Anion-π Interaction-Induced Room-Temperature Phosphorescence of a Polyoxometalate-Based Charge-Transfer Hybrid Material.

Room-temperature phosphorescence (RTP) was realized for the first time in a polyoxometalate-based charge-transfer (CT) hybrid material bearing polyoxometalates (POMs) as electron-donors (D) and rigid naphthalene diimides (NDIs) as electron-acceptors (A), meanwhile, this hybrid material displayed photochromism as well. The significant D-A anion-π interaction induced an additional through-space charge-transfer pathway. The resulting suitable D-A CT states can efficiently bridge the relatively large energy gap between the NDI-localized 1 π-π* and 3 π-π* states and thus trigger the ligand-localized phosphorescence (3 π-π*).

[Limonoids from seeds of Azadirachta indica and their cytotoxic activity].

Eight limonoids were isolated from 95% ethanol extracts of neem(Azadirachta indica) seeds by various chromatographic methods. By comparison of their spectroscopic data with those reported in the literatures, these limonoids were determined as salannin(1), 1-detigloyl-1-isobutylsalannin(2), salannol-3-acetate(3), salannol(4), spirosendan(5), 1-detigloyloxy-3-deacetylsalannin-1-en-3-one(6), nimbin(7) and 6-deacetylnimbin(8). Compounds 2 and 5 were firstly isolated from this genus and 5 represented the only example of its type. And 6 is a new natural product. 6 showed inhibitory activity against HeLa and HL-60 cells, with IC50 of(21.61±4.37) and(27.33±5.74) µmol·L⁻¹, respectively. Both 7 and 8 mildly inhibited the growth of HeLa cells, with IC50 of (33.15±5.24) and (38.56±6.41) µmol·L⁻¹, respectively.

Isolation and purification of two antioxidant peptides from alcalase hydrolysate of Arca subcrenata.

OBJECTIVE: To investigate the constituents with antioxidant activities from alcalase hydrolysate of Arca subcrenata. METHODS: The consecutive chromatographic methods were employed,including ion-exchange chromatography, gel filtration chromatography, and reverse phase high-performance liquid chromatography (RP-HPLC). The amino acid sequences of the purified antioxidant peptides were determined by automated Edman degradation. RESULTS: Under the guidance of the assay of scavenging free radicals, two peptides with antioxidant activities, termed as A-Bg1 and A-Bh, were isolated and purified from the alcalase hydrolysate of Arca subcrenata. CONCLUSION: Constituents from the hydrolysate of Arca subcrenata might be a new potential resource of antioxidants.

[Optimal culture conditions of transgenic Polygonium multiflorum hairy root and the effect of elicitor on its growth].

OBJECTIVE: To optimize the culture medium of transgenic Polygonium multiflorum hairy root and the effect of different elicitors on its growth. METHODS: Measured the growth curve of hairy root in four media, including MS, 1/2 MS, B5 and White and estimated the effects of elicitors on the hairy root biomass. RESULTS: MS medium was the most suitable of the four media for hairy root growth. The different concentrations of elicitors, salicylic acid and methyl jasmonate, inhibited the biomass accumulation of hairy root. CONCLUSION: MS is the optimum medium for transgenic Polygonium multiflorum hairy root. Two usual plant elicitors, salicylic acid and methyl jasmonate, can inhibit the growth of transgenic hairy root.

The ß-catenin-LINC00183-miR-371b-5p-Smad2/LEF1 axis promotes adult T-cell lymphoblastic lymphoma progression and chemoresistance.

BACKGROUND: High-intensity chemotherapy regimens are often used in adult T-cell lymphoblastic lymphoma (T-LBL) patients. Nevertheless, the response rate remains unsatisfactory due to emergence of chemoresistance. Growing evidence has shown that long non-coding RNAs (lncRNAs) are involved in tumor progression and chemoresistance. Herein, we investigated the potential role of lncRNAs in T-LBLs. METHODS: RNAseq was used to screen and identify candidate lncRNAs associated with T-LBL progression and chemoresistance. Luciferase reporter assay was used to examine the binding of miR-371b-5p to the 3'UTR of Smad2 and LEF1, and the binding of TCF-4/LEF1 to the promoter of LINC00183. Chromatin immunoprecipitation assay was undertaken to analyze the connection between LEF1 and the LINC00183 promoter region. RNA immunoprecipitation assays were used to explore the mechanism whereby LINC00183 regulated miR-371b-5p. MTT and flow cytometry assays were used to measure apoptosis of T-LBL cells. RESULTS: LINC00183 was upregulated in T-LBL progression and chemoresistant tissues in both the Sun Yat-sen University Cancer Center dataset and the First Affiliated Hospital of Anhui Medical University dataset. High expression of LINC00183 was correlated with poorer overall survival and progression-free survival of T-LBL patients compared to those with low expression of LINC00183. Furthermore, miR-371b-5p was negatively regulated by LINC00183. In vivo and in vitro assays showed that LINC00183-mediated T-LBL chemoresistance depended on miR-371b-5p expression. The direct binding of miR-371b-5p to Smad2 and LEF1 was verified by luciferase assays. It was shown that TCF4/LEF1 could bind to the LINC00183 promoter site and increase its transcript level. Downregulation of miR-371b-5p led to increased expression of Smad2/LEF1, and in turn increased LINC00183 expression. Additionally, phospho-Smad2 promotes nuclear translocation of ß-catenin, LINC00183 downregulation decreased chemoresistance induced by ß-catenin and TGF-ß1 in T-LBL cells. CONCLUSION: We unraveled a ß-catenin-LINC00183-miR-371b-5p-Smad2/LEF1 feedback loop that promotes T-LBL progression and chemoresistance, indicating that LINC00183 may serve as a potential therapeutic target in T-LBLs.

Hydroxyl octadecenoic acids biosynthesized by crown galls of Panax quinquefolium induced by artermisinic acid.

OBJECTIVE: To investigate the effect of artermisinic acid on the secondary metabolites production of Panax quinquefolium crown galls. METHODS: Artemisinic acid was added into the suspended cells of Panax quinquefolium crown galls and co-culture for two days. Products were isolated with chromatographic method. RESULTS: Three hydroxyl octadecenoic acids [9,12,13-trihydroxy-10-octadecenoic acid (1), 11,12,13-trihydroxy-9-octadecenoic acid (2) and 11-hydroxy-12,13-epoxy-9-octadecenoic acid (3)] were isolated from crown galls of Panax quinquefolium. CONCLUSION: Artermisinic acid as one of the new type of phytohormones that might induce the production of 13-lipoxygenases in crown galls of Panax quinquefolium.

[Construction on the chitosan microparticles of baicalin and comparison of transdermal diffusion in vitro of baicalin in chitosan microparticles and cream].

OBJECTIVE: To construct baicalin chitosan microparticles and compare the in vitro transdermal diffusion of baicalin in microparticles and cream. METHODS: Baicalin chitosan microparticles were constructed by using neutralization method and optimized by orthogonal test; The in vitro transdermal diffusion of baicalin in microparticles and cream was compared by using Franz cell. RESULTS: When the drug:stuff ratio was 1:3, concentration of chitosan was 2 mg/mL, mixed duration was 10 min, both the entrapment efficiency and drug loading efficiency of baicalin chitosan microparticles were over 60%; After 36 h, the cumulative release percentage of baicalin in microparticles and cream in vitro transdermal diffusion was 4.04% and 30%, respectively. The content of drug in microparticles and cream in the skin was 0.11% and 0.14%, respectively. And there was no significant difference (w = 7, P = 0.127) between the content of drug in microparticles and cream in the skin. CONCLUSION: The optimal procedure is simple and convenient with high entrapment efficiency and drug loading efficiency. The drug in the microparticles could be released slower and form local drug reservoir in the skin.

PH-controlled construction of Cu(I) coordination polymers: in situ transformation of ligand, network topologies, and luminescence and UV-vis-NIR absorption properties.

Two new complexes [Cu(I)(3)(L1)I(3)](n) (1, L1 = 2,5-bis(4-pyridyl)-1,3,4-oxadiazole) and [Cu(I)(3)(L2)I(2)](n) (2, L2 = 2,5-bis(4-pyridyl)-1,2,4-triazolate) are controllably formed by using aqueous ammonia to regulate the pH value of the reaction involving CuI and L1. Interestingly, L2 of 2 is in situ generated from the ring transform of L1 when increase the pH value of the reaction. 1 exhibits 2-D layer, while 2 shows 3-D MOFs with a novel 3-nodal 4,4,5-connected net topology of an unprecedented Point (Schlafli) symbol: (4·5(2)·6(2)·7)(5(4)·8(2))(4(3)·5·6(6)). Although both 1 and 2 are built of CuI and similar ligands, different arrangements of CuI chains and ligands endow them with different physical properties. 1 displays a strong pure red luminescence emission, while 2 is nonluminescent and shows a broad absorption band covering the whole UV-vis-NIR spectrum range. The emissive excited states of 1 and the charge transitions of the optical absorption for 2 are solved by DFT calculations.

[Biotransformation of 4-methyl-7-allyloxy coumarin by transgenic hairy roots of Polygonum multiflorum].

OBJECTIVE: To synthesis 4-methyl-7-allyloxy coumarin by Williamson etherification from 4-methyl-7-hydroxy coumarin and apply as a substrate in hairy roots of Polygonum multiflorum. METHODS: The synthesis reaction of 4-methyl-7-allyloxy coumarin used the allyl bromide and potassium carbonate as catalysts, and acetone as solvent reacted for 17 hours, then the product was isolated. 4-methyl-7-allyloxy coumarin was added into the media of supension transgenic hairy roots of Polygonum multiflorum which had been precultured for 8 d, and then co-cultured for another 7 d. The biotransformation products were detected by TLC and HPLC and isolated by various chromatographic methods. RESULTS: Two biotransformation products, 4-methyl-7-hydroxy coumarin and 4-methyl-coumarin-7-O-beta-D-glucoside were isolated and identified. CONCLUSION: Hairy roots of Polygonum multiflorum contains not only glycosyltransferase but also hydrolysis enzymes.

[The purification and characterization of polysaccharides isolated from Ginkgo biloba and their in vitro antioxidant activities].

OBJECTIVE: To isolate and identify the polysaccharides of Ginkgo biloba and determine their antioxidant activities in vitro. METHODS: Used hot extraction and alcohol precipitation to get the crude polysaccharides, removed protein with Sevag method, further purify by column chromatography packed with DEAE-52 and DEAE-Sepharose Fast Flow. The homogeneity and molecular weights were evaluated, configuration and monosaccharide composition were measured by IR and high performance ion chromatography analysis, the scavenging activities of GBPB-S on hydroxyl radical and DPPH were measured. RESULTS: The molecular weights of GBPB-W and GBPB-S were 26 300 and 19 100, and both of them were composed of rhamnose, arabinose, galactose, glucose and mannose with the ratios of (3.48: 8.47:3.73: 1.76: 1) and (5.34: 5.37: 5.27: 1:1.68). GBPB-S had certain scavenging effect on hydroxyl radical and DPPH. CONCLUSION: The polysaccharide isolated from Ginkgo biloba has a direct antioxidant activities in vitro.

[Extraction and antihypertensive activity analysis of chondroitin sulfate from different animals].

OBJECTIVE: Chondroitin Sulfate (CS) from different animals were extracted, which antihypertensive activities were compared. METHODS: CS from the bovine and chicken cartilages were extracted by diluted alkali-enzyme hydrolysis method, with removed free protein by Sevag method, separated and purified by quaternary ammonium complex. Their antihypertensive activities were tested by the modal of SPF rat. RESULTS: The extracted CS didn't have peptide, amino acid or other acid mucopolysaccharides determined by electrophoresis and chromatography, the results of IR was consisted with that of chondroitin sulfate supplied by Sigma Both BCCS and CCCS indicated the antihypertensive activities in the low dosage. Besides, BCCS had faster efficacy but shorter duration than that of CCCS. CONCLUSION: Both BCCS and CCCS had high purity. Animal experiments showed that BCCS and CCCS have the effect of the antihypertensive, which activity of CCCS was more significant than that of BCCS.

Taxol content comparison in different parts of Taxus madia and Taxus chinensis var. mairei by HPLC.

OBJECTIVE: To analysis and compare the taxol content in different parts of Taxus madia and Taxus chinensis var. mairei by High Performance Liquid Chromatography (HPLC). METHODS: 85% EtOH and CH2Cl2 were used for the extraction of taxol. By HPLC, the methodology study and taxol content investigation were performed. RESULTS: The taxol was extracted successfully. One simple and reliable methodology was built up. Basing on these, the taxol content in these two Taxus spp. were analysed and compared, among of which the leaf of Taxus chinensis var. mairei has the highest taxol content (5.18 x 10(-5), w/w). CONCLUSION: Taxol and its content in the original plants can be simply and reliably extracted and investigated by these methods, which also can provided the scientific basis for the rational development of Taxus spp.

[Biotransformation of artemisinic acid by cell suspension cultures of Cephalotaxus fortunei and Artemisia annua].

OBJECTIVE: To investigate the biotransformation of artemisinic acid by cell suspension cultures of Cephalotaxus fortunei and Artemisia annua. METHODS: Artemisinic acid was added into to the media of the suspension cells of Cephalotaxus fortunei and Artemisia annua in their logarithmic growth phase. The biotransfromed product was detected with HPLC and isolated by silica gel column, Sephadex LH20 and ODS chromatography methods. The chemical structure of biotransformed product was elucidated on the basis of physical-chemical properties and spectroscopic data. Otherwise, the influence of co-cultured time on conversion ratio was investigated with HPLC. RESULTS: One biotransformed product, 3-alpha-hydroxyartemisinic acid, was obtained after two days of artemisinic acid administration to the suspension cells of Cephalotaxus fortunei and Artemisia annua. The optimal co-cultured time in suspension cells of Cephalotaxus fortunei was 2 days with the highest biotransformation rate of 8.42%, and in the case of Artemisia annua, it was 3 days and 3.95% respectively. CONCLUSION: It was the first time for the biotransformation of artemisinic acid to 3-alpha-hydroxyartemisinic acid by using cell suspension cultures of Cephalotaxus fortunei and Artemisia annua.

The ß-catenin/TCF-4-LINC01278-miR-1258-Smad2/3 axis promotes hepatocellular carcinoma metastasis.

Hepatocellular carcinoma (HCC) metastasis is largely responsible for HCC-associated recurrence and mortality. We aimed to identify metastasis-related long non-coding RNAs (lncRNAs) to understand the molecular mechanism of HCC metastasis. We first identified that miR-1258 was downregulated in HCC tissues both in The Cancer Genome Atlas (TCGA) and Sun Yat-sen University Cancer Center (SYSUCC) dataset. MiR-1258 expression negatively correlated with recurrence-free survival and overall survival of HCC patients. MiR-1258 overexpression inhibited migration and invasion of HCC cells both in vitro and in vivo, whereas miR-1258 downregulation promoted cell metastasis. Luciferase assays verified direct binding of miR-1258 to Smad2 and Smad3, thereby attenuating TGF-ß/Smad signaling. We further established that lncRNA LINC01278 was a negative regulator of miR-1258. In vivo and in vitro assays demonstrated that LINC01278-mediated HCC metastasis was dependent on miR-1258 expression. Furthermore, miR-1258 downregulation in turn increased LINC01278 expression. We also observed that TCF-4 could bind to the LINC01278 promoter site. In addition, LINC01278 downregulation decreased migration and invasion of HCC cells induced by ß-catenin and TGF-ß1 both in vitro and in vivo. We uncovered a novel mechanism for ß-catenin/TCF-4-LINC01278-miR-1258-Smad2/3 feedback loop activation in HCC metastasis, and the study indicated that LINC01278 could serve as a therapeutic target for HCC metastasis.

Structural, luminescent, and magnetic properties of three novel three-dimensional metal-organic frameworks based on hexadentate N,N'-bis(4-picolinoyl)hydrazine.

Three novel microporous three-dimensional (3-D) metal-organic framework materials [ML](n) [M = Ni, Co, Cd; L = N,N'-bis(4-picolinoyl)hydrazine] were obtained from hydrothermal reactions. The organic ligand L was formed through the in situ ring-opening hydrolysis reaction of 2,5-bis(4-pyridyl)-1,3,4-oxadiazole with the assistance of metal ions. Single-crystal X-ray diffraction studies reveal that complexes 1-3 adopt 6-connected 3-D networks of distorted alpha-Po topology, which are built from non-interpenetrated (4,4) grids cross-linked by zigzag chains. These isomorphic complexes are all of high thermal stability, but some other physical properties are quite different because of their different metal centers. Antiferromagnetic exchange was observed between Ni(II) centers of complex 1, while ferromagnetic for Co(II) centers of complex 2. Complex 3 exhibits strong fluorescence emission.

[Optimization of culture conditions for crown gall of Panax quinquefolium and the content determination of their polysaccharides].

OBJECTIVE: To optimize the culture conditions and determine the content of polysaccharides in crown gall of Panax quinquefolium. METHODS: The orthogonal design was used for the optimization of culture condition (such as media, inoculum amount, pH and the content of inorganic elements in media) and their effects on the polysaccharides content. RESULTS: (1) The crown gall tissue could grow and produce polysaccharides in MS (Murashige & Skoog) solid medium without any hormones; (2) The time-dependent regularity of the growth amount and polysaccharides content of the crown gall tissue in MS solid medium was approached: polysaccharides content was the highest in 21 d and biomass achieved to the greatest in 24 d; (3) The polysaccharides content and growth amount were the highest when pH 5.6 of media; (4) The inoculation of 4 - 7 g (FW/flask) was comparatively advantage to the growth of the crown gall, but no effect on polysaccharides content. CONCLUSION: This method can be used to accumulate the high contents of polysaccharides in crown gall cultures of P. quinquefolium.

Biotransformation of thymol by hairy roots of transgenic Polygonum multiflorum.

OBJECTIVE: The exogenous substrate, thymol, was firstly biotransformed by using suspension hairy roots of transgenic Polygonum multflorum, and its biotransformed situation was also investigated. METHODS: After five days co-cultivated period, the transformed product was isolated by Thin Layer Chromatograph and Column Chromatograph, with the structure elucidated by physic-chemical methods and spectra data. Meanwhile, the time course of biotransformation (T-C) for thymol was also measured by HPLC to illuminate its bio-transformed situation. RESULTS: The glycosylated product, namely DMP, was isolated and purified, which structure was determined as 5-methyl-2-(1-methylethyl) phenyl- beta-D-glucopyranoside. And the distribution of DMP in the medium or culture was varied in different co-cultivated periods, and for five days co-cultivated period, it mainly existed in the medium. CONCLUSION: The hairy roots of Polygonum multiflorum were able to convert the aromatic exogenous substrate, thymol, into its glycoside. Furthermore, the time course indicated the relationship between DMP and co-cultivated period.

[Comparative studies on the amount of ginsenosides between the crown galls and Chinese medicinal materials of Panax quinquefolium].

OBJECTIVE: To provide theoretical basis for the production of ginsenosides by using modern biotechnologies, the comparative studies of the amount of ginsenosides between the crown galls and Chinese medicinal materials of Panax quinquefolium were carried out. METHODS: Total ginsenosides were determined by spectrophotometry, and the contents of ginsenoside Rb1, Rb3, Rc, Re were determined by HPLC. RESULTS: (1) The total ginsenosides in the crown galls of Panax quinquefolium (aftert 27 days' cultivation) was almost as much as that of Chinese medicinal material of Panax quinquefolium. (2) The contents of ginsenoside Rb1, Re in the crown galls were about half of that in Chinese medicinal materials of Panax quinquefolium, and ginsenoside Rc was about 80%. But the amount of ginsenoside Rb3 in the crown galls of Panax quinquefolium was much more than that in Chinese medicinal materials of Panax quinquefolium as almost 15 times higher. CONCLUSION: The crown galls of Panax quinquefolium may be a new potential resource for large-scale production of ginsenosides.

Structural characterization and immunoregulatory activity of a new polysaccharide from Citrus medica L. var. sarcodactylis.

A new homogeneous heteropolysaccharide (CMSPA90-1) was purified from bergamot by DEAE sepharose fast flow and Sephadex G-75 columns, and was shown to have a molecular weight of 17.6 kDa. Its chemical structure was elucidated by acid hydrolysis and methylation analysis, along with high-performance anion-exchange chromatography, Fourier transform infrared spectroscopy coupled with gas chromatography-mass spectrometry, NMR spectroscopies, the Congo red test, and circular dichroism. CMSPA90-1 consisted of a pyranoside and funanside with branches containing α- and ß-configurations simultaneously. Arabinose and glucose might form an arabinoglucan backbone. The ultrastructure of CMSPA90-1 was further characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results of thermogravimetric analysis (TGA) revealed that CMSPA90-1 had good thermal stability. The results of DPPH˙ and ABTS+˙ radical scavenging assays indicated that CMSPA90-1 exhibited free-radical-scavenging properties. Otherwise, CMSPA90-1 could promote the proliferation of mouse splenocytes and the neutral red phagocytosis of RAW264.7 cells, which indicated that CMSPA90-1 could be researched and developed as one of the potential functional foods or natural medicines.

[Biotransformation of furannoligularenone by hairy root cultures of Polygonum multiflorum].

OBJECTIVE: To investigate the biotransformation of furannoligularenone by hairy roots of Polygonum multiflorum. METHODS: Furannoligularenone was added to the medium of hairy roots of P. multiflorum after precultured for 9 days, then they were co-cultured. The products were isolated and identified on the basis of their physical chemical properties and spectroscopic data. The T-C curve of biotransformation was investigated with HPLC. RESULTS: The hairy roots of P. multiflorum transformed the substrate to two products, 3-oxo-eremophila-1,7(11)-dien-12,8-olide(II) and 3-oxo-8-hydroxy-eremophila-1,7(11)-dien-12,8-olide(III). After co-cultured for 3 days, the mole conversion ratio of the substrate reached the highest (27.2%). CONCLUSION: It's possible to biotransform furannoligularenone by hairy roots of P. multiflorum.