Montmorillonite-supported nanoscale zero-valent iron for thiamethoxam removal: response surface optimization and degradation pathway.

As a highly efficient insecticide, thiamethoxam was widely used in the world. However, it was bioaccumulative and toxic to aquatic organisms that must be removed from water. In this work, nanoscale zero-valent iron particles loaded on montmorillonite (nZVI/Mt) were successfully synthesized for effective removal of thiamethoxam. The properties of nZVI/Mt for the removal of thiamethoxam were investigated, and the reaction conditions were optimized through response surface methodology. Furthermore, the degradation products were analyzed by liquid chromatography-mass spectrometry (LC/MS). The results demonstrated that the reaction activity of nZVI was enhanced because the agglomeration and oxidation of nZVI particles were effectively inhibited by using montmorillonite as a support. The significance of the effects of each factor on the removal of thiamethoxam was determined to be in the order of pH Ëƒ temperature Ëƒ reaction time Ëƒ nZVI/Mt dosage. The optimal conditions were as follows: a dosage of nZVI/Mt of 2 g/L, a reaction time of 2 h, a reaction temperature of 35 °C, and a solution pH of 3. The removal efficiency of thiamethoxam (C0 = 20 mg/L) was observed to be as high as 94.29% under the optimal conditions, which was close to the value of 94.47% that was predicted using the mathematical model, indicating that the model could accurately predict the removal efficiency of thiamethoxam. The degradation mechanism involved the -NO2 group on the thiamethoxam molecule was reduced and eliminated by nZVI/Mt.

Ultrasound-promoted two-step synthesis of 3-arylselenylindoles and 3-arylthioindoles as novel combretastatin A-4 analogues.

A series of 3-(3'-hydroxy-4'-methoxyphenyl)selenyl-5,6,7-trimethoxy-1H-indoles and 3-(3'-hydroxy-4'-methoxyphenyl)thio-5,6,7-trimethoxy-1H-indoles were obtained as a new class of combretastatin A-4 (CA-4) analogues via a convenient ultrasound (US)-assisted two-step process involving 3-selenenylation/sulfenylation followed by O-deallylation. With the assistance of US irradiation, both the reaction rates and yields of selenenylation, sulfenylation and O-deallylation could be significantly improved. A comparison of the reaction rates of O-deallylation and ester reduction demonstrated that O-deallylation was more sensitive to US irradiation. Finally, these products were evaluated for their antiproliferative activities, and most of them showed moderate to potent activities against three human cancer cell lines in vitro.

Synthesis and Biological Evaluation of 3-Alkyl-1,5-Diaryl-1H-Pyrazoles as Rigid Analogues of Combretastatin A-4 with Potent Antiproliferative Activity.

A series of novel 3-alkyl-1,5-diaryl-1H-pyrazoles were synthesized as combretastatin A-4 (CA-4) analogues and evaluated for antiproliferative activity against three human cancer cell lines (SGC-7901, A549 and HT-1080). Most of the target compounds displayed moderate to potent antiproliferative activity, and 7k was found to be the most potent compound. Structure-activity relationships indicated that compounds with a trimethoxyphenyl A-ring at the N-1 position of the pyrazole skeleton were more potent than those with the A-ring at the C-5 position. Tubulin polymerization and immunostaining experiments revealed that 7k potently inhibited tubulin polymerization and disrupted tubulin microtubule dynamics in a manner similar to CA-4. Computational modelling demonstrated that the binding of 7k to the colchicine binding site on microtubules may involve a similar mode as CA-4.

3-(3,4,5-Trimethoxyphenylselenyl)-1H-indoles and their selenoxides as combretastatin A-4 analogs: microwave-assisted synthesis and biological evaluation.

A series of 3-(3,4,5-trimethoxyphenylselenyl)-1H-indoles and their selenoxides were designed as a new class of combretastatin A-4 (CA-4) analogs. The B ring and the cis double bond of CA-4 were replaced by an indole moiety and selenium atom, respectively. A facile and efficient microwave-assisted synthesis of 3-arylselenylindoles was developed to prepare the target compounds, which were then evaluated for antiproliferative activity against three human cancer cell lines using an MTT assay. Most of these compounds exhibited significant antiproliferative activity, with some showing nanomolar IC50 values. Tubulin polymerization and immunostaining experiments revealed that 13a potently inhibited tubulin polymerization and disrupted tubulin microtubule dynamics in a similar manner to CA-4. Docking studies demonstrated that 13a adopts an orientation similar to that of CA-4 at the colchicine binding site on tubulin.

Preparation, characterization and anticancer activity of norcantharidin-loaded poly(ethylene glycol)-poly(caprolactone) amphiphilic block copolymer micelles.

In this study, a novel amphiphilic block copolymer biomaterial - poly (ethylene glycol)-poly (caprolactone) (PEG-PCL), was used to entrap norcantharidin (NCTD), taking advantage of self-assembly theory. Dialysis and volatilization dialysis were used to prepare copolymer micelles. Drug-loaded micelles were compared with blank micelles in terms of their particle diameter, morphology and IR spectral characteristics. The results revealed that there was no significant difference in respect of morphology and IR spectrum, but particle size differed. Drug-loaded micelles had a smaller particle size than blank micelles. Three important factors influencing particle size, the drug loading content (LC) and the drug entrapment efficiency (EE) of the NCTD-loaded micelles, were studied. The results indicated that the method of preparation and the type of organic solvent had a significant influence on the size of the micelles. LC and EE were greatly affected by the ratio of NCTD to copolymer. In vitro release of NCTD from the conjugate micelles showed that its release rate depended on the pH of the phosphate buffer solution (PBS). The amount released was higher at lower pH than under neutral conditions. In vitro antitumor activity of the NCTD conjugate against human hepatoma (HepG2) cell line and human lung cancer (A549) cell line was evaluated by the MTT method. Micelles loaded with NCTD demonstrated greater and more satisfactory cell viability inhibition than the free drug. In vivo antitumor activity of drug-loaded micelles was investigated in mice bearing S180 mouse sarcoma. NCTD-loaded micelles displayed tumor inhibition effects, better than the free drug. As a new drug delivery system, copolymer micelles present many advantages including easy formulation, good water solubility, low toxicity and high treatment efficacy, and show great potential as carriers of hydrophobic drugs.