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A new glycoside, named as CG-1, was separated from Imperial Chrysanthemum with silica gel column chromatography. The purity was detected by TLC and HPLC. The crystal shape of CG-1 was consisting of a quadrangular and two rectangular pyramids. The analysis of DSC and TGA showed that the melting point of CG-1 crystal was 150.22 °C and had good thermal stability. The monosaccharide conformation analysis showed that it was d-glucose. The structure characteristics were compared by FT-IR, NMR spectroscopy and LC-MS and a molecular structure has been deduced which consistent with spectroscopic results. In vitro antioxidant results suggested that the glycoside extracted from Imperial Chrysanthemum could be effectively employed as natural antioxidant in health or functional food. This work is of significance to keep the antioxidant activity in the processing and application of Imperial Chrysanthemum.

Selenium (Se) has been recognized as an essential element. Animals and humans absorb and retain more organic Se than inorganic Se. Bio-transformation is a major approach to transform inorganic Se to organic Se. Cordyceps gunnii (C. gunnii), well known as a Chinese edible and medicinal fungus, has a variety of biological functions. C. gunnii and selenium were combined through liquid-fermentation to obtain selenium-enriched C. gunnii. A novel Se-polysaccharide (SeCPS-II) was extracted from selenium-enriched C. gunnii. The molecular weight, sugar content and selenium content of SeCPS-II were 4.12 × 103 kDa, 17.89 μg g-1 and 90.75%, respectively. The structure of SeCPS-II was characterized using FT-IR, NMR, GC and GC-MS studies. SeCPS-II was composed of pyranose, which contained α-l-rhamnose, α-d-mannose, α-d-glucose and β-d-galactose at a ratio of 4.33 : 12.62 : 27.50 : 18.99. SeCPS-II contained α-(1 → 4)-d-glucose, α-(1 → 3)-d-glucose, β-(1 → 6)-d-galactose, α-(1 → 6)-d-mannose, and α-(1 → 4)-l-rhamnose, and the main chain was composed of α-(1 → 4)-d-glucose. An MTT assay indicated that SeCPS-II could influence the cell viability of SKOV-3 cells, H1299 cells and HepG2 cells in a dose-dependent and time-dependent manner. Morphologic changes (AO/EB staining and DAPI staining) and an MMP assay (JC-1 staining) of SKOV-3 cells treated with SeCPS-II were performed to research the antitumor activity of SeCPS-II. SeCPS-II could significantly induce apoptosis in SKOV-3 cells with typical apoptotic characteristics. To study the mechanism, the expressions of caspase-3, caspase-9, PARP, p53, Bax and Bcl-2 in SKOV-3 were studied via western blotting. SeCPS-II can stimulate the apoptosis of SKOV-3 cells through the p53-Bax-caspase pathway. Animal experiments revealed that SeCPS-II inhibits tumors within an ovarian tumor model rat, modeled with SKOV-3 cells. All the results indicated that selenium-enriched C. gunnii can be used to develop new selenium-containing additives.

Four ring-closed analogs of natural prenylated chalcone desmethylxanthohumol (1) and their dimers were synthesized from the commercially available 1-(2,4,6-trihydroxyphenyl)ethan-1-one in five and six linear steps, respectively. The structures of the eight new derivatives were confirmed using1H NMR, 13C NMR and HRMS. The antioxidant activity of the new chalcone derivatives were evaluated in a PC12 cell model of H2O2-induced oxidative damage. The SAR studies suggested that the catechol motif was essential for the antioxidant activity. Moreover, the dimers showed better antioxidant activity than their corresponding monomers did. Among them, compound 14d was the most potent and increased PC12 cell viability from 25% to 85%. Flow cytometric analysis showed that compound 14d, the most potent compound, decreased the apoptotic PC12 cell percentage and significantly reduced the LDH release and 8-OHdG generation but increased the GSH levels in H2O2-treated PC12 cells. Furthermore, compound 14d had a higher FRAP value than that of gallic acid. It also reduced the stable ABTS+ free radical with a lower EC50 than that of gallic acid.

In the present study, the crude polysaccharide was extracted from Fagopyrum tartaricum and purified by Sephadex G-25 and G-75 column to produce a polysaccharide fraction termed TBP-II. Its average molecular weight was 26 kDa. The structural characterization of TBP-II was investigated by gas chromatography, periodate oxidation-Smith degradation, Methylation and NMR. Congo red was applied to explore its advanced structures. The results revealed that chemical composition and structural characteristic of TBP-II was mainly consisted of galactose, arabinose, xylose and glucose with a molar ratio of 0.7:1:6.3:74.2. The backbone of TBP-II was composed of (1 → 4)-linked α- d -glucopyranosyl (Glcp), while the branches comprised of (1 → 3)-linked α- d -glucopyranosyl (Glcp), (1 → 6)-linked α- d -galactopyranosyl (Galp) and (1 → 2,4)-linked α- d -rhamnopyranosyl (Rhap). The structure of TBP-II was 1,3 and 1,6-branched-galactorhamnoglucan that had a linear backbone of (1 → 4)-linked α- d -glucopyranose (Glcp). Using Congo red assay showed that it was absent of triple helix structure. The α- d -glucosidase inhibitory activity of TBP-II was determined using acarbose as positive control. The result showed that the inhibition rate depended on the concentration of polysaccharides.

The effects of culture medium composition (i.e., carbon and nitrogen sources) on the growth of mycelia, molecular weight distribution and antitumor activity of intracellular polysaccharides (IPS) from Cordyceps gunnii were investigated. Sucrose and peptone were proved to be the best carbon and nitrogen sources for mycelia growth and remarkably improved IPS production. When the sucrose concentration was 2.0%, the mycelium yield reached up to 15.94 ± 1.26 g/L, but with lower IPS yield; whereas the sucrose concentration was 4.5%, IPS yield reached to a maximum of 138.78 ± 3.89 mg/100 mL. The effects of different carbon/nitrogen (C/N) ratios with equal amounts of carbon source matter on the mycelia and IPS formation were optimized. It found that the yield of mycelia and IPS were both reached to the highest at a C/N ratio of 10:3. In addition, the IPS had the highest macro molecular polysaccharide content and antitumor activity when sucrose concentration was 3.5% and the C/N ratio was 10:1.5. Thus, there was a positive correlation between molecular weight distribution and antitumor activity of IPS by C. gunnii.

The cytotoxic activity of camptothecin derivatives is so high that these compounds need to be further modified before their successful application as anti-cancer agents clinically. In this study, we reported the synthesis and biological evaluation of a novel camptothecin derivative called compound 2-47. The changes in structure did not reduce its activity to inhibit DNA topoisomerase I. Compound 2-47 induced apoptosis of many tumor cells including leukemia cells K562, Jurkat, HL-60, breast cancer cell BT-549, colon cancer cell HT-29 and liver cancer cell HepG2 with a half maximal inhibitory concentration (IC50) of 2- to 3-fold lower than HCPT as a control. In particular, 2-47 inhibited the proliferation of Jurkat cells with an IC50 of as low as 40 nM. By making use of Jurkat cell as a model, following treatment of Jurkat cells, compound 2-47 activated caspase-3 and PARP, resulting in a decreased Bcl-2/Bax ratio. These data showed that compound 2-47 induces Jurkat cell death through the mitochondrial apoptotic pathway. In addition, compound 2-47 showed a decreased cytotoxic activity against normal cells and an improved solubility in low-polar solvent. For example, compound 2-47 solutes in CHCl3 130-fold higher than HCPT. Taken together, our data demonstrated that camptothecin derivative 2-47 notably inhibits the tumor cell proliferation through mitochondrial-mediated apoptosis in vitro.

This study was to investigate the effects of different extraction methods on the yield, chemical structure and antitumor activity of polysaccharides from Cordyceps gunnii (C. gunnii) mycelia. Five extraction methods were used to extract crude polysaccharides (CPS), which include room-temperature water extraction (RWE), hot-water extraction (HWE), microwave-assisted extraction (MAE), ultrasound-assisted extraction (UAE) and cellulase-assisted extraction (CAE). Then Sephadex G-100 was used for purification of CPS. As a result, the antitumor activities of CPS and PPS on S180 cells were evaluated. Five CPS and purified polysaccharides (PPS) were obtained. The yield of CPS by microwave-assisted extraction (CPSMAE) was the highest and its anti-tumor activity was the best and its macromolecular polysaccharide (3000-1000kDa) ratio was the largest. The PPS had the same monosaccharide composition, but their obvious difference was in the antitumor activity and the physicochemical characteristics, such as intrinsic viscosity, specific rotation, scanning electron microscopy and circular dichroism spectra.

HSP-III, a novel homogeneous polysaccharide with 513.89 kDa molecular weight, was fractionated from submerged cultures of Hirsutella sinensis by Sevag and chromatography on Sephadex G-100 column. The total sugar content of HSP-III was amounted to 89.87%. Based on the results of high performance gel permeation chromatogram (HPGPC), FT-IR, NMR spectroscopy, GC, periodate oxidation-smith degradation and methylation analysis, it showed that HSP-III was mainly composed of mannose and galactose, and a small amount of rhamnose, arabinose, xylose, and glucose. The molar ratio of Rha:Ara:Xyl:Man:Glu:Gal was 1.00:2.44:13.11:74.13:13.80:54.39. The main chain of HSP-III was majorly composed of (1→3) glucose. The tumor inhibition ratio on H22 cell was 79.04% at 100 μg/mL of HSP-III.

An acid polysaccharide, named R-PL, was extracted from rose buds by hot water (80 °C) extraction and purified by Sephadex G-200. R-PL, extracted with a total yield of 1.90%, is a highly pure polysaccharide with a total sugar content of 92.51%. A single and symmetrically sharp peak in its high-performance gel-permeation chromatography (HPGPC) spectrum indicates that R-PL is a homogeneous polysaccharide with a molecular weight of 7.727 × 105 Da. Monosaccharide composition analysis shows that it consists of D-arabinose, D-xylose, D-glucose, D-galactose, D-galacturonic acid, and D-glucuronic acid with a molar ratio of 4.6 : 1.4 : 5.22 : 4.81 : 1 : 1.86. Structure analysis, such as FTIR spectroscopy, periodic acid oxidation, Smith degradation, methylation, and NMR analysis, reveals that R-PL has a backbone of →1)-α-D-Glcp-(6→ with side chains of →1)-β-D-Galp-(4,6→, →1)-β-D-Araf-(5→, →1)-α-D-Xylp-(4→, →1)-α-D-GlcpA-(2→ and →1)-α-D-GalpA-(4→. Its morphological characteristics were identified by Congo red experiments and scanning electron microscopy (SEM) analysis. The results show that R-PL does not have a triple-helical conformation in solution; its shape resembles twisted ribbons. Anti-oxidative and anti-aging analyses show that R-PL has significant antioxidant and anti-aging abilities in vivo.

Three series of prenylated and/or geranylated flavonoids were synthesized and evaluated for their α-glucosidase inhibitory activity. The 3',5'-digeranylated chalcone (16) was identified as a new α-glucosidase inhibitor whose activity (IC50=0.90 μM) was 50-fold more than that of acarbose (IC50=51.32 μM). Molecular docking studies revealed the existence of strong hydrophobic interaction and H-bonding between compound 16 and α-glucosidase's active site. The inhibitory mode analysis showed that 16 exhibited a competitive inhibitory mode.

Two novel flavonoids (±)-Anastatins A and B as well as 14 analogs, which containing a benzofuran moiety, were synthesized by using halogenation, Suzuki coupling reaction and an oxidation/Oxa-Michael reaction cascade as the key steps. The structures of the new flavonoids were confirmed by 1 H NMR, 13 C NMR and HRMS. The antioxidant activities of them as well as the key intermediates were evaluated by ferric reducing antioxidant power (FRAP) assay and the active compounds were evaluated in the PC12 cell model of hydrogen peroxide (H 2 O 2 )-induced oxidative damage. SAR studies suggested that, for in vitro antioxidant activity, aurone derivatives showed better bioactivity than flavone counterparts. However, cyclization to benzofuran and connecting the two conjugated parts as a whole conjugated system by a double bond diminished the in vitro antioxidant activity. Among them, the most potent compound 24c was significantly decreased H 2 O 2 -caused cell injury. The apoptotic rate (Annexin V + ) of H 2 O 2 -damaged PC12 cells was 60.7% while that of the compound 24c -treated cells decreased to 5.9% and 4.1% at 10 μM and 100 μM respectively.

In the present work, three fractions of selenized Cordyceps militaris polysaccharides (SeCPS) named SeCPS- I, SeCPS- II and SeCPS- III were isolated and purified by ultra-filtration. Their selenium content were measured as 541.3, 863.7 and 623.3μg/g respectively by a graphite furnace atomic absorption spectroscopy. The monosaccharide comformation analysis showed that they were mainly consisted of D-Mannose, D-Glucose, and D-Galactose in mole ratios of 1:7.63:0.83, 1:1.34:0.31 and 1:3.77:0.41 respectively. Their structure characteristics were compared by IFR and NMR spectroscopy. Scanning electron microscopy (SEM) and Congo red (CR) spectrophotometric method were used to investigate their morphological characteristics and conformational transition. SeCPS-II showed the strongest anti-tumor effects judging from the result of in vitro anti-tumor assays against two tumor cell lines (hepatocellular carcinoma HepG-2 cells and lung adenocarcinom A549 cells).

A purified selenium-containing derivatives of Cordyceps militaris polysaccharide synthesized using H2SeO3/HNO3 and BaCl2 as a catalyst was investigated in this paper. The reaction condition was optimized by selecting different reaction temperature and period. Afterward, the one with the highest Se content was purified by ultra-filtration device with a molecular cut off size of 10KDa. Followed by its structural characterizations. Results of IFR and 13C NMR spectroscopy indicated that C-6 substitution was predominant in selenized polysaccharide. The modified polysaccharide with molecular weight of 1998 KDa was mainly consisted of mannose, glucose and galactose in the mole ratios of with the mole ratios of 1:28.63:1.41. Thermogravimetric and morphological analyses of the samples were carried out by AFS, SEM and AFM. In addition, the in vitro antioxidant results suggested that selenium-containing polysaccharide should be applied as a novel selenium source in dietary supplements, with potent antioxidant properties.

The structural properties and the inhibition on α-d-glucosidase activity of the low molecular weight (LCMPs-II) obtained from the optimized acid hydrolysis of the Cordyceps militaris polysaccharides (CMPs) were investigated in this paper. The LCMPs-II with a molecular weight of 28 KDa mainly composed of rhamnose, xylose and glucose with the molar ratio of 1: 2.19: 6.73 was separated from LCMPs-I which was the acid hydrolysis product of CMPs by chromatography on Sephadex G-100 column. The solubility of LCMPs-II was tested to be 32.12±1.05g in 100mL distilled water under 25°C. Its solubility was almost as twice as that of CMPs. Afterward, the structural features of LCMPs-II was investigated by a combination of chemical and instrumental analysis such as the specific rotation determination, FT-IR, periodate oxidation-Smith degradation, Congo-red, GC, scanning electron microscope and NMR. The results showed that the optical rotation of LCMPs-II was +25° and it was 1,3-branched-rhamnoxyloglucan which had a linear backbone of (1→4)-linked α-d-glucopyranose (α-d-Glcp units).

A chemically new sulfated polysaccharide (SPS50) was prepared from the water soluble polysaccharide (PS50), isolated from Cordyceps_gunnii mycelia, by concentrated sulfuric acid method. The yield of crude SPS50 was 62.34% and its specific rotation was [α](D)(20)=-36.75°. The structural characteristics of this chemically sulfated polysaccharide were determined based on the infrared analysis (IR), high performance liquid chromatography (HPLC) and sodium dodecyl sulfate polyacrylamide gel electropheresis (SDS-PAGE). Its biological properties including anti-oxidant and anti-tumor activities were also investigated. The results showed that the anti-oxidant capacity of SPS50 was not as good as SP50 and the anti-tumor activity of SPS50 was much better than PS50. SPS50 showed evident growth inhibition on K562 cells. The tumor inhibition ratio of SPS50 against K562 cells was 69.92%.

Chrysin-β-D-galactopyranoside was efficiently synthesized, evaluated for its inhibitory activities against H22 cell lines compared with chrysin, the scavenging of hydroxyl radical, DPPH radical and superoxide anion, inhibitory effect against bacteria and fungi. The structures of all compounds were fully characterized by spectroscopic data (NMR, MS). The anti-tumor, antioxidant and antimicrobial activities of chrysin-β-D-galactopyranoside were proved to be enhanced significantly compared with chrysin.

A novel homogeneous polysaccharide fraction (APS) was extracted from Astragalus by hot water and purified by Sephadex G-100 and G-75 column. Its molecular weight was 693kDa. APS and APS with ultra-high pressure treatment exhibited significant inhibitory abilities on a-glucosidase, inhibition rate from high to low in order was 400MPa-APS, 300MPa-APS, 500MPa-APS and APS. The inhibition ​percentage of 400MPa-APS (1.5mg/mL) was 49% (max.). This suggested that the inhibitory activity of APS on a-glucosidase was improved by ultra-high pressure treatment. FT-IR, SEM, CD spectra, atomic force microscope and Congo red test analysis of APS and 400MPa-APS showed ultra-high pressure treatment didn't change the preliminary structure but had an effect on its advanced structure.

The influence of different fermentation conditions on intracellular polysaccharide (IPS) production and activities of the phosphoglucomutase (PGM), UDPG-pyrophosphorylase (UGP), phosphoglucose isomerase (PGI), UDPG-dehydrogenase (UGD), and glucokinase (GK) implicated in metabolite synthesis in Cordyceps militaris was evaluated. The highest IPS production (327.57 ± 6.27 mg/100 mL) was obtained when the strain was grown in the optimal medium containing glucose (40 g · L(-1)), beef extract (10 g · L(-1)), and CaCO3 (0.5 g · L(-1)), and the initial pH and temperature were 7 and 25 °C, respectively. The activities of PGM, UGP, and PGI were proved to be influenced by the fermentation conditions. A strong correlation between the activities of these enzymes and the production of IPS was found. The transcription level of the pgm gene (encoding PGM) was 1.049 times and 1.467 times compared to the ugp gene and pgi gene (encoding UGP and PGI), respectively, in the optimal culture medium. This result indicated that PGM might be the highly key enzyme to regulate the biosynthesis of IPS of C. militaris in a liquid-submerged culture. Our study might be helpful for further research on the pathway of polysaccharide biosynthesis aimed to improve the IPS production of C. militaris.

A series of novel di- or trisubstituted isatin derivatives were designed and synthesized in 5-6 steps in 25-45% overall yields. Their structures were confirmed by 1H NMR and 13C NMR as well as LC-MS. The anticancer activity of the fourty-three new isatin derivatives against human T lymphocyte cells Jurkat was evaluated by MTT assay in vitro. SAR study suggested that the combination of 1-benzyl and 5-[trans-2-(methoxycarbonyl)ethen-1-yl] substitution greatly enhanced their cytotoxic activity. Among them, compound 2h was shown to have a significant cytotoxic activity with an IC50 value of 0.03 μM, more than 330-fold higher than that of it's mother molecule isatin. Investigation of the cell morphology changes and annexin-V/PI staining study demonstrated that compound 2h inhibited the proliferation of Jurkat cells by inducing apoptosis. Since compound 2h induced the dissipation of mitochondrial membrane potential and the activation of caspase-3, it was obvious that compound 2h inhibited the proliferation of Jurkat cells through the mitochondrial apoptotic pathway. Other than this, compound 2h exerted inhibition effect to many other tumor cells and only showed weak cytotoxic to human normal cells suggesting that compound 2h possessed a broad range of anticancer spectrum and high safety to normal cells.

Ergosterol-3-O-(β-D-galactopyranosyl-(1→4)-β-D-glucopyranoside) was efficiently synthesized and evaluated for its inhibitory activities against S180 cell lines compared with ergosterol. The structures of all synthesized compounds were fully characterized by spectroscopic data (NMR, MS). The antitumor activity of the new derivative was significantly enhanced compared with ergosterol.

The parasitic fungus, Paecilomyces sinensis, is used to produce Cordyceps materials as a succedaneum of natural Cordyceps sinensis (C. sinensis) in China. In this work, a glycopeptide (CPS-II) was isolated and purified from Paecilomyces sinensis. The result of HPLC indicated that CPS-II was a glycopeptide. The estimated average molecular weight of CPS-II was 2 × 10(6) Da. FTIR, methylation, periodate oxidation, Smith degradation, (1)H NMR, (13)C NMR and CD were used for its structural analysis. The glycopeptide CPS-II was mainly composed of (1 → 3), (1 → 4) connected glucose and galactose as the backbone, there are (1 → 2,3,6) connected glucose, (1 → 3,6) connected mannose, and (1 → 6) connected galactose. Cell proliferation assay and morphological observations indicated that in a certain range of concentrations and time, CPS-II can significantly improve the proliferation activity of RAW264.7 cells.

Chrysin is a plant flavone that possesses some significant biological activities. β-Cyclodextrin (β-CD) due to its property of encapsulating molecules that are hydrophobic in nature is widely applied as drug delivery vehicle. The paper presents the preparation, characterization and properties of chrysin-β-cyclodextrin inclusion complex. The stoichiometry of the inclusion complex has been established to be 1:3 (chrysin to β-cyclodextrin), with the inclusion rate of 90.5 ± 2.63 at 55 °C. The process of inclusion not only increased the solubility of chrysin but also its antioxidant potential, antimicrobial activity and anti-tumor activity.

Four new naphthoquinones (1–4), including a dimeric one, shikometabolin G (1), together with six known ones (6–10), were isolated from the methanol extract of Onosma paniculatum. Their structures were established based on the analysis of NMR and MS spectroscopic data. All of the compounds were evaluated for inhibitory effects on NO production in murine macrophage RAW 264.7 cells. Compounds 2, 3, 5, 6, 7, 8, and 10 displayed good activity on the inhibition of NO production (IC50 = 0.4–16.5 µM), suggesting the potential property of anti-inflammation.

Paris Saponin I (PSI), a steroidal saponin derivative extracted from a traditional Chinese herbal Paris polyphylla, has shown cytotoxic effects on several tumor cell lines. However, the mechanisms of its antitumor activity especially for lung cancers remain to be elucidated. In this present investigation, we continue to explore the efficacy and mechanisms underlying the cytotoxic effects of PSI in lung cancer cell lines. Three non-small cell lung cancer (NSCLC) cells (H1299, H520, H460) and one small cell lung cancer (SCLC) cell (H446) were treated with PSI for the first time. PSI significantly induced cell cycle arrest at the G2/M phase and mitochondrial-related apoptosis NSCLC cells but not SCLC cells. Additionally, PSI reduced phosphorylation of AKT in NSCLC and ERK in SCLC in general. Interestingly, we observed that PSI influenced different signaling pathways among the four kinds of lung cancer cells. After PSI treatment, p38 MAPK and ERK activation were observed in H1299, while p38 MAPK increased and JNK decreased in H520. On the contrary, we found JNK activation in H460 cells with PSI. However, PSI upregulated the AKT activity and inhibited the JNK expression in H446 cells. The results indicate that PSI exhibits the cytotoxicity in different pathways depending on the cancer types.

Ergosterol 3-O-β-D-glucopyranoside (1a) and ergosterol 3-O-β-D-galactopyranoside (1b) were highly efficiently synthesized and evaluated for their inhibitory activities against two tumor cell lines. The structures of these compounds were extensively confirmed by (1)H, (13)C NMR, IR, and HRMS. Compounds 1a and 1b exhibited interesting cytotoxic profiles. The antitumor activity of compound 1a was higher than that of 1b.

Cordyceps gunnii (berk.) Berk (C. Gunnii) is well known as a Chinese rare caterpillar fungus and has similar pharmacological activity with C. sinensis. In this work, a high-molecular-weight polysaccharide (CPS) was isolated and purified from the mycelia of C. gunnii. The total sugar content of CPS was amounted to 92.84%. The result of HPLC indicated that CPS was a homogeneous polysaccharide. The estimated average molecular weight of CPS was 3.72 × 106 Da. The specific rotation of CPS was recorded [ α ] D 25 = + 134.2 ° . Its characteristic was determined by chemical analysis, gas chromatography, IR spectroscopy and NMR data. The results showed that CPS was mainly composed of glucose, and a small amount of rhamnose, arabinose, xylose, mannose and galactose with a molar ratio of Rha:Ara:Xyl:Man:Glu:Gal = 3.0:2.6:1.0:1.3:106.0:2.8. The main chain of CPS was majorly composed of α-(1 → 4) glucose. The tumor inhibition ratio on K562 cell by CPS was 56.65%.

The structural properties of polysaccharides, respectively, obtained from the fermented mycelium and cultivated fruiting bodies of the Cordyceps militaris were investigated and compared in this paper. First, the crude polysaccharides were extracted from the mycelium and the fruiting bodies, respectively. The polysaccharides were successively purified by Sevag and chromatography on Sephadex G-100 column to produce two polysaccharides fractions termed CMPS-II and CBPS-II, respectively. The average molecular weights of CMPS-II and CBPS-II were 1.402×10(3) kDa and 1.273×10(3) kDa, respectively, and they were mainly composed of mannose, glucose and galactose in the mole ratios of 1:28.63:1.41 and 1:12.41:0.74, respectively, for CMPS-II and CBPS-II. Afterward, the structural features of CMPS-II and CBPS-II were investigated by a combination of chemical and instrumental analysis, such as FT-IR, periodate oxidation-Smith degradation, GC-MS, NMR and methylation analysis. The results indicated that structurally, both CMPS-II and CBPS-II were 1,3-branched-galactomannoglucan that had a linear backbone of (1→4)-linked α-D-glucopyranose (Glcp). Congo-red test revealed that CMPS-II and CBPS-II existed as triple-helical chains in 0.05-0.15 M NaOH solution.

Two polysaccharides: APS-I and APS-II, were obtained after a successive purification consisting of (1) fractional precipitation using ethyl alcohol; (2) filtration through DEAE-Sephadex A-25 and Sephadex G-100 eluted by water. The molecular weights of APS-I and APS-II were 4.77 × 106 and 8.68 × 103 Da, respectively, and they were mainly composed of glucose, and a small amount of arabinose and xylose, with their molar ratios of 0.54:1:18.14 and 0.23:1:29.39, respectively for APS-I and APS-II. FTIR, methylation, periodate oxidation, Smith degradation, 1H NMR and 13C NMR were used in their structure analysis. The results indicated that structurally, APS-I and APS-II were similar, with their main chains mainly composed of major α-(1 → 3) glucose and a few 1 → 4, 1 → 6 glucoses, while the side chain contained arabinoses and xyloses. The tumor inhibition ratios of APS-I and APS-II were 55.47% and 47.72%, respectively.

Cordyceps sinensis is a well-known tonic food or invigorant with broad-spectrum medicinal properties that is widely used in China. Cordyceps gunnii (berk.) Berk is also well known as the Chinese rare caterpillar fungus and has similar pharmacological activities with C. sinensis. The water-soluble polysaccharide CPS50-I was extracted from the mycelia of C. gunnii and further purified by diethylaminoethyl -Sephadex A-25 and Sephadex G-75. Its characteristics were determined by chemical analysis, gas chromatography, high-performance size-exclusion chromatography and infrared spectroscopy. The results showed that CPS50-I is a white powder containing 94.57% carbohydrate which is composed of four kinds of monosaccharides including xylose, mannose, glucose and galactose with a molar ratio of 0.13:0.89:0.54:1. CPS50-I had a molecular weight of ∼9874 Da and [α]D20 = +85 (c 0.5, H2O). The protective effect of CPS50-I against oxidation resistance in D-galactose (D-gal)-induced aging mice was investigated. The results showed that CPS50-I had a significant protective effect against D-gal-induced aging mice. PRACTICAL APPLICATIONS In this work, a water-soluble polysaccharide CPS50-I was extracted from the mycelia of Cordyceps gunnii and further purified by diethylaminoethyl-sephadex A-25 and sephadex G-75. For antioxidant testing in vivo, the protective effect of CPS50-I was investigated against oxidation resistance in D-galactose (D-gal)-induced aging mice. It showed that CPS50-I had an obviously protective effect against D-gal-induced aging mice. The results suggest that the water-soluble polysaccharide CPS50-I provide a source of natural antioxidants with potential value for health foods and therapeutics and may contribute to be used as a dietary supplement to delay the process of aging.

This paper describes an efficient synthesis of carbohydrate fatty acid esters based on a highly stereo- and regio-selective esterification. The suitably protected glycosyl was esterified with stearic acid to give mainly the β-anomer in good yield using p-toluenesulfonic acid as catalyst. The structures of these compounds were fully confirmed by 1H, 13C NMR, mass spectra and HRMS.

Using the low-valent titanium reagent (Zn/TiCl4), dichlorophenylsilane underwent a reductive polymerization reaction to give Si–H functional poly(phenylsilane) (Mw/Mn=2.5, Mn=2400) in a moderate yield. Applying this method, the corresponding organosilane copolymers (2b–2f) were also obtained. The absorption maxima of these organosilane copolymers are remarkably hypsochromically shifted in comparison with those of poly(diarylsilane)s.

Four natural chalcones bearing prenyl or geranyl groups, i.e., bavachalcone (1a), xanthoangelol (1b), isobavachalcone (1c), and isoxanthoangelol (1d) were synthesized by using a regio-selective iodination and the Suzuki coupling reaction as key steps. The first total synthesis of isoxanthoangelol (1d) was achieved in 36% overall yield. A series of diprenylated and digeranylated chalcone analogs were also synthesized by alkylation, regio-selective iodination, aldol condensation, Suzuki coupling and [1,3]-sigmatropic rearrangement. The structures of the 11 new derivatives were confirmed by 1H NMR, 13C NMR and HRMS. The anticancer activity of these new chalcone derivatives against human tumor cell line K562 were evaluated by MTT assay in vitro. SAR studies suggested that the 5′-prenylation/geranylation of the chalcones significantly enhance their cytotoxic activity. Among them, Bavachalcone (1a) displayed the most potent cytotoxic activity against K562 with IC50 value of 2.7 μM. The morphology changes and annexin-V/PI staining studies suggested that those chalcone derivatives inhibited the proliferation of K562 cells by inducing apoptosis.

Two new flavonols japonicins, A (1) and B (2), along with nine known flavonoids were isolated from an antidepressant fraction, which was separated from the 70% alcohol extract of the flowers of Inula japonica Thumb. The structures of compounds 1 and 2 were determined as 3,3',4',5,9,10-hexahydroxy-12-methylchroman[2,3-h]flavone and 8-(1-(3,4-dihydroxyphenyl)ethyl)-3,3',4',5,7-pentahydroxyflavone by the analyses of physical constants and spectral data. The special flavonoid structure having the substituent 1-phenylethyl at C-8 position was discovered for the first time.

A simple and convenient procedure for stereoselective synthesis of (Z)-allyl selenides has been developed by a one-pot reaction of diselenides with Baylis-Hillman adducts in the presence of samarium metal-trimethylsilyl chloride under mild conditions. Presumably, the diselenides are cleaved by Sm/TMSCl system to form selenide anions, which then undergo S(N)2' substitution of Baylis-Hillman adducts to produce the (Z)-allyl selenides.

Azobenzene compounds without big substituents were conveniently reduced by a system consisting of SmI 2 /THF and successively reacted smoothly with analogous aliphatic acyl chlorides or acid anhydrides to afford corresponding mono-acyl symmetrical hydrazobenzene under mild and neutral conditions in one pot; while other azo compounds reacted under similar conditions, amides were the terminate products.

Taking mycelial polysaccharides from Cordyceps gunnii (C. gunnii) as the study subject, the effect of ultrasonic power, time and concentration of polysaccharides on antitumor activity of the polysaccharides was investigated. The ultrasonic processing condition of the polysaccharides was optimized by using orthogonal test design, and determined to be 400 W, 15 min and 1g/L. The change of structures of polysaccharides before and after ultrasonic treatment was also studied. Results show that ultrasonic treatment did not change the characteristic attribute of polysaccharides from C. gunnii. The composition of monosaccharide residues and the category of glycosidic bond have not been changed. But the molecular weight and intrinsic viscosity was reduced, and the alpha-helicity was enhanced after ultrasonic treatment. It was possible that ultrasonic treatment is an effective way for enhancing antitumor activity of polysaccharides.

Cathode plasma of high current electron beam diode is an important research on high power microwave and strong pulsed radio accelerator. It is a reliable method to study cathode plasma by diagnosing the cathode plasma parameters with non-contact spectroscopy measurement system. The present paper introduced the work principle, system composition and performance of the nanosecond (ns) time-resolved spectroscopy diagnosis system. Furthermore, it introduced the implementing method and the temporal relation of lower jitter synchronous trigger system. Simultaneously, the authors designed electromagnetic and radio shield room to protect the diagnosis system due to the high electromagnetic and high X-ray and γ-ray radiation, which seriously interferes with the system. Time-resolved spectroscopy experiment on brass (H62) cathode shows that, the element and matter composition of cathode plasma is clearly increase with the increase in the diode pulsed voltage and current magnitude. The spectroscopy diagnosis system could be of up to 10 ns time resolve capability. It's least is 2 ns. Synchronous trigger system's jitter is less than 4 ns. The spectroscopy diagnosis system will open a new way to study the cathode emission mechanism in depth.

Azo compounds were conveniently reduced by a system consisting of Sm/TiCl 4 to produce aniline anions. This anion species reacted smoothly with aliphatic acyl chlorides or acid anhydrides to afford corresponding amides under mild and neutral conditions.

Alpha-diketones and beta-diketones react with Grignard reagents in the presence of a catalytic amount of Cp2TiCl2 to yield alpha-ketols and corresponding ketones respectively. Sulfoxides can be deoxygenated by Cp2TiCl2/Al system. The possible mechanisms are also discussed.

Highlights: • 5-(2-Carboxyethenyl) isatin derivative (HKL 2H) inhibited K562’s proliferation. • HKL 2H caused the morphology change of G{sub 2}/M phase arrest and typical apoptosis. • HKL 2H induced G2/M cell cycle phase arrest in K562 cells. • HKL 2H induced apoptosis in K562 cells through the mitochondrial pathway. - Abstract: Our previous study successfully identified that the novel isatin derivative (E)-methyl 3-(1-(4-methoxybenzyl)-2,3-dioxoindolin-5-yl) acrylate (HKL 2H) acts as an anticancer agent at an inhibitory concentration (IC{sub 50}) level of 3 nM. In this study, the molecular mechanism how HKL 2H induces cytotoxic activity in the human chronic myelogenous leukemia K562 cells was investigated. Flow cytometric analysis showed that the cells were arrested in the G{sub 2}/M phase and accumulated subsequently in the sub-G{sub 1} phase in the presence of HKL 2H. HKL 2H treatment down-regulated the expressions of CDK1 and cyclin B but up-regulated the level of phosphorylated CDK1. Annexin-V staining and the classic DNA ladder studies showed that HKL 2H induced the apoptosis of K562 cells. Our study further showed that HKL 2H treatment caused the dissipation of mitochondrial membrane potential, activated caspase-3 and lowered the Bcl-2/Bax ratio in K562 cells, suggesting that the HKL 2H-causing programmed cell deathmore » of K562 cells was caused via the mitochondrial apoptotic pathway. Taken together, our data demonstrated that HKL 2H, a 5-(2-carboxyethenyl) isatin derivative, notably induces G{sub 2}/M cell cycle arrest and mitochondrial-mediated apoptosis in K562 cells, indicating that this compound could be a promising anticancer candidate for further investigation.« less

Our previous study successfully identified that the novel isatin derivative (E)-methyl 3-(1-(4-methoxybenzyl)-2,3-dioxoindolin-5-yl) acrylate (HKL 2H) acts as an anticancer agent at an inhibitory concentration (IC50) level of 3nM. In this study, the molecular mechanism how HKL 2H induces cytotoxic activity in the human chronic myelogenous leukemia K562 cells was investigated. Flow cytometric analysis showed that the cells were arrested in the G2/M phase and accumulated subsequently in the sub-G1 phase in the presence of HKL 2H. HKL 2H treatment down-regulated the expressions of CDK1 and cyclin B but up-regulated the level of phosphorylated CDK1. Annexin-V staining and the classic DNA ladder studies showed that HKL 2H induced the apoptosis of K562 cells. Our study further showed that HKL 2H treatment caused the dissipation of mitochondrial membrane potential, activated caspase-3 and lowered the Bcl-2/Bax ratio in K562 cells, suggesting that the HKL 2H-causing programmed cell death of K562 cells was caused via the mitochondrial apoptotic pathway. Taken together, our data demonstrated that HKL 2H, a 5-(2-carboxyethenyl) isatin derivative, notably induces G2/M cell cycle arrest and mitochondrial-mediated apoptosis in K562 cells, indicating that this compound could be a promising anticancer candidate for further investigation.

The reductive desulfonylation of α-phenylsulfonylcinnamates promoted by Sm/HOAc led to the corresponding (E)-cinnamates stereoselectively in good yields under mild conditions.

A series of 5,7-disubstituted chrysin, 7-monosubstituted chrysin, 5-monosubstituted chrysin derivatives were synthesized by alkylation, acetylation, benzoylation, carboxymethylation, and evaluated on their antitumor activity of H22 cells in the search for potential antitumor agents. Among them, compound 3 (5,7-diacetyl chrysin) displayed the most potent antitumor activity with IC50 value of 141 μM. Moreover, there is significant up-regulation of G2 in cell cycle of H22.