The uncontrolled release of pharmaceutical drugs into the environment raised serious concerns in the last decades as they can potentially exert adverse effects on living organisms even at the low concentrations at which they are typically found. Among them, platinum based cytostatic drugs (Pt CDs) are among the most used drugs in cancer treatments which are administered via intravenous infusion and released partially intact or as transformation products. In this review, the studies on environmental occurrence, transformation, potential ecotoxicity, and possible treatment for the removal of platinum cytostatic compounds are revised. The analysis of the literature highlighted the generally low total platinum concentration values (from a few tens of ng L−1 to a few hundred μg L−1) found in hospital effluents. Additionally, several studies highlighted how hospitals are sources of a minor fraction of the total Pt CDs found in the environment due to the slow excretion rate which is longer than the usual treatment durations. Only some data about the impact of the exposure to low levels of Pt CDs on the health of flora and fauna are present in literature. In some cases, adverse effects have been shown to occur in living organisms, even at low concentrations. Further ecotoxicity data are needed to support or exclude their chronic effects on the ecosystem. Finally, fundamental understanding is required on the platinum drugs removal by MBR, AOPs, technologies, and adsorption.
Access to the enthalpy and entropy of the formation of metal complexes in solution is essential for understanding the factors determining their thermodynamic stability and speciation. As a case study, in this report we systematically examine the complexation of silver(I) in acetonitrile (AN) with the following monoamines: n-propylamine (n-pr), n-butylamine (n-but), hexylamine (hexyl), diethylamine (di-et), dipropylamine (di-pr), dibutylamine (di-but), triethylamine (tri-et) and tripropylamine (tri-pr). The study shows that the complex stabilities are quite independent of the length of the substitution chain on the N atom and demonstrates that, in general, the overall enthalpy terms associated with the complex formation are strongly exothermic, whereas the entropy values oppose the complex formations. In addition, we examined the similarity of the formation constants of AgL complexes of the primary monoamines in AN, dimethylsulfoxide (DMSO) and water, which were unexpected on the basis of the difference between the donor properties of solvents.
Two cationic enantiomeric complexes [(R,R)-[YbL]Cl and (S,S)-[YbL]Cl with L = N,N′-bis(2-pyridylmethyl)-1,2-(R,R or S,S)-cyclohexanediamine functionalized at sp3 N with picolinate antennae] have been synthesized and spectroscopically characterized in polar protic solvents, such as water and methanol. The Yb(III) luminescence at about 980 nm is efficiently sensitized upon excitation of the picolinate antenna in the UV spectral region around 330 nm. The complexes exhibit good CPL activity for the 2F5/2 → 2F7/2 magnetic dipole (MD) allowed transition (glum values of |0.02| and |0.04| at 984 nm and 1021 nm, respectively) and high solubility in aqueous solution. The YbL species is largely predominant at physiological pH (7.4), given its high thermodynamic stability (log βYbL = 20.98). As elucidated by DFT calculations, among the possible isomeric species the one characterized by the cis-O, O–N, N geometry was found to be dominant. Furthermore, one solvent molecule is bound to Ln(III) in water, giving rise to 9-fold coordination at the metal ion. The enantiomeric (R,R)-[YbL]Cl and (S,S)-[YbL]Cl complexes can be considered promising candidates as NIR-to-NIR chiroptical bioprobes also for in vivo experiments.
The room temperature ionic liquid trihexyl(tetradecyl)phosphonium decanoate ([P66614][Dec]) was employed in the liquid-liquid extraction of Co(II) from hydrochloric acid solutions in the presence of Ni(II). The extraction performance in liquid-liquid separations showed a strong dependence on the acid content of the feed aqueous solution. The best performance in terms of extracted cobalt and selectivity was obtained when the feed contained a HCl concentration above 6 M On the contrary, when the experiment was performed in absence of HCl, a lower extraction and Co/Ni selectivity were obtained. This behavior has been rationalized by considering the protonation of the [Dec]− anion and the different Co(II)/Ni(II) speciation in HCl media. Moreover, polymer inclusion membranes (PIMs) were prepared using PVC and [P66614][Dec] at different weight rations. Only the PIM formulated with a 30:70/PVC:[P66614][Dec] weight ratio demonstrated effective extraction of Co(II) from the HCl solution. The extraction efficiency and selectivity of the PIM was comparable to that from biphasic liquid experiments at 8 M HCl. The results of this study constitute a promising background for further practical developments of carboxylate-based ILs applied in Co/Ni separations.
A multi-analytical approach was used to comprehensively characterize the acid-base, thermal, and surface properties of agri-food processing wastes (i.e., original and pre-treated bergamot, grape and olive pomaces). These biomasses, often underutilised and inadequately studied in terms of their physicochemical properties, were investigated under varying ionic strength conditions at t = 25 °C. This investigation uniquely integrates multiple advanced techniques: Brunauer–Emmett–Teller porosimetry, Scanning Electron Microscopy, Thermogravimetric Analysis coupled with Fourier Transform Infrared Spectroscopy, Differential Scanning Calorimetry, Attenuated Total Reflectance Fourier-Transform Infrared, and potentiometry to provide a holistic understanding of these biomasses potential for environmental remediation. The modelling of ionic strength-dependent acid-base behaviour, established using an extended Debye–Hückel-type equation, revealed the dominant role of carboxylic groups as active sites across all pomace types, although with variations in abundances across the different samples. Additionally, morphological analysis highlighted the presence of irregularly shaped particles, heterogeneous size distributions, and distinct thermal stability trends, with grape pomace exhibiting the highest mass loss. These findings underscore the significant potential of these biomasses for the remediation of cationic pollutants from natural waters. Moreover, this comprehensive characterisation not only advances the understanding of agri-food waste valorisation but also provides a robust framework for designing targeted strategies in environmental applications.
Despite the globally increasing use of platinum-based cytostatic drugs in the treatment of several types of cancer, only limited attention has been paid to developing a treatment for contaminated liquid samples originating from hospitals, laboratories and manufacturing facilities before and after their administration. In this work, we assess the efficiency of a low-cost adsorbent material, a dithiocarbamate-functionalized silica, in removing cisplatin from a solution containing it in the 0.5–150 mg L−1 concentration range. The advantage of having a surface-functionalized silica is that adsorption can occur by either non-covalent interaction or surface complexation. In the latter case platinum(II) is de-complexed and the original drug is no longer present. Adsorption occurs through a first rapid step, followed by a second slower process. This is likely due to the fact that in our operating conditions (0.9% w/v NaCl), only the original compound is present, for which ligand substitution is known to proceed slowly. The interesting performance, even at low metal concentration, and facile synthesis of the material mean it could be adapted for other applications where the recycling of platinum can be realized.