A passive sampling device, a polar organic chemical integrative sampler (POCIS), was used to monitor 13 pharmaceuticals and 8 transformation products in upstream and downstream wastewater treatment plant effluent. A POCIS laboratory calibration study was performed to determine uptake behavior and the effect of water flow on the sampling rate. Most compounds showed a linear accumulation, and the sampling rate values ranged from 0.031 to 0.559 L/day. The developed POCIS samplers were used in field experiments in a wastewater-impacted river. Using the calculated sampling rates, the time-weighted average concentration values were measured by three different approaches: (1) laboratory calibration sampling rates (2) performance reference compound (PRC) correction sampling rates and (3) field calibration sampling rates. Nine deuterated compounds (acetaminophen-d3, antipyrine-d3, sulfamethoxazole-d4, carbamazepine-d10, diclofenac acid-d4, clofibric acid-d4, bezafibrate-d6, ibuprofen-d3 and naproxen-d3) were studied as PRCs. Antipyrine-d3 was successfully tested as a PRC for sulfamethoxazole, ibuprofen, 2-hydroxy ibuprofen, diclofenac acid, 4-hydroxydiclofenac acid, carbamazepin, carbamazepin 10,11-epoxide, sulfadiazine, 1-naphthol, antipyrine, naproxen and 4-chlorobenzoic acid. Finally, the POCIS was used to monitor target compounds in river water and measure their attenuation. For most compounds, the POCIS attenuation results were not significantly different from those of the spot samples, which demonstrated that a POCIS with a PRC correction can determine the attenuation of organic micropollutants in rivers.

Numerous catalysts have been successfully introduced into CO2 fixation in aqueous or organic systems. However, one single catalyst owning both activities is still rarely seen, to the best of our knowledge. In this report, we develop a core-shell structured AgNWs/NC700 composite using Ag nanowires core encapsulated by nitrogen-doped carbon shell. Through contrast experiments and DFT calculations, it was confirmed that Ag nanowires worked as the active sites for CO2 fixation and the uniformly coating of nitrogen-doped carbon created a CO2-rich environment around Ag nanowires, which could significantly improve the catalytic activity of Ag nanowires for electrochemical CO2 fixation. Under mild conditions, up to 96% Faradaic efficiency of CO, 95% yield of Ibuprofen and 92% yield of propylene carbonate could be obtained in electrochemical CO2 direct reduction, carboxylation and cycloaddition, respectively, at the same AgNWs/NC700 catalyst. These results might provide an alternative strategy for efficient chemical fixation of CO2.

Metal-ligand coordination involving hydrogen bond functionalized ligands was employed rationally to get an easy access to a series of metallogelators derived from 3-pyridyl derivatives of non-steroidal-anti-inflammatory drugs (NSAIDs) [e.g. ibuprofen, sulindac and flurbiprofen designated as 3-pyIBU, 3-pySUL and 3-pyFLR, respectively] and biogenic metal centers [Zn(II), Cu(II), Mn(II) and Ag(I)]. Thirteen metallogels (MG1-MG13) were obtained by allowing the ligands and the metal salts to react in DMSO/water at room temperature. Slightly different solvent system (DMSO/water/MeOH) afforded four crystalline coordination complexes of 3-pyIBU namely [{Cu(3-pyIBU)4(DMSO)2}(NO3)2] (CC1), [{Ag(3-pyIBU)2}(BF4)] (CC2), [{Ag(3-pyIBU)2}(ClO4)] (CC3) and [{Cu(3-pyIBU)4(CH3OH)2}(OTf)] (CC4) that were fully characterized by single crystal X-ray diffraction (SXRD). However, none of these coordination complexes produced metallogels - the results corroborated well with the rationale based on which the metallogelators were obtained. Two selected metallogels (MG3 and MG9) could be leached out from the corresponding metallogels to the bulk solvent to the extent of 51 and 59 %, respectively after 24 h of incubation at 37 0 C indicating their plausible use in topical application. Moreover, one of the selected metallogelators i.e. MG9 displayed anti-inflammatory response and was able to inhibit the migration of highly aggressive human breast cancer cells MDA-MB-231 suggesting its plausible use as anti-cancer agent.

This study examines the photocatalytic activity of titanium dioxide (TiO2) semiconductor supported on borosilicate tubes (cut-off 290 nm) towards removal of a mix of persistent organic pollutants (POPs) from water. For this purpose, two widely used analgesic and anti-inflammatory drugs (NSAIDs), ibuprofen (IBU) and mefenamic acid, along with MCPA sodium monohydrate, which is a common herbicide frequently used in the agricultural activities, were selected as a case study. Borosilicate tubes were coated with titanium oxide through two different approaches: sol-gel dip-coating and a hybrid nanoparticle dip-coating and plasma-enhanced chemical vapour deposition (PECVD) process. The photochemical reactor that hosts the titania-coated tubes was designed to permit continuous throughput of liquid feed stream. The photodegradation experiments were performed in laboratory conditions under artificial irradiation simulating solar light. The efficiency of direct photolysis and heterogeneous photocatalysis (TiO2) was investigated, and the performance of each coating method was evaluated. Kinetic studies for each experiment were accomplished, the overall results showed poor efficiency and insufficient removal for NSAIDs through direct photolysis, whereas applying heterogeneous photacatalysis with TiO2 coated on borosilicate tubes was found to accelerate their degradation rate with complete decomposition. Concomitantly, kinetic experimental results showed a critical difference of performance for the two coating methods used; in particular, the degradation rates of pollutants by the sol-gel-coated tubes were much faster than the degradation by the nanoparticle/PECVD-coated tubes. Using TiO2 supported on borosilicate tubes appears to be a promising alternative to conventional TiO2 suspension and avoid post-separation stages. The results achieved in this study can be used to optimise large-scale applications, and expanding the study to cover a wide range of pollutants will lead to achieve more representative results.

In order to obtain a non-toxic amphiphilic calixresorcinarene capable to form nanoconjugates for drug encapsulation, tetraundecylcalixresorcinarene functionalized by methoxy poly(ethylene glycol) chains has been synthesized. The macrocycle obtained is characterized by low hemotoxicity. In aqueous solution it forms nanoassociates that are able to encapsulate organic substrates of different hydrophobicity, including drugs (doxorubicin, naproxen, ibuprofen, quercetin). The micelles of the macrocycle slowed down the release of the hydrophilic substrates in vitro. In physiological sodium chloride solution and phosphate-buffered saline, the micelles of the macrocycle acquire thermoresponsive properties and exhibit a temperature-controlled release of doxorubicin in vitro. The combination of the low toxicity and the encapsulation properties of the obtained calixresorcinarene-mPEG conjugate shows promising potential for the use as a supramolecular drug-delivery system.

Fenton based reactions are effective for pharmaceutical removals, but traditional Fenton processes have drawbacks of pH adjustment and large amount of produced iron sludge. To overcome these challenges, a heterogeneous electro-Fenton process was proposed for effective contaminant degradation at circumneutral pH without iron sludge production. The anti-inflammatory drug ibuprofen (a common pharmaceutical in natural waters) was used as a representative contaminant. Activated carbon fibers (ACFs) supported ferric citrate (Cit-Fe/ACFs) was synthesized and used as the cathode, and RuO2/Ti was used as the anode. H2O2 was electro-generated in situ from O2 reduction and the production rate of OH per unit area was 6.8 μM W-1 cm-2 using Cit-Fe/ACFs cathode. A maximal ibuprofen degradation of 97% was obtained after 120 min at the current density of 7 mA cm-2. The electrical energy per order (EEO) varied from 0.24±0.03 to 2.65±0.04 kWh log-1 m-3 when the current density ranged from 1 to 7 mA cm-2. The Cit-Fe/ACFs cathode showed relatively good reusability and ∼85% IBP removal was achieved after 6 cycles of degradation. Our results showed that the prepared Cit-Fe/ACFs cathode was promising for the treatment of pharmaceutical contaminants.