A novel supramolecular AIE π-gel for fluorescence detection and separation of metal ions from aqueous solution.

A novel supramolecular aggregation induced emission (AIE) π-gel (ONT) was constructed by using a functionalized trimesic amide (TCP) molecule assembled with a bis-pyridine functionalized naphthalene diimide (ND) molecule using a non-covalent interaction. The ONT showed strong AIE at 468 nm. Furthermore, the ONT could detect and adsorb ferric (Fe3+) or cupric (Cu2+) ions from water. Meanwhile, a thin film based on supramolecular AIE π-gel ONT was prepared, which could be used as a fluorescent security display material for detecting Fe3+ or Cu2+. Thus, the AIE π-gel ONT shows potential for practical applications in efficient multi-analyte detection and separation and as a fluorescent display material.

Rationally introduce AIE into chemosensor: A novel and efficient way to achieving ultrasensitive multi-guest sensing.

Recently, ultrasensitive detection and multi-guest sensing have received extensive attention due to their high sensitivity and efficiency. Herein, we report a novel approach to achieve ultrasensitive detection of multi-analyte. This approach is concluded as "rationally introduce Aggregation-Induced Emission (AIE) into chemosensor". According to this approach, by rationally introducing self-assembly moiety, the obtained chemosensor DNS could serve as a novel AIEgen and show strong AIE in DMSO/H2O (water fraction 80%) binary solution. Interestingly, a simple fluorescent sensor array based on the DNS has been developed. This sensor array could selectively sense Fe3+, Al3+, H2PO4- and L-Arg in water solution. More importantly, this sensor array shows ultrasensitive detection for Fe3+, Al3+ and L-Arg. The LODs of the sensor array for Fe3+, Al3+ and L-Arg are in the range of 3.54×10-9M to 9.42×10-9M. Moreover, H2PO4- could realize the reversible detection of Fe3+ in the DMSO/H2O (water fraction 80%) solution. Meanwhile, DNS-based test papers and thin films were prepared, which could serve as test kits for convenient detection Fe3+, Al3+, and L-Arg in water. In addition, they could also act as efficient erasable fluorescent display materials.

Pillar[5]arene-based spongy supramolecular polymer gel and its properties in multi-responsiveness, dye sorption, ultrasensitive detection and separation of Fe3.

Herein, a novel way to design and construct multi-functional spongy supramolecular polymer gels through an easy to make tripodal guest (TA) and a naphthalimide functionalized-pillar[5]arene host (AP5) has been developed. According to this approach, a novel pillar[5]arene-based supramolecular polymer gel (SHG) was constructed via multi-non-covalent interactions such as host-guest inclusion, C-Hπ, ππ and hydrogen bonds and so on. Interestingly, the SHG exhibits a spongy structure and strong aggregation induced emission (AIE). Furthermore, the SHG also exhibited multi-responsiveness toward outer stimuli such as heating-cooling, pH, competitive agents and mechanical. More importantly, the SHG xerogel shows separation properties for Fe3+, methyl orange, methylene blue and sudan I dyes. The separation rates of SHG xerogel for Fe3+ ions and organic dyes can reach up to 99.8%. Simultaneously, the SHG could ultrasensitively detect Fe3+ (LOD is 0.9 nM). In addition, a thin film based on SHG was also prepared, which was confirmed to be a convenient test kit for detecting Fe3+.

Anion induced supramolecular polymerization: a novel approach for the ultrasensitive detection and separation of F.

A novel approach for the ultrasensitive detection and separation of F- has been successfully developed. F- could induce a tripodal naphthalene imide sensor (TNA) to result in supramolecular polymerization, leading to strong AIEE. The TNA could act as an excellent recyclable material for F- detection and separation.

Acylhydrazone functionalized benzimidazole-based metallogel for the efficient detection and separation of Cr3.

Chromium(iii) is a kind of microelement and can be converted to the more toxic chromium(vi), which is a carcinogen, by redox cycling. Thus, the development of novel materials for the detection and removal of Cr3+ is a very important issue. A novel metallogel chemosensor (BMG-Fe) based on functionalized benzimidazole (BM) and Fe3+ was constructed, which could fluorescently detect and separate Cr3+. The detection limit of BMG-Fe for Cr3+ is 2.62 × 10-8 M, and it exhibited high sensitivity and selectivity for Cr3+. Meanwhile, the absorbing percentage of BMG-Fe for Cr3+ is 96.36%, indicating a high separation rate. Interestingly, the sensitivity and ingestion capacity of BMG-Fe for Cr3+ are better than that of the simple organogel (BMG). So, the metallogel BMG-Fe could be utilized for the efficient removal of heavy metal ions from waste water.

One-pot synthesis and biological evaluation of N-(aminosulfonyl)-4-podophyllotoxin carbamates as potential anticancer agents.

A series of N-(aminosulfonyl)-4-podophyllotoxin carbamates were synthesized via the Burgess-type intermediate, and their antiproliferative activities were evaluated. Most of them possessed more potent cytotoxic effects against four human tumor cell lines (HeLa, A-549, HCT-8 and HepG2) and less toxic to normal human fetal lung fibroblast WI-38 cells than etoposide. In particular, N-(morpholinosulfonyl)-4-podophyllotoxin carbamate (9) exhibited the most potent activity towards these four tumor cells with IC50 values in the range of 0.5-16.5µM. Furthermore, immunofluorescence analysis revealed that 9 induced cell apoptosis by up-regulating the expression of p53 and ROS. Meanwhile, 9 effectively inhibited tubulin polymerization and microtubule assembly at cellular levels in HeLa cells. In addition, 9 could induce cell cycle arrest in the G2/M phase in HeLa cells by up-regulating levels of cyclinB1 and cdc2 and decreasing the expression of p-cdc2. These results indicated that 9 had potential for further development as anticancer agents.

Investigation of the anti-angiogenesis effects induced by deoxypodophyllotoxin-5-FU conjugate C069 against HUVE cells.

We have found that the deoxypodophyllotoxin-5-fluorouracil conjugate, 4'-O-demethyl-4-deoxyppodophyllotoxin-4'-yl 4-((6-(2-(5-fluorouracil-yl)acetamido) hexyl)amino)-4-oxobutanoate (C069), possessed superior cytotoxicities and less toxicity compared with etoposide. In this paper, the anti-angiogenic and vascular disrupting activities of C069 were examined with several in vitro and in vivo models. First, we demonstrated that C069 significantly inhibited the proliferation, migration, tube formation and disrupted the formed tube-like structures of HUVE cells, and inhibited angiogenesis in chicken chorioallantoic membrane assay. Furthermore, we found that C069 inhibited tube formation of HUVE cells by down-regulating the MMP-2, MMP-9, and phosphorylation of Akt and ß-catenin. These results provided the initial evidence that C069 exerts potent anti-angiogenic and vascular disrupting effects.

Conjugates of podophyllotoxin and norcantharidin as dual inhibitors of topoisomeraseâ ¡ and protein phosphatase 2A.

A series of novel conjugates of podophyllotoxin and norcantharidin was designed using association strategy, and synthesized by coupling 4'-demethylepipodophyllotoxin with N-amino acid norcantharimides, and their cytotoxicitiy was evaluated against four human tumor cell lines (A-549, HepG2, HeLa and HCT-8) and normal human diploid fibroblast line WI-38. These compounds exhibited potent cytotoxic effects on tumor cell lines, whereas it was less toxic to WI-38 cells than anticancer drug VP-16 or its parent compound norcantharidin. Furthermore, conjugates 7a, 7c, 7f, 7j, 7k and 7l displayed excellent PP2A inhibition activity with IC50 values of 0.49-9.52 µM. The most potent compound 7l also exhibited topoisomeraseⅡinhibition activity. In addition, compound 7l induced cell-cycle arrest in the G2/M phase in HepG2 by regulating levels of cyclinB1 and cdc2.

Synthesis of hybrid 4-deoxypodophyllotoxin-5-fluorouracil compounds that inhibit cellular migration and induce cell cycle arrest.

A series of deoxypodophyllotoxin-5-fluorouracil hybrid compounds were synthesized, and their cytotoxic activity was evaluated using four human cancer cell lines (HeLa, A549, HCT-8, and HepG2) and the human normal cell line WI-38. The synthesized compounds exhibited greater cytotoxic activity in tumor cells and reduced toxicity in the normal cell line compared with the anticancer drug VP-16 and 5-FU. Additionally, the most potent of these compounds-4'-O-demethyl-4-deoxypodophyllotoxin-4'-yl 4-((6-(2-(5-fluorouracil-yl) acetamido) hexyl) amino)-4-oxobutanoate (compound 22)-induced cell-cycle arrest in the G2/M phase by regulating levels of cdc2, cyclinB1, and p-cdc2 in A549 cells. Furthermore, compound 22 may inhibited the migration of A549 cells via down-regulation of MMP-9 and up-regulation of TIMP-1.

Synthesis and biological evaluation of norcantharidin derivatives as protein phosphatase-1 inhibitors.

Cantharidin and norcantharidin display anticancer activity against a broad range of tumor cell lines. In this study, we have synthesized a series of norcantharidin derivatives and evaluated their cytotoxic effects on four human tumor cell lines together with the genetically normal human diploid fibroblast line WI-38. One of our compounds (1S,4R)-3-((4-(4-(4-fluorophenyl)piperazin-1-ylsulfonyl) phenyl)carbamoyl)-7-oxa-bicyclo[2.2.1]heptane-2-carboxylic acid (12) exhibited potent cytotoxic effects on the tumor cell lines A-549, HepG2, HeLa, and HCT-8, whereas it was less toxic to WI-38 cells than its parent compound, norcantharidin. In addition, this compound inhibited protein phosphatase-1 activity and microtubule formation in HeLa cells, and it also interacts with calf thymus DNA.