Combinatorial drug delivery is a way of advanced cancer treatment that at present represents a challenge for researchers. Here, we report the efficient entrapment of two clinically used single-agent drugs, doxorubicin and sorafenib, against hepatocellular carcinoma. Biocompatible and biodegradable polymeric nanoparticles provide a promising approach for controlled drug release. In this study, doxorubicin and sorafenib with completely different chemical characteristics were simultaneously entrapped by the same polymeric carrier, namely poly(d,l-lactide-co-glycolide) (PLGA) and polyethylene glycol-poly(d,l-lactide-co-glycolide) (PEG-PLGA), respectively, using the double emulsion solvent evaporation method. The typical mean diameters of the nanopharmaceuticals were 142 and 177 nm, respectively. The PLGA and PEG-PLGA polymers encapsulated doxorubicin with efficiencies of 52% and 69%, respectively, while these values for sorafenib were 55% and 88%, respectively. Sustained drug delivery under biorelevant conditions was found for doxorubicin, while sorafenib was released quickly from the PLGA-doxorubicin-sorafenib and PEG-PLGA-doxorubicin-sorafenib nanotherapeutics.

Due to the growing concerns about pharmaceutical contamination and its devastating impact on the economy and the health of humans and the environment, developing efficient approaches for removing such contaminants has become essential. Adsorption is a cost-effective technique for removing pollutants. Thus, in this work, banana peels as agro-industrial waste were utilized for synthesizing activated carbon for removing pharmaceuticals, namely amoxicillin and carbamazepine from different water matrices. The chemically activated carbon by phosphoric acid (H₃PO₄) was carbonized at temperatures 350 °C, 450 °C and 550 °C. The material was characterized by several techniques such as scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS), Fourier transform infrared spectroscopy (FTIR), Boehm titration, point of zero charge (pH_PZC), BET surface area (S_BET), the proximate and ultimate analyses, X-ray powder diffraction (XRD), and thermos-gravimetric analysis (TGA). The SEM of banana peel activated carbon (BPAC) depicted a semi-regular and heterogeneous morphology, characterized by an abundance of pores with diverse forms and sizes. Boehm titration revealed an increase in the amounts of acidic groups by 0.711 mmol/g due to activation by H₃PO₄. FTIR recorded different peaks suggesting significant modifications in the spectroscopic characteristics of the BPAC surface due to the successful activation and adsorption of the pollutant molecules. The pHpzc of BPAC was calculated to be 5.005. The S_BET surface area dramatically increased to 911.59 m²/g after the activation. The optimum conditions were 25 °C, a materials dosage of 1.2 g/L, a saturation time of 120 min, a pollutants mixture of 25 mg/L, and a pH of 5. Langmuir exhibits a slightly better fit than Freundlich with a low value of the residual sum of squares (SSE) and the data were better fitted to the pseudo-second-order kinetic. Furthermore, the efficacy of BPAC in eliminating pharmaceuticals from Milli Q water, lake water, and wastewater was successfully investigated over the seven cycles. The results of the present work highlighted a potential usage of agro-industrial waste in eliminating organic micropollutants while exhibiting sustainable management of this waste.

This study examined the use of modified multiwall carbon nanotubes (M-MWCNTs) with immobilized laccase (L@M-MWCNTs) for removing ciprofloxacin (Cip), carbamazepine (Cbz), diclofenac (Dcf), benzo[a]pyrene (Bap), and anthracene (Ant) from different water samples. The synthesized materials were characterized using an array of advanced analytical techniques. The physical immobilization of laccase onto M-MWCNTs was confirmed through Scanning electron microscope (SEM)-dispersive X-ray spectroscopy (EDS) analysis and Brunner-Emmet-Teller (BET) surface area measurements. The specific surface area of M-MWCNTs decreased by 65% upon laccase immobilization. There was also an increase in nitrogen content seen by EDS analysis asserting successful immobilization. The results of Boehm titration and Fourier transform infrared (FTIR) exhibited an increase in acidic functional groups after laccase immobilization. L@M-MWCNTs storage for two months maintained 77.8%, 61.6%, and 57.6% of its initial activity for 4 °C, 25 °C, and 35 °C, respectively. In contrast, the free laccase exhibited 55.3%, 37.5%, and 23.5% of its initial activity at 4 °C, 25 °C, and 35 °C, respectively. MWCNTs improved storability and widened the working temperature range of laccase. The optimum removal conditions of studied pollutants were pH 5, 25 °C, and 1.6 g/L of M-MWCNTs. These parameters led to >90% removal of the targeted pollutants for four treatment cycles of both synthetic water and spiked lake water. L@M-MWCNTs demonstrated consistent removal of >90% for up to five cycles even with spiked wastewater. The adsorption was endothermic and followed Langmuir isotherm. Oxidation, dehydrogenation, hydroxylation, and ring cleavage seem to be the dominant degradation mechanisms.

The olive stone is a large waste product of the olive oil extraction industry. The present study investigates developing activated carbon from olive stone waste (OSAC) to remove pharmaceuticals from water. Different temperatures and olive stone: KOH ratios were studied. The OSAC produced at 750 °C and 1:3 ratio was found to have the highest porosity and surface area and was tested in the adsorption process. Diclofenac and ciprofloxacin were selected as model contaminants. The adsorption process was optimized with regards to OSAC dosage, pH, temperature, and initial concentration of adsorbate. The OSAC was found to be effective for a wide pH range (2-11) with an optimum dosage of 1 g/L at 25 °C. The pharmaceuticals were almost completely removed in 75 min. The adsorption was endothermic and followed first-order kinetics with physical mechanisms such as electrostatic possibly being the main driver. The optimum conditions were applied to test the removal of diclofenac and ciprofloxacin in synthetic water, lake water (Lake Balaton, Hungary) and secondary wastewater for seven cycles. There was little difference between the removal of the tested water matrices highlighting the potency of OSAC as an adsorbent for pharmaceutical removal in industrial applications. The removal dropped from >99% for the first cycle to 20-30% for the seventh cycle.

The ongoing discharge of containments into the environment has raised concerns about the potential harm they pose to various organisms. In the framework of eliminating pharmaceutical chemicals from aqueous solutions, enzymatic degradation by laccase is an environmentally friendly option. In this investigation, laccase immobilized on biochar derived from agricultural waste (orange peels, OPs) was used for the first time to remove carbamazepine and diclofenac from aqueous media. Different characterizations, such as Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM-EDS), X-Ray diffraction (XRD), specific surface area (S_BET), Boehm titration, proximate and ultimate analysis, as well as the point of zero-charge (pH_PZC) analysis, were used in this study. The immobilization of laccase results in enhanced stability with respect to storage, temperature, and pH compared to laccase in its free form. The findings showed that the ideal conditions for immobilization were a pH of 4, a temperature of 30 °C, and a laccase concentration of 4.5 mg/mL. These parameters led to an immobilization yield of 63.40%. The stability of laccase immobilized on biochar derived from orange peels (LMOPs) was assessed over a period of 60 days, during which they preserved 60.2% and 47.3% of their initial activities when stored at temperatures of 25 °C and 4 °C, respectively. In contrast, free laccase exhibited lower stability, with only 33.6% and 15.4% of their initial activities maintained under the same storage conditions. Finally, the use of immobilized laccase proved to be effective in eliminating these pollutants in up to five cycles. Upon comparing the two systems, namely LMOPs and modified orange peels (MOPs), it becomes apparent that LMOPs exhibit an estimated 20% improvement in removal efficiency. These results affirmed the viability of activated carbon derived from OPs as a cost-effective option for immobilizing laccase. This approach could potentially be further scaled up to effectively eliminate organic pollutants from water sources.

The industrial and environmental applications of laccase, especially in wastewater treatment, have gained focus in recent years. Therefore, developing the proper laccase immobilization techniques, which could improve the stability of the enzymes and simplify the required downstream processes, is needed. A novel two-step immobilization process was developed, resulting in cross-linked enzyme aggregates (CLEA) in the pores of the membrane. Laccase adsorption on a biodegradable cellulose acetate microfiltration membrane along with cross-linking was investigated to maximize the enzyme load and immobilization efficiency. The optimization was done regarding the: pH, temperature, enzyme concentration, adsorption time, cross-linker concentration, and temperature. It was concluded that the highest immobilization efficiency (76%) could be achieved in acidic buffers at 29 ${}^{°}$C with high surface activity (1174 U·m${}^{-2}$) at the cost of partial denaturation and membrane fouling. The membrane was successfully utilized for the enzymatic treatment of diclofenac, and 58% removal efficiency was achieved. The results indicated that cellulose acetate is a suitable carrier for adsorption-based immobilization of laccase for the potential for environmental utilisation.