Synthesis of recyclable and light-weight graphene oxide/chitosan/genipin sponges for the adsorption of diclofenac, triclosan, and microplastics.

Emerging micropollutants, such as pharmaceuticals and microplastics (MPs), have become a pressing water environmental concern. The aim of this study is to synthesize chitosan sponges using graphene oxide (GO) and genipin (GP) for the removal of pharmaceuticals (diclofenac (DCF) and triclosan (TCS)) and MPs, verify their adsorption mechanisms, evaluate the effects of temperature, pH, and salinity on their adsorption capacities, and determine their reusability. The GO5/CS/GP sponge exhibited a macroporous nature (porosity = 95%, density = 32.6 mg/cm3). GO and cross-linker GP enhanced the adsorption of DCF, TCS, and polystyrene (PS) MPs onto the CS sponges. The adsorption of DCF, TCS, and PS MPs involved multiple steps: surface diffusion and pore diffusion of the sponge. The adsorption isotherms demonstrated that Langmuir model was the most fitted well model to explain adsorption of TCS (qm = 7.08 mg/g) and PS MPs (qm = 7.42 mg/g) on GO5/CS/GP sponge, while Freundlich model suited for DCF adsorption (qm = 48.58 mg/g). DCF adsorption was thermodynamically spontaneous and endothermic; however, the adsorption of TCS and PS MPs was exothermic (283-313 K). The optimal pH was 5.5-7 due to the surface charge of the GO5/CS/GP sponge (pHzpc = 5.76) and ionization of DCF, TCS, and PS MPs. As the salinity increased, DCF removal efficiency drastically decreased due to the weakening of electrostatic interactions; however, TCS removal efficiency remained stable because TCS adsorption was mainly caused by hydrophobic and π-π interactions rather than electrostatic interaction. The removal of PS MPs was enhanced by the electrostatic screening effects of high Na+ ions. PS nanoplastics (average size = 26 nm) were removed by the GO5/CS/GP sponge at a rate of 73.0%, which was better than that of PS MPs (41.5%). In addition, the GO5/CS/GP sponge could be recycled over five adsorption-desorption cycles.

Coupled adsorption-photocatalysis process for the removal of diclofenac using magnetite/reduced graphene oxide nanocomposite.

Diclofenac (DCF) is frequently detected in water bodies (ng/L to g/L) as it is not completely removed by conventional wastewater treatment plants. Adsorption and photocatalysis have been studied as promising methods for treating DCF; however, both processes have limitations. Thus, in this study, the removal efficiency of DCF is evaluated using a magnetite/reduced graphene oxide (Fe3O4/RGO) nanocomposite via a coupled adsorption-catalysis process. The Fe3O4/RGO nanocomposite was successfully synthesized using a microwave-assisted solvothermal method and exhibited a bandgap of 2.60 eV. The kinetic data best fitted the Elovich model (R2 = 0.994, χ2 = 0.29), indicating rapid adsorption. The maximum DCF adsorption capacity calculated using the Langmuir model was 80.33 mg/g. An ultraviolet C (UVC) light source and 0.1 g/L of Fe3O4/RGO nanocomposite were the optimum conditions for the removal of DCF (C0 = 30 mM) by a coupled adsorption-photocatalysis process (first-order rate constant (k) = 0.088/min), which was greater than the single adsorption (k = 0.029/min) and pre-adsorption and post-photocatalysis (k = 0.053/min) processes. This indicates that the adsorbed DCF did not hamper the photocatalytic reaction of the Fe3O4/RGO nanocomposite, but rather enhanced the coupled adsorption-photocatalytic reaction. DCF removal efficiency was higher at acidic conditions (pH 4.3-5.0), because high H+ promotes the generation of certain reactive oxygen species (ROS) and increases of electrostatic interaction. The presence of NaCl and CaCl2 (10 mM) did not notably affect the total DCF removal efficiency; however, Ca2+ affected the initial DCF adsorption affinity. Scavenger experiments demonstrated O2∙- and h+ play a key ROS than ·OH to degrade DCF. The acute toxicity of DCF towards Aliivibrio fischeri gradually decreased with increasing treatment time.

Adsorption behavior of triclosan on microplastics and their combined acute toxicity to D. magna.

Microplastics (MP) have been recently identified as emerging water contaminants in worldwide. Owing to its physicochemical properties, MP have been considered as a vector of other micropollutants and may affect their fate and ecological toxicity in the water environment. In this study, triclosan (TCS), which is a widely-used bactericide, and three frequently found types of MP (PS-MP, PE-MP, and PP-MP) were investigated. The adsorption behavior of TCS on MP was investigated by the effect of reaction time, initial concentration of TCS, and other water chemistry factors. Elovich model and Temkin model are the most fitted well with kinetics and adsorption isotherms, respectively. The maximum TCS adsorption capacities were calculated for PS-MP (9.36 mg/g), PP-MP (8.23 mg/g), and PE-MP (6.47 mg/g). PS-MP had higher affinity to TCS owing to hydrophobic and π-π interaction. The TCS adsorption on PS-MP was inhibited by decreasing concentrations of cations, and increasing concentration of anion, pH, and NOM concentration. At pH 10, only 0.22 mg/g of adsorption capacity was obtained because of the isoelectric point (3.75) of PS-MP and pKa (7.9) of TCS. And almost no TCS adsorption occurred at NOM concentration of 11.8 mg/L. Only PS-MP had no acute toxic effect on D. magna, whereas TCS showed acute toxicity (EC50,24h of TCS = 0.36 ± 0.4 mg/L). Although survival rate increased when TCS with PS-MP due to lower the TCS concentration in solution via adsorption, PS-MP was observed in intestine and body surface of D. magna. Our findings can contribute to understanding the combined potential effects of MP fragment and TCS to aquatic biota.

Adsorption of Hg(II) on polyethyleneimine-functionalized carboxymethylcellulose beads: Characterization, toxicity tests, and adsorption experiments.

Mercury (Hg) is widely used in many industrial processes and is released into the environment. Therefore, efficient removal of Hg from water is of vital importance worldwide. Here, we explored the adsorption characteristics of Hg(II) on polyethyleneimine-functionalized carboxymethylcellulose (PEI-CMC) beads and studied the toxicity of the beads toward Daphnia magna and Pseudokirchneriella subcapitata. The PEI-CMC beads had an average particle size of 2.04 ± 0.25 mm, a point of zero charge (pHpzc) of 5.8, and a swelling ratio of 2.45. Acute toxicity tests demonstrated that the PEI-CMC beads had no toxic effects on D. magna. The growth inhibition tests revealed that growth inhibition of P. subcapitata could be attributed to adsorption of trace elements in growth media on the PEI-CMC beads. The adsorption experiments exhibited that the Matthews and Weber model best described the kinetic data, whereas the Redlich-Peterson model was well fitted to the isotherm data. The theoretical maximum Hg(II) adsorption capacity of the PEI-CMC beads was 313.1 mg/g. The thermodynamic experiments showed endothermic nature of the Hg(II) adsorption on the PEI-CMC beads at 10-40 °C. The adsorption experiments exhibited that the Hg(II) adsorption capacity decreased gradually as pH increased from 2 to 12. The adsorption of Hg(II) on the PEI-CMC beads can occur through chelation and electrostatic attraction. The FTIR and XPS spectra before and after Hg(II) adsorption confirmed that chelation of neutral Hg(II) species (HgCl2, HgClOH, and Hg(OH)2) can occur with amino and oxygen-containing functional groups on the PEI-CMC beads. Considering species distribution of Hg(II) and the pHpzc of the PEI-CMC beads, electrostatic attraction between the positively-charged beads and anionic Hg(II) species (HgCl3- and HgCl42-) can take place in highly acidic solutions. The PEI-CMC beads were regenerated and reused for Hg(II) adsorption using 0.1 M HCl.

Mechanism of Lakoochin A Inducing Apoptosis of A375.S2 Melanoma Cells through Mitochondrial ROS and MAPKs Pathway.

Malignant melanoma is developed from pigment-containing cells, melanocytes, and primarily found on the skin. Malignant melanoma still has a high mortality rate, which may imply a lack of therapeutic agents. Lakoochin A, a compound isolated from Artocarpus lakoocha and Artocarpus xanthocarpus, has an inhibitory function of tyrosinase activity and melanin production, but the anti-cancer effects are still unclear. In the current study, the therapeutic effects of lakoochin A with their apoptosis functions and possible mechanisms were investigated on A375.S2 melanoma cells. Several methods were applied, including 3-(4,5-Dimethylthiazol-2-yl)-2,5- diphenyltetrazolium bromide (MTT), flow cytometry, and immunoblotting. Results suggest that lakoochin A attenuated the growth of A375.S2 melanoma cells through an apoptosis mechanism. Lakoochin A first increase the production of cellular and mitochondrial reactive oxygen species (ROSs); mitochondrial ROSs then promote mitogen-activated protein kinases (MAPKs) pathway activation and raise downstream apoptosis-related protein and caspase expression. This is the first study to demonstrate that lakoochin A, through ROS-MAPK, apoptosis-related proteins, caspases cascades, can induce melanoma cell apoptosis and may be a potential candidate compound for treating malignant melanoma.