, and Quercus alba. Extracts of these species were tested for the ability to inhibit growth in three species of multidrug-resistant pathogenic bacteria associated with wound infections: Staphylococcus aureus, Klebsiella pneumoniae, and Acinetobacter baumannii. Extracts were also tested for biofilm and quorum sensing inhibition against S. aureus. Q. alba extracts inhibited growth in all three species of bacteria (IC50 64, 32, and 32 µg/mL, respectively), and inhibited biofilm formation (IC50 1 µg/mL) in S. aureus. L. tulipifera extracts inhibited biofilm formation (IC50 32 µg/mL) in S. aureus. A. spinosa extracts inhibited biofilm formation (IC50 2 µg/mL) and quorum sensing (IC50 8 µg/mL) in S. aureus. These results support that this selection of plants exhibited some antiseptic properties in the prevention and management of wound infections during the conflict.

Xylanase Treatment Suppresses Light- and Heat-Induced Yellowing of Pulp.

Xylanase is commonly applied in pulp and paper industries to ease cost-related and environmental pressures. The effect of xylanase treatment on pulp bleaching is well-established, however, few studies were conducted on the effects of xylanase treatment in pulp yellowing, especially the mechanism of pulp yellowing inhibition by xylanase treatment. In this study, pure xylanase (EC 3.2.1.8) was applied to treat wheat straw chemical pulp (CP) and poplar chemi-thermo-mechanical pulp (CTMP) to determine their effects on pulp brightness and on light- and heat-induced yellowing. The xylanase treatment decreased the post-color number of the pulps during light- and heat-induced yellowing. However, differences were observed in the yellowing inhibition between the wheat straw CP and poplar CTMP. The changes in chemical components of pulps after the xylanase treatment, for example, lignin, hemicellulose, and HexA contents, and analysis of UV-vis absorption spectra and Fourier transform infrared-attenuated total reflectance spectrum were used to explore the pulp yellowing inhibition causes by the xylanase treatment.

Hydrolysis kinetics of tulip tree xylan in hot compressed water.

Lignocellulosic biomass, a promising renewable resource, can be converted into numerous valuable chemicals post enzymatic saccharification. However, the efficacy of enzymatic saccharification of lignocellulosic biomass is low; therefore, pretreatment is necessary to improve the efficiency. Here, a kinetic analysis was carried out on xylan hydrolysis, after hot compressed water pretreatment of the lignocellulosic biomass conducted at 180-220°C for 5-30min, and on subsequent xylooligosaccharide hydrolysis. The weight ratio of fast-reacting xylan to slow-reacting xylan was 5.25 in tulip tree. Our kinetic results were applied to three different reaction systems to improve the pretreatment efficiency. We found that semi-continuous reactor is promising. Lower reaction temperatures and shorter space times in semi-continuous reactor are recommended for improving xylan conversion and xylooligosaccharide yield. In the theoretical calculation, 95% of xylooligosaccharide yield and xylan conversion were achieved simultaneously with high selectivity (desired product/undesired product) of 100 or more.

Bioethanol production from deacetylated yellow poplar pretreated with oxalic acid recovered through electrodialysis.

Electrodialysis (ED) was used to develop a multistage oxalic acid recovery and pretreatment system to produce ethanol from deacetylated yellow poplar. Pretreatment of the biomass was performed at 150°C for 42 min using 0.16 M oxalic acid. The efficiency of oxalic acid recovery from the hydrolysate reached up to 92.32% in all the stages. Ethanol production and ethanol yield of ED-treated hydrolysate in each stage showed a uniform pattern ranging from 6.81 g/L to 7.21 g/L and 0.40 g/g to 0.43 g/g, respectively. The results showed that efficiency of ethanol production increased when deacetylated biomass and ED process was used. Ethanol yield from the pretreated biomass using simultaneous saccharification and fermentation (SSF) was in the range of 80.59-83.36% in all the stages. The structural characterization of the pretreated biomass at each stage was investigated and structural changes were not significantly different among the various pretreated biomass.

CD-200 induces apoptosis and inhibits Bcr-Abl signaling in imatinib-resistant chronic myeloid leukemia with T315I mutation.

Chronic myeloid leukemia (CML) is characterized by a constitutively active Bcr-Abl tyrosine kinase. Although Imatinib has been proven to be an effective drug against CML, its resistance has been observed with disease relapse due to T315I predominant point mutation. Liriodendron tulipifera L., one of the fastest growing hardwood tree species, exerts antioxidant activity and anti-inflammatory effects. However, its anticancer effect has been minimally reported. In this study, we extracted CD-200 from Liriodendron tulipifera L. and investigated its effect on cell survival or apoptosis in CML cells with Bcr-Abl/T315I (BaF3/T315I) as well as wild-type Bcr-Abl (BaF3/WT). CD-200 inhibited cell proliferation in the BaF3/WT cells, and also in the BaF3/T315I cells with Imatinib resistance. Moreover, it strongly inhibited Bcr-Abl signaling pathways in a dose-dependent manner. Also, it significantly increased the sub-G1 phase and the expression of cleaved PARP and caspase-3, as well as the TUNEL-positive apoptotic cells. In addition, we observed that CD-200 induced apoptosis with a loss of mitochondrial membrane potential by decreasing the expression of Mcl-1 and survivin. Furthermore, CD-200 showed a significant inhibition in tumor growth, compared to Imatinib in BaF3/T315I mouse xenograft models. Taken together, our study demonstrates that CD-200 exhibits apoptosis induction and anti-proliferative effect by blocking the Bcr-Abl signaling pathways in the Bcr-Abl/T315I with resistance to Imatinib. We suggest that CD-200 may be a natural product to target Bcr-Abl and overcome Imatinib resistance in CML patients.

(+)- and (-)-liriodenol, a pair of novel enantiomeric lignans from Liriodendron hybrid.

(+)- and (-)-liriodenol, a pair of unprecedented enantiomeric lignans bearing a 1,1-disubstituted olefinic group, were isolated from the barks of Liriodendron hybrid. The structure and relative configurations were determined by comprehensive analysis of MS and NMR spectroscopy. The cytotoxicity of these three lignans ((±)-, (+)-, and (-)-liriodenol) was evaluated in vitro against four selected human tumor cell lines, where (+)-liriodenol showed more significant cytotoxic effects than the (±)- and (-)-liriodenol enantiomers.

Stemflow acid neutralization capacity in a broadleaved deciduous forest: the role of edge effects.

Atmospheric deposition is an important pathway for moisture, nutrient, and pollutant exchange among the atmosphere, forest, and soils. Previous work has shown the importance of proximity to the forest edge to chemical fluxes in throughfall, but far less research has considered stemflow. This study examined the difference in acid neutralization capacity (ANC) of stemflow of nineteen Liriodendron tulipifera L. (yellow poplar) trees between the forest edge and interior in a rural area of northeastern Maryland. We measured ANC directly via potentiometric titration. Stemflow from trees at the forest edge was found to have significantly higher and more variable pH and ANC than in the forest interior (p < 0.01). No mathematical trend between ANC and distance to the forest edge was observed, indicating the importance of individual tree characteristics in stemflow production and chemistry. These results reaffirm the importance of stemflow for acid neutralization by deciduous tree species.

Morphological and proteomic analysis reveal the role of pistil under pollination in Liriodendron chinense (Hemsl.) Sarg.

Pollination is an important physiological process during which interaction between pollen and pistil occurs. This interaction could determine whether or not fertilization will occur and hence the ratio of plant seed setting. Liriodendron chinense (Hemsl.) Sarg. (L. chinense) exhibits a distinct phenomenon where seed setting ratio is not more than 10% in natural environment. To explore the origin of this phenomenon, we conducted a comparative morphological and proteomic analysis on L. chinense pistils upon pollination. The morphological analysis showed that pollen grows well in vitro, but much slower on pistil or nutrient medium containing pistil extract. Proteomic analysis showed that 493 proteins had changed the expression after pollination. Among them, 468 and 51 proteins were identified by isobaric tags for relative and absolute quantitation and two-dimensional gel electrophoresis respectively, and 26 proteins were common in the two methods. After proteins functional categorization, 66 differentially expressed proteins that are involved in reproduction process were found. Further analysis showed that among the reproductive process related proteins, protein disulfide-isomerase A6 and four embryo-defective proteins showed closer relations with the low seed setting phenomenon. The results indicated that the element from pistil might be the main reason leading to low seed setting in L. chinense, which will provide new insights in the mechanisms underlying L. chinense reproduction process.

Antioxidant and anticancer constituents from the leaves of Liriodendron tulipifera.

Sixteen compounds were extracted and purified from the leaves of Liriodendron tulipifera. These compounds include aporphines, oxoaporphine, coumarin, sesquiterpene lactone, benzenoids, cyclitol and steroids. (+)-Norstephalagine (2) (an aporphine) and scopoletin (8) (a coumarin) were isolated from Liriodendron tulipifera leaves from the first time. The identified compounds were screened for their antiradical scavenging, metal chelating and ferric reducing power activities. The results have showed that these compounds have antioxidative activity. The study has also examined the chemopreventive property of the isolated compounds against human melanoma cells A375. The results shown that (-)-anonaine (1), (-)-liridinine (3), (+)-lirinidine (6), lysicamine (7) and epitulipinolide diepoxide (9) significantly inhibited the proliferation of melanoma cells. These results revealed that these compounds have antioxidative activity and chemopreventive activity in skin melanoma cells.

An integrated detoxification process with electrodialysis and adsorption from the hemicellulose hydrolysates of yellow poplars.

An integrated detoxification process with electrodialysis (ED) followed by adsorption was performed to remove fermentation inhibitors from hemicellulose hydrolysates. The hydrolysates were prepared by oxalic acid pretreatment of yellow poplars at different temperatures. Of fermentation inhibitors, acetic acid showed high removal efficiency of about 90% and high transport rate during the ED process without membrane fouling. The integration of the detoxification processes increased up to the ethanol yield of 0.33g/g sugar, the ethanol production of about 9g/L, and the productivity of 0.12g/Lh, while the fermentation of non-detoxified hydrolysates did not produce bioethanol. The influence of inhibitor concentration on the fermentability showed that HMF had the highest inhibition effect. The results clearly showed that an integrated detoxification process with ED followed by adsorption removed fermentation inhibitors with high efficiency and increased the fermentability of the oxalic acid pretreated hemicellulose hydrolysates.

Pyrolysis kinetics of coking coal mixed with biomass under non-isothermal and isothermal conditions.

To investigate the kinetic characteristics of coking coal mixed with biomass during pyrolysis, thermogravimetric (TG) and thermo-balance reactor (TBR) analyses were conducted under non-isothermal and isothermal condition. Yellow poplar as a biomass (B) was mixed with weak coking coal (WC) and hard coking coal (HC), respectively. The calculated activation energies of WC/B blends were higher than those of HC/B blends under non-isothermal and isothermal conditions. The coal/biomass blends show increased reactivity and decreased activation energy with increasing biomass blend ratio, regardless of the coking properties of the coal. The different char structures of the WC/B and HC/B blends were analyzed by BET and SEM.

Evaluation of hot compressed water pretreatment and enzymatic saccharification of tulip tree sawdust using severity factors.

Tulip tree sawdust was pretreated using hot compressed water with different pretreatment severities (LogR0, 3.05-5.01) by varying reaction temperatures (180-220°C) and residence time (1-30 min). It is found that the chemical composition and physicochemical properties of the pretreated products can be characterized and correlated with severity. Removal of most of the xylan and other hemicellulosic sugars from the raw material was observed at a severity of 4.5. Thus, the residual solids were recovered with increased cellulose and lignin contents. Nearly complete glucan conversion was achieved after 48 h of hydrolysis with 10 FPU/g of wet residual solid obtained above a severity of 4.8. The characteristics of the pretreated solids according to the pretreatment severity were strongly related with the glucose yield. The removal of structural barriers to the enzyme attack was the dominant factor affecting enzyme accessibility to the substrate.

Impact of bleaching on subcritical water- and Formosolv-pretreated tulip tree to enhance enzyme accessibility.

A novel method was developed for fractionating cellulose microfibrils from forest residue (tulip tree sawdust) to enhance cellulose digestibility, particularly at minimum enzyme loadings. This method involved three main stages: selective hemicellulose solubilization by subcritical water (SCW) pretreatment, delignification of the SCW-pretreated solids using the Formosolv process, and deformylation/bleaching of the cellulose pulp with alkaline hydrogen peroxide solution. This process produced nearly 98% white cellulose microfibrils with 23-fold higher conversion to glucose as compared to the raw substrate after 72 h of enzymatic hydrolysis. This study showed that cellulose swelling had the greatest effect on the enzymatic hydrolysis efficiency of delignified pulp obtained by the Formosolv process.

In vitro tumor cytotoxic activities of extracts from three Liriodendron plants.

The extracts prepared from Liriodendron tulipifera Linn., L. chinense (Hemsl.) Sarg., and their hybrid L. chinense x L. tulipifera, were investigated for their cytotoxic abilities in vitro against five human cancer cell lines: MDA-MB-231 and MCF-7 breast cancer cells, SGC-7901 gastric cancer cells, HuH-7 hepatocarcinoma cells, and HCT-15 colon carcinoma cells, and then measured their phenols and alkaloids contents. Of these plant extracts, some of them, especially the lower polar extracts from barks, exhibited potent cytotoxic effects on five tested tumor cell lines.

Biofunctional constituents from Liriodendron tulipifera with antioxidants and anti-melanogenic properties.

From the stems of Liriodendron tulipifera, seventeen known compounds have been extracted, isolated and purified. By using spectroscopic analysis, the structures of these pure constituents were determined as three lignans, four steroids and ten benzenoids. Identified compounds were screened for antioxidant abilities using: 1,1-diphenyl-2-picrylhydrazul (DPPH) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) scavenging free radical activity assays; metal chelating power test; and ferric reducing/antioxidant power (FRAP) examination. The result revealed that seventeen compounds had potential anti-oxidative capabilities. In addition, the anti-tyrosinase effect was determined by calculating the hydroxylation of L-tyrosine to L-dopa and the oxidization of L-dopa to dopaquinone, according to in vitro mushroom tyrosinase evaluation platform. Furthermore, based on assays on B16F10 cell line, our data suggest that five compounds isolated from L. tulipifera would be able to inhibit tyrosinase activity and reduce the melanin content in animal cells. Therefore, some of the examined compounds could be potentially used in the cosmetic skin whitening business, therapeutic applications or the food industry.