Chemical Engineering Journal 472 (2023) 144894 Contents lists available at ScienceDirect Chemical Engineering Journal journal homepage: www.elsevier.com/locate/cej Trace cisplatin and carboplatin removal by 3-mercaptopropionic acid and L-cysteine functionalized sponges: Adsorption behaviour and mechanism Dong Han a, Montserrat López-Mesas a, *, Roberto Boada a, Tania Farías b, Ana R. Lazo Fraga b, Manuel Valiente a a GTS-UAB Research Group, Department of Chemistry, Faculty of Science, Universitat Autònoma de Barcelona, Bellaterra, (Cerdanyola del Vallès), 08193 Barcelona, Spain b Institute of Materials Science and Technology, University of Havana, 10400 Havana, Cuba A R T I C L E I N F O A B S T R A C T Keywords: This study presents functionalized open-celled cellulose Metalzorb® sponge (Sponge) with 3-mercaptopropionic Adsorption acid (MPA) and L-Cysteine (Cys), and the resulting MPA@Sponge and Cys@Sponge showed significantly Cisplatin improved removal efficiency towards trace cisplatin and carboplatin against Sponge. MPA@Sponge achieved Carboplatin maximum removal of 88.9 ± 0.5% for cisplatin and 85.2 ± 0.4% for carboplatin, while Cys@Sponge achieved Pt-based cytostatics maximum removal of 75 ± 2% and 59 ± 1%. In contrast, Sponge only achieved removal of 29 ± 4% and 4 ± 1%, Thiol-functionalization XAS respectively. It suggests that thiol groups serve as favourable binding sites for Pt complexation. Carboplatin exhibits lower adsorption compared to cisplatin due to its limited hydration. However, the presence of Cl− in stock and high temperature facilitate the hydration and the formation of active derivatives of carboplatin, thereby enhancing its adsorption. The rapid adsorption processes of cisplatin and carboplatin are well described by the pseudo-second-order kinetic model involving diffusion and chemisorption. The results from adsorption isotherms revealed a monolayer adsorption that aligns with the principles proposed by the Langmuir model. High temperature significantly enhances the adsorption, and the positive enthalpies indicate that the binding of Pt with thiol groups is endothermic process. X-ray absorption spectroscopy measurements at the Pt L3-edge revealed a similar coordination environment of the adsorbed Pt on both functionalized adsorbents, which can be attrib­ uted to the formation of four Pt-S bonds during the adsorption. To assess the validity of the adsorption results under realistic medium conditions, an adsorption study was carried out by using diluted urine spiked with trace platinum cytostatic drugs to simulate hospital wastewater. 90.2 ± 0.3% of cisplatin and 77.0 ± 0.2% of car­ boplatin was effectively removed by MPA@Sponge from diluted urine. 1. Introduction domestic wastewaters (the latter contaminated by ambulatory patients), as has been proved by many researchers over the last two decades, with Cisplatin and carboplatin, well-known platinum cytostatic drugs (Pt- concentrations varying between ng‧L− 1 to 250 μg‧L− 1 [5]. Furthermore, CDs), are widely utilized in cancer therapy and characterized for pos­ several investigations have verified the harmful impacts of cisplatin and sessing genotoxicity, mutagenicity, carcinogenicity, and teratogenicity carboplatin on certain aquatic invertebrates, even at low levels, in both as they attack not only cancer cells but also healthy cells [1]. The freshwater and marine ecosystems [6–12]. Limited efforts have been presence of these substances in aquatic environments has been identified taken to investigate the viability of efficient wastewater remediation as a significant hazard to both humans and aquatic organisms that are methods for Pt-CDs, utilizing diverse techniques such as adsorption exposed to them, thereby posing a serious threat [2,3]. Pharmacokinetic [13–17], membrane separation [18,19], ozonation [20] and electrolysis investigations provide substantiation that approximately 10–40% of Pt- [21,22]. Among them, adsorption, a well-established technology, is CDs administered to patients are excreted via urine, either in their frequently considered a favorable approach due to its inherent original form or as metabolites [4]. These compounds are ultimately simplicity of operation, low cost, easy scalability, and significant treat­ released into the environment through the discharge of hospital or ment efficiency. In fact, some pioneering studies on the adsorption of Pt- * Corresponding author. E-mail address: montserrat.lopez.mesas@uab.cat (M. López-Mesas). https://doi.org/10.1016/j.cej.2023.144894 Received 9 June 2023; Received in revised form 14 July 2023; Accepted 16 July 2023 Available online 17 July 2023 1385-8947/© 2023 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by- nc-nd/4.0/). D. Han et al. Chemical Engineering Journal 472 (2023) 144894 CDs using various materials have already been conducted. As early as 2. Materials and methods 2005, Lenz et al., evaluated the adsorption of three cancerostatic plat­ inum compounds (concentrations ranging from 4.7 to 145 μg‧L− 1) by 2.1. Reagents and materials activated sludge, and after 24 h of incubation time, the removal rates reached 96%, 70% and 74% for cisplatin, carboplatin and oxaliplatin Cisplatin (99%, CAS: 15663–27–1) and carboplatin (99%, CAS: respectively [15]. Ogata et al., prepared calcined gibbsite for the 41575–94–4) were acquired from STREM Chemicals. The compounds adsorption of cisplatin (initial concentration of 10 mg‧L− 1) and achieved were utilized in their as-received form without undergoing any further a removal efficiency of about 90% [14]. Biomass-derived materials such purification. Stock solutions of cisplatin and carboplatin (Pt 100 mg‧ as activated carbon, biochar, chitosan, and wood ash were proposed for L− 1), were firstly prepared in 0.2 mol‧L− 1 HCl and Milli-Q water adsorption of inorganic PtCl2-6 as a model of Pt-CDs (initial concentration respectively and were subsequently diluted to the required concentra­ of Pt within the range of 1 to 10 mg‧L− 1), with adsorption capacities tion. MetalZorb® Sponge (Sponge) was generously provided by Clean­ ranging from 0.23 to 0.97 mg‧g− 1 of Pt at an adsorbent dose of 10 g‧L− 1 Way Environmental Partners, Inc. (Portland, USA). Acetic anhydride [16]. Cryogels were synthesized to adsorb cisplatin (250 to 2000 mg‧ (Ac2O, ≥ 99%), 3-mercaptopropionic acid (MPA, ≥ 99%) and L-Cysteine L− 1), and the maximum adsorption capacity was discovered to be 150 (Cys, 97%) were acquired from Sigma-Aldrich. Throughout the experi­ mg‧g− 1, attributed to the formation of a stable complex between Pt and mental procedure, Milli-Q water with a resistivity of 18.2 MΩ‧m− 1 was the carboxyl group on methacrylic acid [13], where similar strategies utilized, unless explicitly stated otherwise. were previously used to synthesize carriers for cisplatin drug delivery [23,24]. Recently, a study proposed ion-imprinted mesoporous orga­ 2.2. Preparation of thiol-functionalized sponges nosilica for adsorption of PtCl2- 4 as a model of Pt-CDs and a maximum adsorption capacity of 76.4 mg‧g− 1 was attained [17]. Another recent The original Sponge utilized in this study has a cube-shaped structure study reported the synthesis of dithiocarbamate-modified silica for the composed of an open-celled cellulose substrate. The dimensions of the removal of cisplatin at varying concentrations (ranging from 5 to 150 cubes were measured to be 13 ± 2 (L) × 10 ± 1 (W) × 7 ± 1 (H) mm on mg‧L− 1 Pt in NaCl 0.9% w/v). The maximum adsorption capacity of the average, with an average weight of 0.20 ± 0.02 g per cube. In order to adsorbent was determined to be 15.6 mg‧g− 1, and removal efficiency of minimize the usage of expensive and toxic Pt-CDs in the adsorption up to 85% was observed at a dose of 10 g‧L− 1 of adsorbent and contact experiments, sponges were employed in powdered form to reduce scale. time of 1 h [25]. The cubes underwent mechanical grinding in a commercial blender Upon reviewing the aforementioned studies, it becomes evident that using knife milling, followed by sieving to achieve the desired particle the majority of the adsorption experiments predominantly occurred size of ≤ 0.5 mm. The resulting fine sponge powders were washed once within the mg‧L− 1 concentration range. The establishment of adsorption with 1.0 mol‧L− 1 HCl and three times with Milli-Q water. After the systems and the elucidation of adsorption mechanisms were based on washing process, the Sponge powders were dried at 353 K for a duration concentrations that surpassed those observed in actual environmental of 24 h and subsequently stored for further use. As illustrated in Fig. 1, scenarios. However, the performance assessment of these approaches in the process of thiol-functionalization of Sponge was carried out through the actual treatment of low-concentration Pt-CDs remains unclear. In esterification, utilizing a modified version of the procedure described in view of the trace concentration (less than 1 mg‧L− 1) of Pt-CDs, a notable previous studies [32–35]. In a glass tube with screw cap, 10 mL of MPA challenge exists in establishing an efficient and rapid adsorption system, (114.8 mmol) or 2.5 g of Cys (20.6 mmol) was mixed with 10 mL of Ac2O owing to the limited concentration gradient at the interface between the and 50 μL of concentrated sulfuric acid. Ac2O serves as a reaction me­ liquid and solid phases. Hence, further research efforts ought to be dium, simultaneously consuming the water generated during the ester­ directed towards developing adsorbents that exhibit high selectivity and ification reaction. When cooled to room temperature, 0.5 g of sponge strong affinity. To attain this goal, exploring and interpreting the powder was added, and the mixture was stirred in an oven at 338 K for 4 adsorption mechanism assumes critical significance. Additionally, it is days. The two products generated, namely MPA@Sponge and imperative to consider the economic and operational convenience as­ Cys@Sponge, were subjected to sequential washing with acetone, pects, to strike a balance between efficiency and cost-effectiveness. alcohol, and Milli-Q water, and subsequently dried at 353 K overnight. In our previous study, we conducted a comparative analysis of three commercially available materials, namely 3-(diethylenetriamino)pro­ 2.3. Characterization of sponges pyl-functionalized silica gel, cysteine-functionalized silica gel, and open- celled cellulose MetalZorb® sponge (Sponge), for their adsorption ca­ To obtain the Fourier Transform Infrared Spectroscopy (FTIR) pabilities towards trace amounts of cisplatin and carboplatin [26]. Our spectra and identify the functional groups present in Sponge, MPA@S­ results suggest that the presence of thiol groups as affinity sites offered ponge, and Cys@Sponge; FTIR equipped with Attenuated Total Reflec­ the potential for complexation of the target Pt species [26]. Moreover, tance (ATR) module (ATR-FTIR, Tensor 27, Bruker, Germany) was following intravenous administration of Pt-CDs, investigations have utilized. The quantification of sulfur content was performed utilizing an demonstrated their interaction with diverse constituents of the blood, element analyzer (Flash EA 2000 CHNS, Thermo Fisher, America). The like human serum albumin (HSA). HSA, being the predominant protein point of zero charge (pHpzc) of sponges were measured using pH drift in human blood, comprises cysteine residues that can interact with method [36]. Specifically, pHpzc was determined using 0.1 mol‧L− 1 NaCl administered Pt complexes [27–30]. In addition, according to Hard-Soft solutions spanning pH 2–9. pH adjustments were achieved using either Acid-Base (HSAB) theory [31], Pt(II) as a “soft” acid has a high affinity 0.1 mol‧L− 1 HCl or 0.1 mol‧L− 1 NaOH solutions. A total of 20 mL of each for sulfur donors (“soft” bases) e.g. thiols and thioethers. Inspired by solution was brought into contact with 0.1 g of the sample, followed by these findings, the current study sought to improve the adsorption 24 h of stirring. Subsequently, the sponge was separated via filtration, properties of cheap and commercially available Sponge through func­ and the pH of the filtrate was measured. The pHpzc value was obtained tionalization with thiol-containing compounds, as 3-mercaptopropionic by plotting the initial pH of solution against the difference in pH values. acid (MPA) and L-Cysteine (Cys). The resulting materials, namely The morphological analysis of the sponges was performed using a Field MPA@Sponge and Cys@Sponge, respectively, were then evaluated for Emission-Scanning Electron Microscope (FE-SEM, MERLIN, Zeiss) with their capacity to remove trace cisplatin and carboplatin from aqueous a resolution of 1.4 nm at 1 kV. The probe current ranges from 4 pA to solutions, and compared to raw Sponge. Moreover, the adsorption 100 nA, while the accelerating voltage varies from 0.2 to 30 kV. The mechanisms have been explained by the results obtained from syn­ specific surface areas of sponges were determined using N2 adsorp­ chrotron X-ray absorption spectroscopy (XAS) technique. tion–desorption experiments conducted on a Micromeritics ASAP 2460 analyzer at a temperature of 77 K. All sponges were degassed 12 h under 2 D. Han et al. Chemical Engineering Journal 472 (2023) 144894 Fig. 1. Schematic illustration of the preparation procedure for MPA@Sponge and Cys@Sponge. a vacuum at 423 K before the measurement. The specific surface area average along with the corresponding relative standard deviations were was calculated utilizing the Brunauer-Emmett-Teller (BET) method. computed. To fully comprehend the adsorption behaviour of Pt-CDs, fitting 2.4. Batch adsorption Pt-CDs analysis was conducted on the adsorption data collected at different contact time using pseudo-first-order (PFO) and pseudo-second-order The adsorption behavior of cisplatin and carboplatin was investi­ (PSO) kinetic models. Additionally, isotherm models such as Langmuir gated under different experimental conditions, including pH (ranging and Freundlich were employed to fit the data derived from diverse initial from 2 to 6), contact time (from 1 min to 24 h), initial concentration concentrations. All chosen model formulations are described in Sup­ (varying from 47 μg‧L− 1 to 500 mg‧L− 1, expressed as Pt for both Pt-CDs), plementary data. and solution temperature (293, 318, and 343 K). The pH of the solution was controlled by using 0.1 mol‧L− 1 NaOH and/or 0.1 mol‧L− 1 HCl to 2.5. Synchrotron X-ray absorption spectroscopy (XAS) achieve the desired pH, which was monitored using a pH meter (Crison, Spain) prior to, during, and after the adsorption. Batch adsorption ex­ X-ray absorption spectroscopy (XAS) experiment was carried out at periments were conducted by adding 10 mg of the adsorbent to 2 mL of BL22 CLÆSS beamline of ALBA CELLS synchrotron [37]. Pt L3-edge XAS Pt solution (either cisplatin or carboplatin) in a plastic centrifuge tube. measurements were conducted to investigate the chemical state and The mixture was subjected to mechanical agitation at 300 rpm at a coordination environment of adsorbed cisplatin and carboplatin. The specific temperature. Following a predetermined duration, typically 24 measurements were collected on adsorbents that had been exposed to an h (except in the case of kinetic studies), the adsorbent was separated initial concentration of 235 μg‧L− 1 Pt. Samples were pressed into a 13 from the solution by a 0.22 μm membrane filter. The remaining Pt mm pellet to facilitate handling. A Si(3 1 1) double crystal mono­ concentration of the filtrate was quantified by means of Inductively chromator was employed for the measurements. The measurements Coupled Plasma Mass Spectrometry (ICP-MS, Thermo XSeries II, Thermo were performed at a temperature of liquid nitrogen to mitigate potential Scientific, USA). radiation-induced damage. Given the relatively low Pt concentration in The equilibrium adsorption capacity qe (μg‧g− 1) of Pt was determined the samples, the measurements were conducted in fluorescence mode by applying Eq. (1): utilizing a multi-element silicon drift detector equipped with Xspress3 (c0 − ce ) electronics. qe = ×V (1) Solid Pt references (K2PtCl4, cisplatin, carboplatin) were measured in m transmission mode at room temperature, and their solutions in different where c0 and ce represent the initial and equilibrium Pt concentrations mediums (cisplatin in 0.2 mol‧L− 1 HCl, carboplatin in 0.2 mol‧L− 1 HCl (μg‧L− 1), respectively, V indicates the volume of solution (mL), and m and Milli-Q water, Pt concentration of 100 mg‧L− 1) were loaded into the denotes the adsorbent dosage (mg). In the case of kinetic studies, ce is in-house designed 3D-printed liquid cell [38] and then collected in substituted by the remaining Pt concentration at time t, ct (μg‧L− 1), to fluorescence mode at room temperature. calculate the corresponding adsorption capacity (qt, μg‧g− 1). The X-ray absorption near edge structure (XANES) data were sub­ Subsequently, the removal ratios were determined by Eq. (2): jected to normalization and background subtraction procedures utilizing the Athena software, while the extended X-ray Absorption fine structure (c0 − ce ) Removal ratio = × 100% (2) (EXAFS) data were processed through the Artemis software [39]. The c0 pseudoradial distribution functions presented as the module of the All adsorption experiments were performed in triplicate, and the Fourier transform of the EXAFS signal are not phase-shift corrected. 3 D. Han et al. Chemical Engineering Journal 472 (2023) 144894 2.6. Removal of Pt-CDs from urine and diluted urine the Table S6 in Supplementary data. Subsequently, 10 mg of the chosen adsorbent was added to 2 mL of The study intended to assess the feasibility and effectiveness of thiol the Pt-spiked urine samples, and the mixture was continuously stirred functionalized sponge in eliminating cisplatin and carboplatin from for 24 h at 343 K. The resultant samples were then filtered via 0.22 μm urine. Experiments were conducted using spiked urine samples obtained filters before being collected using sterile plastic bottles. The Pt con­ from a healthy male, as collecting urine samples from patients under­ centration of the samples was subsequently determined using a stan­ going Pt cytostatic treatment proved challenging. The spiked samples dardized analytical technique that has been detailed in previous used in the study consisted of cisplatin, carboplatin, and their mixtures. literature [40,41]. In detail, a 100 μL sample was subjected to equili­ Each sample had an initial total Pt concentration of 235 μg‧L− 1, which bration at room temperature and then was digested with 200 μL of HNO3 closely resembled the concentrations typically found in hospital waste­ (69.0–70.0%, for trace metal analysis), at a temperature of 363 K for 1 h. waters. Additionally, to assess the matrix effect and simulate possible The resultant digested samples were then diluted to a final concentration dilution in hospital wastewater, the same procedure was applied to urine of 2% v/v HNO3 by diluting to 10 mL with Milli-Q water. The concen­ samples diluted ten-time and 100-time using tap water. Ion chroma­ tration of Pt was immediately determined by ICP-MS, with external tography (Dionex Aquion, Thermo Scientific, America) was chosen as calibration over a concentration range of 1 to 150 μg‧L− 1. Indium (In) the analytical technique for quantifying the levels of commonly occur­ and Rhodium (Rh) were employed as internal standard elements. Then ring cations and anions in urine samples as well as two synthetic ana­ the removal ratio was determined by Eq. (2). logues of hospital wastewater, and further information can be found in pH Fig. 2. (a) FTIR spectra of Sponge, cellulose, MPA, Cys, MPA@Sponge, and Cys@Sponge; (b) pHpzc determination of Sponge, MPA@Sponge, and Cys@Sponge by pH drift method; SEM images of (c) Sponge, (d) MPA@Sponge, and (e) Cys@Sponge. 4 D. Han et al. Chemical Engineering Journal 472 (2023) 144894 3. Results and discussion determined to be 1.55, 1.66, and 1.65 m2‧g− 1, respectively. 3.1. Characterization of sponges 3.2. Adsorption of Pt-CDs Fig. 2a presents the spectra resulting from the FTIR analysis of 3.2.1. Effect of pH values Sponge, cellulose, MPA, Cys, MPA@Sponge and Cys@Sponge. Relevant The pH value is a crucial parameter governing the interaction be­ patents and studies [42–47] suggest that the porous cellulose sponge is tween adsorbate and adsorbent. Through protonation or deprotonation composed of a thermally induced amide-forming, insoluble, water- processes, it can induce changes in surface charge, thereby affecting the swellable polymer, polyethyleneimine, physically bound to the sponge adsorption efficiency. Additionally, in the case of Pt-CDs, the pH also (see in Fig. S1). This polymer product is claimed to exhibit high affinity impacts the hydration of Pt complexes. for the adsorption of transition metal ions [42–47]. Regarding Sponge, Upon comparing the adsorption capacity of the sponge before and compared to pure cellulose, the FTIR analysis revealed absorbances at after functionalization shown in Fig. 3, it becomes apparent that the 3435, 2891, 1365, 1157, and 1024 cm− 1, which can be attributed to the adsorption of the two Pt-CDs was enhanced when MPA and Cys were cellulose substrate [48]. The notable absorption band observed at a introduced. According to HSAB theory [31], Pt (II) exhibits character­ wavenumber of 3435 cm− 1 can be ascribed to the stretching vibration of istics of a “soft” acid, displaying a pronounced propensity for forming the O-H bond. This band is broader in Sponge than in cellulose, which is stable complexes with sulfur donors, which are classified as “soft” bases. attributed to the overlap of the band corresponding to N-H stretching Notably, the improvement observed in the case of MPA@Sponge is vibrations. This feature is ascribed to the polyethyleneimine on the markedly superior to that observed in the case of Cys@Sponge. This is surface of the Sponge. Alkanes C-H bond stretching vibration is because MPA@Sponge has a higher sulfur loading rate than responsible for the peak with a center value of 2891 cm− 1. The ab­ Cys@Sponge, as shown by EA (1.23 ± 0.07 and 0.59 ± 0.03 wt% of sorption band observed at a wavenumber of 1365 cm− 1 is assigned to the sulfur content in MPA@Sponge and Cys@Sponge, respectively), bending of the O-H bond, whereas the peak observed at 1157 cm− 1 providing more adsorption sites. Moreover, it has been proposed that the corresponds to the antisymmetric stretching of the C-O-C bridge. The three sponge materials demonstrated superior capabilities in the prominent peak recorded at a wavenumber of 1024 cm− 1 arises due to adsorption of cisplatin compared to carboplatin. This distinction can be the skeletal vibration of the C-O-C pyranose ring [48]. Moreover, the attributed to the inherent tendency of cisplatin to undergo hydration. absorption spectrum of Sponge exhibits an additional peak at 1637 The dissimilarity arises from the differences between the chloride li­ cm− 1, in contrast to cellulose, and can be assigned to the stretching vi­ gands of cisplatin and the bidentate chelated ligand 1,1-cyclobutanedi­ bration of the C = O bond. Additionally, the peak experiences a shift carboxylato (CBDCA) of carboplatin. Specifically, the chloride ligands of towards higher wavenumbers (due to the electron-donating character­ cisplatin are more prone to hydration, while the CBDCA ligand of car­ istics of nitrogen), indicating the presence of an amide structure in the boplatin exhibits lesser susceptibility to hydration [58–63]. Conse­ polymer formed through the reaction between nitrilotriacetic acid and quently, the hydration-resistant nature of carboplatin impedes the polyethyleneimine. substitution by the thiol group, leading to the observed disadvantage in Both functionalization reagents exhibit a modest absorption peak of adsorption capacity. around 2550 cm− 1, which is associated with the S-H bond stretching The impact of pH on the adsorption of cisplatin onto the three vibration. In addition, MPA also exhibits an absorption peak at 1701 sponges is evident from the findings illustrated in Fig. 3a. As the pH cm− 1, which is due to the stretching vibration of the C = O bond in the value rises, a slight increase in cisplatin adsorption can be observed. This carboxyl group [49]. In contrast, the spectrum of Cys exhibits two observation can be attributed to the favourable influence of high pH distinct peaks at 1576 and 1391 cm− 1, which are attributed to the levels and low Cl− concentration on the hydration of cisplatin, thereby asymmetric and symmetric stretching vibrations of carboxyl (–COO-) enhancing its reactivity and facilitating complexation with the sponges groups, respectively [50–53]. The limited loading of the functionalized [28,64–68]. The impact of pH variation on carboplatin adsorption is sponges resulted in the almost negligible presence of the characteristic negligible (see Fig. 3b), except for pH 2, wherein MPA@Sponge exhibits peaks of thiols at 2550 cm− 1. However, the detection of a new peak at a higher adsorption capacity compared to the values obtained at other 1730 cm− 1 in MPA@Sponge and Cys@Sponge spectra, which is attrib­ pH values. The observed phenomenon is attributed to the introduction uted to the C = O stretching vibration of the ester group, serves as ev­ of additional HCl at a pH of 2, resulting in partial displacement of idence for successful esterification. Stated differently, the anchoring of CBDCA ligand on carboplatin, and rendering its molecular conformation MPA and Cys on the substrate was accomplished successfully. And, more similar to that of cisplatin, and this transformation has been similar FTIR spectral characteristics were also presented in different already detected by chromatography [61] and XAS techniques [69]. studies on thiol-functionalized cellulose materials [34,35,54–56]. As listed in Table S1, elemental analysis (EA) measurements showed 3.2.2. Adsorption kinetics that 1.23 ± 0.07 and 0.59 ± 0.03 wt% of sulfur were present in The kinetic parameter plays a pivotal role in assessing the efficiency MPA@Sponge and Cys@Sponge after functionalization, respectively. and mechanism of adsorption processes, which is a critical aspect to These results also validate the successful anchoring of MPA and Cys on consider when scaling up Pt-CDs removal for industrial applications. The the substrate, as the sulfur content in the original sponge is negligible. adsorption kinetic curves for cisplatin and carboplatin onto Sponge, The lower sulfur content observed in Cys@Sponge after functionaliza­ MPA@Sponge, and Cys@Sponge are presented in Fig. 4. The results tion is attributed to the necessity of employing less Cys compared to demonstrate rapid adsorption kinetics for all materials. During the MPA, due to the low solubility of Cys in Ac2O medium. According to initial few minutes, there is a notable rise in adsorption capacity as a Fig. 2b, the pHpzc values of Sponge, MPA@Sponge, and Cys@Sponge are result of the ample presence of active adsorption sites on the surfaces of approximately 3.2, 2.1, and 3.1, respectively. Therefore, when the so­ sponges. However, as the adsorption proceeds, the growth rate pro­ lution pH is lower than these values, the surface of the sponges will gressively decelerates until it reaches equilibrium after approximately 3 become positively charged, primarily due to the protonation of amino h. This is primarily due to the decrease in available active sites, resulting groups [57]. As depicted in Fig. 2c-e, all sponges demonstrate a porous in a reduction in the rate of adsorption. Despite its fast kinetics, the structure featuring an intricate network of interconnected channels with adsorption of carboplatin exhibits certain limitations when compared to diameters ranging approximately from 1 to 5 μm. Furthermore, after that of cisplatin. As depicted in Fig. 4, the adsorption capacities (at 24 h) modification, these pore characteristics are retained. The N2 adsorp­ of MPA@Sponge and Cys@Sponge for carboplatin were merely 6.3 ± tion–desorption isotherms are illustrated in Fig. S2, and the BET specific 0.8 and 5.7 ± 0.1 μg‧g− 1, respectively, compared to 29.8 ± 0.1 and 21.4 surface areas of Sponge, MPA@Sponge, and Cys@Sponge were ± 0.3 μg‧g− 1 for cisplatin. Similar behavior was also observed in the 5 D. Han et al. Chemical Engineering Journal 472 (2023) 144894 qe Fig. 3. pH effect on adsorption capacities of sponges on (a) cisplatin and (b) carboplatin. Fig. 4. Adsorption capacities of (a) MPA@Sponge, (b) Cys@Sponge, and (c) Sponge on cisplatin and carboplatin at different contact time. adsorption on Sponge (Fig. 4c). As previously explained, this can be column of Fig. 5, a slight increase in the adsorption capacity of carbo­ attributed to the low hydration rate of carboplatin. platin was observed as the temperature was elevated from 293 K to 318 It can be concluded that the PSO model was more suitable for fitting K. However, an appreciable enhancement in the adsorption capacity was the data than the PFO model based on the coefficients of determination noted upon further raising the temperature to 343 K, particularly within R2 shown in Table S2 (see Supplementary data). The PSO model pos­ the lower concentration regime, as depicted in Fig. 5d and h. As shown tulates that the rate-limiting step entails chemisorption, involving in another study [76], comparable distinctions were also noted during valence forces that result from the electrons sharing or exchanging be­ an investigation of the impact of temperature on the interplay between tween the adsorbent and adsorbate [36,70,71]. On the other hand, the cisplatin and carboplatin with cellular DNA [76]. It can be explained PFO model is suitable for characterizing the early phase of adsorption, that the influence of temperature on the adsorption of carboplatin is not wherein the rate-controlling step is external/internal diffusion, and the only reflected in the promotion of complexation of Pt-S, but it also has a adsorbate typically exhibits a high initial concentration [70,72]. On the notable effect on the hydration of carboplatin [77], which is crucial to contrary, the present study involved a low initial concentration (235 μg‧ the complexation process that follows. It can be inferred that when the L− 1) of the target Pt-CDs and an abundance of active sites in the ad­ temperature rose to 318 K, the bidentate-chelated CBDCA of carbopla­ sorbents. This scenario signifies that the adsorption is primarily gov­ tin, hindered the subsequent ligand replacement conferring carboplatin erned by the bonding process of the adsorbate to the active sites, thus resistance to hydration. However, at 343 K, the CBDCA ring was opened aligning with assumptions of the PSO model. and hydrated [77], resulting in derivatives with greater activity. Consequently, the adsorption of carboplatin was significantly enhanced, 3.2.3. Adsorption isotherms to a degree comparable to that of cisplatin (as evidenced by the com­ Adsorption isotherm characterizes the equilibrium relationship be­ parison displayed in Fig. 5c and d at 343 K). tween the adsorbate present in the liquid phase and the adsorbate Fig. 5 also depicts the fitting curves for the adsorption processes, adsorbed on solid adsorbent at constant temperature [73]. Fig. 5 illus­ while Table S3 (Supplementary data) summarizes the parameters trates an increase in adsorption capacity as the initial concentration derived from the isotherm models used. By comparison, the coefficient increases. This phenomenon can be accounted for by the presence of a of determination for the Langmuir model (R2 > 0.96) typically surpasses higher concentration gradient occurring at the interface between the that of the Freundlich model, thereby suggesting a superior fit of the solid and liquid phases, which drives the mass transfer of Pt-CDs towards Langmuir isotherm model to the experimental data, except for adsorp­ the adsorbent surface, which satisfies the generalized Fick Law [74,75]. tion of cisplatin on MPA@Sponge at 318 K, where the Freundlich model By comparing the adsorption isotherms at varying temperatures, a shows slightly better fitting. These findings suggest that the adsorption discernible increase in adsorption can be observed with rising temper­ of two Pt-CDs by MPA@Sponge and Cys@Sponge occurs via monolayer ature. Nevertheless, distinct patterns can be observed in the impact of adsorption. Furthermore, in the low concentration range (Fig. 5c, d, g temperature on the adsorption processes of cisplatin and carboplatin. It and h), the adsorption isotherms exhibit linear characteristics, consis­ has been observed that the adsorption of cisplatin proportionally in­ tent with the description of Henry’s law, thereby indicating a monolayer creases with the temperature rise (left column in Fig. 5). The observed adsorption as well [78]. The Langmuir separation factor RL values for phenomenon is ascribed to the temperature-favoured complexation of both Pt-CDs adsorptions on the two materials, within the concentration the center Pt of cisplatin with thiol groups present on the surfaces of the range investigated, range from 0 to 1, demonstrating favourable MPA@Sponge and Cys@Sponge, and the same explanation also applies adsorption. The theoretical maximum adsorption capacities (qm) esti­ to the adsorption of carboplatin. In contrast, as illustrated in the right mated by the Langmuir model closely approximates, albeit slightly 6 D. Han et al. Chemical Engineering Journal 472 (2023) 144894 Fig. 5. Adsorption equilibriums of (a) cisplatin on MPA@Sponge, (b) carboplatin on MPA@Sponge, (e) cisplatin on Cys@Sponge and (f) carboplatin on Cys@Sponge and isotherm models fitting. Fig. (c), (d), (g) and (h) below each depict the magnified interval (with an initial concentration range of 47–14100 μg‧L− 1). exceeds, the experimentally obtained actual maximum adsorption ca­ chemisorption processes of Pt-CDs on MPA@Sponge and Cys@Sponge pacities. The favourable nature of all adsorption processes is indicated were primarily governed by chelation, which exhibited a thermophilic by the Freundlich constant, as the value of 1/n is less than 1. nature. Thus, it was observed that high temperatures promoted the complexation reaction between Pt and S originating from the thiol 3.2.4. Adsorption thermodynamics group. However, the adsorption capacities of Pt-CDs on Sponge were To further understand adsorption characteristics, experimental only found to increase with an increase in temperature from 293 K to thermodynamic studies were carried out at various temperatures. The 318 K. This limited increase was attributed to the promotion of impact of temperature on the adsorption efficacy of unfunctionalized complexation between Pt and the amine groups on Sponge surface at and functionalized sponges is divergent. The experimental findings 318 K. However, it is worth noting that the complexation was limited presented in Fig. 6 show that the thiol-modified sponges display a d due to the inherent “hard” basic character of N and its relatively lower temperature-favoured behaviour. Conversely, the original sponge ex­ bonding affinity with the “soft” acid Pt, as compared to S [31,79,80]. hibits an adsorption trend that initially increases with temperature, but The adverse effects of reduced van der Waals adsorption become more subsequently decreases. It can be readily comprehended that the pronounced when the temperature is further elevated to 343 K, resulting 7 D. Han et al. Chemical Engineering Journal 472 (2023) 144894 1 Fig. 6. Effect of temperature on the adsorption capacity of cisplatin and carboplatin. Initial Pt concentration of cisplatin: (a) 235 μg‧L− and (c) 470 μg‧L− 1; of carboplatin: (b) 235 μg‧L− 1 and (d) 470 μg‧L− 1. in a decline in adsorption capacity. [81]. Moreover, upon comparing the solid and solution phases during the adsorption process of Pt-CDs onto adsorption of cisplatin and carboplatin on functionalized sponges, it is MPA@Sponge and Cys@Sponge. The process of binding Pt-CDs onto a noteworthy that the role of temperature in enhancing the process sponge surface should be associated with a decrease in entropy due to manifests itself in distinct manners. Specifically, while the adsorption of the restriction on their conformational space, which consequently cisplatin exhibits a gradual increase with each increment in tempera­ resulted in a negative contribution to the ΔS◦ . However, the restricted ture, the adsorption of carboplatin experiences a substantial surge only degree of freedom of Pt-CDs in solution implies that their entropy when the temperature surpasses the threshold of 318 K. This observation change upon adsorption is comparatively low when compared to that of suggests that the impact of temperature on carboplatin extends beyond water. Evidently, the positive contribution to ΔS◦ is a result of water the complexation reaction to other associated processes. For instance, molecules being excluded from the hydration layers of both the sponges the promotion of hydration due to an increase in temperature, as pre­ and Pt-CDs upon adsorption. The exchange of molecules between the Pt- viously described, facilitates the pre-morphological transformation of CDs and functional groups on the sponge surface facilitates the libera­ carboplatin. tion of water molecules, resulting in an increase in disorderliness at the Furthermore, the determination of three fundamental thermody­ solid/fluid interface [83]. Similar results were also found in other namic parameters, namely ΔG◦ (Gibbs free energy), ΔH◦ (enthalpy studies using cellulose [87] or lignocellulosic waste [88] as adsorbents. change), and ΔS◦ (entropy change), was carried out using the equations detailed in the Supplementary data. The values of ΔG◦ presented in Table S4 indicate that the adsorption 3.3. X-ray absorption spectroscopy of adsorbed Pt-CDs process of cisplatin onto the two modified sponges was predominantly spontaneous, except for Cys@Sponge at a temperature of 293 K. The findings derived from the batch adsorption experiments con­ Conversely, the adsorption of carboplatin was found to be non- ducted at the macro scale reveal that the adsorption behaviour of trace spontaneous, only except at highest 343 K, where the system exhibited Pt-CDs follows a chemisorption mechanism, which dependents on the an energy gain from the surroundings [82–85]. Moreover, the ΔG◦ formation of Pt-S bonds. However, to gain deeper insights into the values exhibited a decrease as the temperature increased, suggesting molecular-level adsorption process regarding the coordination envi­ that higher temperatures promote the spontaneity of adsorption [86]. ronment and the chemical state of Pt in the adsorbed Pt-CDs, Pt L3-edge The adsorption of cisplatin or carboplatin is an endothermic process XAS measurements were performed. based on positive ΔH◦ values. Additionally, a comparison of the ΔH◦ of Fig. 7a presents Pt L3-edge XANES spectra of Pt-CDs adsorbed on the cisplatin and carboplatin reveals a significant difference between the different sponges, along with Pt(II) reference compounds (K2PtCl4, two compounds. Specifically, the adsorption of cisplatin is generally cisplatin, and carboplatin). Generally, the XANES spectra of the adsor­ characterized by a lower energy requirement, which is consistent with bed Pt resemble those of the Pt(II) standards, albeit with slight de­ previous explanations. On the other hand, the adsorption of carboplatin viations in the configuration of the white line, demonstrating the is hindered by a higher heat threshold, necessitating the promotion of unchanged Pt valence. Consequently, unaltered Pt valence indicated the carboplatin hydration to facilitate its activation for subsequent adsorp­ adsorption of Pt-CDs onto sponges did not entail any oxidation or redox tion processes. reaction. The spectral profiles of cisplatin and carboplatin absorbed by The positive value of the change in standard entropy (ΔS◦ ) suggests functionalized sponges are very similar. The temperature of adsorption an enhanced inclination towards disorder at the interface between the only affects the intensity of the white-line in the case of MPA@Sponge. However, the adsorbed Pt-CDs at low temperature manifests more noise 8 D. Han et al. Chemical Engineering Journal 472 (2023) 144894 k2 (k) k2 (k) R k2 (k) k (k) k R Fig. 7. Pt L3-edge (a) XANES spectra, (b) module of the Fourier transformed EXAFS signal of Pt references (K2PtCl4, cisplatin and carboplatin in solid) and Pt-CDs adsorbed on sponges, (c) EXAFS signals, (d) imaginary part and module of the Fourier transformed EXAFS of Pt-CDs adsorbed on sponges at 343 K (the line represents the best fit), (e) schematic representation of Pt-CDs adsorption mechanisms by thiol-functionalized sponges. due to the low adsorption capacities. The presence of inherent noise in amplitude which is like the Pt-Cl contribution in the K2PtCl4. In our case, low Pt-loaded samples posed a challenge for the identification of oscil­ this can be attributed to Pt-S bond. In order to establish the Pt coordi­ lations, thus EXAFS fitting analysis was feasible only on samples ob­ nation structure, EXAFS fitting analysis was conducted. The findings tained at high-temperature adsorption. Fig. 7b depicts the module of the revealed that, on average, each Pt atom was coordinated by approxi­ Fourier transformed (FT) EXAFS signal, which offers valuable insights mately four sulfur atoms within the first coordination shell at ~ 2.30 Å into the coordination environment of adsorbed Pt. The dominant shell of (as illustrated in Fig. 7c and d, and presented in Table S5). These results Pt-loaded on MPA@Sponge and Cys@Sponge appears at a distance and suggest the cisplatin and carboplatin adsorption process at low 9 D. Han et al. Chemical Engineering Journal 472 (2023) 144894 concentrations proceeds in a manner depicted by Fig. 7e. The initial adsorbent dosage of 10 mg, solution volume of 2 mL, pH 3, 24 h, and stage involves hydration of both Pt-CDs, followed by complexation with 293 K). Their adsorption capacities were determined and compared, as the thiol groups present on the surface of functionalized sponge by depicted in Fig. 8a. activated Pt aqua-derivatives. With prolonged heating, a portion of MPA Upon introduction of HCl to the stored solution, there was a notable and Cys undergoes thermal decomposition (confirmed by EA, S content improvement in the adsorption of carboplatin by both adsorbents. of MPA@Sponge and Cys@Sponge decreased about 47% and 39%, Specifically, the adsorption capacity of MPA@Sponge and Cys@Sponge respectively, after stirring in 343 K solution without Pt for 24 h), giving increased significantly from 5.8 ± 0.1 and 4.7 ± 0.1 to 13.9 ± 0.9 and rise to sulfur-containing fragments in solution, such as sulfides [89–92], 9.4 ± 0.2 μg‧g− 1, respectively. By analyzing XANES spectra of carbo­ which subsequently displace the ammonia ligand despite its inertness. platin stocks in the presence and absence of HCl, as illustrated in Fig. 8b, it is observed that carboplatin manifests distinct spectral features 3.4. Effect of Cl− presence in stock solution on carboplatin adsorption compared to carboplatin in H2O stock solution, but shares similarities with cisplatin when exposed to HCl. The mechanism of the carboplatin As elaborated previously, the derivatives of cisplatin and carboplatin transformation was proposed by Curis et al., [69] to explain their XAS demonstrated a facile complexation behaviour attributed to the Pt-S results on carboplatin decomposition in chloride medium. And it was bond formation after hydration activation. However, it is noteworthy also previously corroborated by chromatographic techniques [61]. It that the adsorption capacity of cisplatin always surpassed that of car­ can be inferred that the stability of carboplatin was affected by this boplatin. The observed contrast can be attributed to the influence of transformation (Fig. 8c), which resulted in the formation of an open-ring distinct ligands on the hydration rate. In particular, relative to the Cl structure that demonstrated enhanced adsorption activity. Nonetheless, ligand present in cisplatin, the CBDCA ligand found in carboplatin the introduction of an equivalent concentration of Cl ions in the form of demonstrated higher resistance to hydration. Consequently, CBDCA NaCl to the original solution did not result in the anticipated increase in tended to remain bound, thus resulting in more pronounced steric hin­ adsorption. Although a slight increase was observed with ageing of the drance during subsequent complexation reactions. stock up to 40 days, it suggested that acidity and Cl jointly played a In order to verify the proposed hypothesis, chloride ions (at a con­ crucial role in the conversion process. Similarly, Curis et al., did not find centration of 0.2 mol‧L− 1 in either the form of HCl or NaCl) were that carboplatin had the same transformation in neutral NaCl solution as introduced into the stock solution of carboplatin (Pt 100 mg‧L− 1) to in HCl solution [69]. expedite the hydration process of carboplatin. The adsorption experi­ ment was conducted under identical conditions to those of the carbo­ platin Cl-free stock solution (initial Pt concentration of 235 μg‧L− 1 obtained through dilution of the stock solution with Milli-Q water, Fig. 8. (a) Effect of Cl ions in the stock solution on the adsorption capacity of carboplatin; (b) XANES spectra of cisplatin stock solution in 0.2 mol‧L− 1 HCl, car­ boplatin stock solution in H2O, and cisplatin stock solution in 0.2 mol‧L− 1 HCl; (c) the transformation of carboplatin to cisplatin within an HCl-containing medium; (d) removal of cisplatin, carboplatin, and their mixtures from spiked urine samples by MPA@Sponge. 10 D. Han et al. Chemical Engineering Journal 472 (2023) 144894 3.5. Experimental verification of Pt-CDs removal from urine and diluted CDs. Pre-displacing ligands in an aqueous solution can result in the urine production of more active derivatives, which in turn facilitate subse­ quent complexation. Therefore, the distinct hydration patterns of As present in Fig. 8d, there is a noteworthy augmentation in the cisplatin and carboplatin lead to the preferential adsorption of cisplatin adsorption capacity of MPA@Sponge towards Pt with the dilution of the over carboplatin. The higher hydration resistance of CBDCA ligand from urine matrix. This effect signifies a considerable reduction in the inter­ carboplatin accounts for the adsorption disadvantages observed. Further ference intensity of the matrix effect. The matrix effect observed in the elevating the temperature to 343 K promoted the adsorption of Pt-CDs experiment is unequivocally attributed to the intricate nature of the by MPA@Sponge, resulting in the removal of 88.9 ± 0.5% and 85.2 urine composition (listed in Table S6). One of the potential factors that ± 0.4%, respectively (while 75 ± 2% and 59 ± 1% for Cys@Sponge). may impede the removal of cisplatin and carboplatin is the presence of This was due to the temperature-enhanced chelation reaction of Pt-S. trace proteins like Tamm-Horsfall protein in urine [93,94], which con­ Adsorption thermodynamic studies also confirmed that adsorption is a tains cysteine residues that may pre-chelate a portion of these drugs. thermally favoured endothermic reaction. Moreover, the adsorption of Furthermore, the presence of components like NH+ 4 and Cl in the urine − both Pt-CDs conforms to the Pseudo-second-order kinetic model and the matrix may interfere with the substitution of cisplatin and carboplatin Langmuir isotherm model. In summary, the elimination of Pt-CDs at ligands., thereby adversely affecting their complexation with the trace concentrations is associated with a hydration process and a MPA@Sponge surface [40]. In addition, the coexistence of ions such as chelation-dominant chemisorption. Significantly, the examination of the Na+, K+, Mg2+, and Ca2+ in urine results in competitive adsorption, Pt-spiked urine treatment has demonstrated the potential utilization of thereby slightly impeding the adsorption of cisplatin and carboplatin MPA@Sponge for the purpose of treating urine samples from patients [95]. that contain cisplatin and/or carboplatin, as well as hospital wastewater Additionally, the results reveal that the rise in mixed carboplatin contaminated with these substances. To summarize, our study has leads to a notable reduction in the Pt adsorption capacity. Nonetheless, introduced innovative methods for effectively managing wastewater this declining pattern appears to mitigate in 100-fold diluted urine, polluted with Pt-CDs, thereby offering a practical strategy to tackle this whereby the reduction decreases from 90.0 ± 0.3% to 77.0 ± 0.2% emerging environmental threat that has been persistently overlooked. while the values decrease from 34 ± 5% to 3 ± 1% in non-diluted urine and from 82 ± 2% to 38 ± 2% in ten-fold diluted urine, respectively. Declaration of Competing Interest The present finding demonstrates that the matrix effect may exert a greater influence on the pre-hydration activation of carboplatin, in The authors declare that they have no known competing financial comparison to aforementioned interference factors like protein interests or personal relationships that could have appeared to influence complexation and competitive adsorption which are expected to impede the work reported in this paper. the adsorption of the two Pt-CDs to a similar degree. In essence, the impurities in the urine maintained the rigidity of the carboplatin Data availability structure. Data will be made available on request. 3.6. Comparison of thiol-functionalized sponges with commercial adsorbents Acknowledgements The efficacy of MPA@Sponge and Cys@Sponge for cisplatin removal was compared with that of two commercially available adsorbents, This study was conducted within the scope of the RECOPHARMA namely 3-Mercaptopropyl-functionalized silica gel (Si-SH) and cysteine- project (grant agreement #778266) under the European Community’s functionalized silica gel (Si-Cys), and results were summarized in H2020 Program H2020-MSCA-RISE 2017. D. Han acknowledges the Table S7. MPA@Sponge exhibits significant efficiency in the removal support from the China Scholarships Council (No. 201906450024). The process (71.5 ± 0.2%), which is comparable to Si-Cys (76.3 ± 0.2%), authors would like to express their gratitude to the ALBA synchrotron but noticeably lower than Si-SH (98.7 ± 0.1%). This disparity can be facility for providing beamtime (No. 2022085922) at the BL22-CLÆSS attributed to the much higher sulfur loading of Si-SH (4.97 ± 0.07 wt%) beamline, and to Carlo Marini for his assistance as the scientific local than that of MPA@Sponge (1.23 ± 0.07 wt%) and Si-Cys (1.30 ± 0.02 contact. The authors would like to thank Cristina Navarro Senent from wt%). While the performance of functionalized sponges is slightly the Servei de Microscòpia of Universitat Autònoma de Barcelona (UAB). inferior to commercial adsorbents, cost considerations must be taken All the authors are grateful to the Servei d’Anàlisi Química of the UAB into account. From a cost perspective, our proposed materials offer for the analysis. All authors thank Yunhui Yang for his help on BET considerable advantages. Furthermore, the removal efficiency of Si-Cys analysis. Additionally, the authors extend their appreciation to Markel on Pt-CDs, in comparison with other reported adsorbents, has been Luaces, Yusleydi Enamorado, and Alejandro Barragán Beltri for their previously published in prior research study [26]. assistance during the experiment. Open Access funding provided thanks to the agreement CRUE- CSIC with Elsevier. 4. Conclusions Appendix A. Supplementary data The coupling of MPA and Cys with Sponge via a simple one-step esterification reaction has been demonstrated as a feasible and suc­ Supplementary data to this article can be found online at https://doi. cessful process. The presence of an implanted high-affinity thiol group org/10.1016/j.cej.2023.144894. has been demonstrated to significantly enhance the adsorption of both cisplatin and carboplatin, suggesting that Pt-S complexation plays a References pivotal role in chelation-dominated chemical adsorption. Then the uti­ [1] E. Heath, M. Isidori, T. Kosjek, M. Filipič (Eds.), Fate and Effects of Anticancer lization of synchrotron XAS has enabled the investigation of the coor­ Drugs in the Environment, Springer International Publishing, Cham, 2020. dination environment of Pt-CDs loaded at extremely low concentrations. [2] T.I.A. Gouveia, A.M.T. Silva, M.G. Freire, A.C.A. Sousa, A. Alves, M.S.F. Santos, In particular, EXAFS analysis provides insight into the formation of Pt-S Multi-target analysis of cytostatics in hospital effluents over a 9-month period, bonds after adsorption, allowing for a persuasive explanation of the J. Hazard. Mater. 448 (2023), 130883, https://doi.org/10.1016/j. jhazmat.2023.130883. molecular-level adsorption mechanism. Besides complexation, the pro­ [3] D. Li, H. Chen, H. Liu, D. Schlenk, J. Mu, S. Lacorte, G.G. Ying, L. Xie, Anticancer cess of removing Pt-CDs also involves a hydration process for both Pt- drugs in the aquatic ecosystem: environmental occurrence, ecotoxicological effect 11 D. Han et al. Chemical Engineering Journal 472 (2023) 144894 and risk assessment, Environ. Int. 153 (2021), 106543, https://doi.org/10.1016/j. [27] T.C. Johnstone, K. Suntharalingam, S.J. Lippard, The next generation of platinum envint.2021.106543. drugs: targeted Pt(II) agents, nanoparticle delivery, and Pt(IV) prodrugs, Chem. [4] C.W.P. Schmidt, Pediatric oncologic pharmacy, springer international publishing, Rev. 116 (2016) 3436–3486, https://doi.org/10.1021/acs.chemrev.5b00597. Cham (2019), https://doi.org/10.1007/978-3-030-10988-2. [28] L. Kelland, The resurgence of platinum-based cancer chemotherapy, Nat. Rev. [5] V. Queirós, U.M. Azeiteiro, A.M.V.M. Soares, R. Freitas, The antineoplastic drugs Cancer. 7 (2007) 573–584, https://doi.org/10.1038/nrc2167. cyclophosphamide and cisplatin in the aquatic environment – review, J. Hazard. [29] B.P. Espósito, R. Najjar, Interactions of antitumoral platinum-group metallodrugs Mater. 412 (2021) 125028. with albumin, Coord. Chem. Rev. 232 (2002) 137–149, https://doi.org/10.1016/ [6] M. Kundi, A. Parrella, M. Lavorgna, E. Criscuolo, C. Russo, M. Isidori, Prediction S0010-8545(02)00049-8. and assessment of ecogenotoxicity of antineoplastic drugs in binary mixtures, [30] A.I. Ivanov, J. Christodoulou, J.A. Parkinson, K.J. Barnham, A. Tucker, Environ. Sci. Pollut. Res. 23 (2016) 14771–14779, https://doi.org/10.1007/ J. Woodrow, P.J. Sadler, Cisplatin binding sites on human albumin, J. Biol. Chem. s11356-015-4884-x. 273 (1998) 14721–14730, https://doi.org/10.1074/jbc.273.24.14721. [7] C. Russo, M. Isidori, J.A. Deaver, H.C. Poynton, Toxicogenomic responses of low [31] Ž.D. Bugarčić, J. Bogojeski, B. Petrović, S. Hochreuther, R. van Eldik, Mechanistic level anticancer drug exposures in Daphnia magna, Aquat. Toxicol. 203 (2018) studies on the reactions of platinum(ii) complexes with nitrogen- and sulfur-donor 40–50, https://doi.org/10.1016/j.aquatox.2018.07.010. biomolecules, Dalt. Trans. 41 (2012) 12329, https://doi.org/10.1039/c2dt31045g. [8] S. Kolarević, Z. Gačić, J. Kostić, K. Sunjog, M. Kračun-Kolarević, M. Paunović, [32] Z. Wu, Z. Cheng, W. Ma, Adsorption of Pb(II) from glucose solution on thiol- J. Knežević-Vukčević, B. Vuković-Gačić, Impact of common cytostatics on DNA functionalized cellulosic biomass, Bioresour. Technol. 104 (2012) 807–809, damage in freshwater mussels unio pictorum and unio tumidus, Clean - Soil, Air, https://doi.org/10.1016/j.biortech.2011.10.100. Water. 44 (2016) 1471–1476, https://doi.org/10.1002/clen.201500482. [33] Z. Li, L. Wu, H. Liu, H. Lan, J. Qu, Improvement of aqueous mercury adsorption on [9] C. Trombini, T. Garcia da Fonseca, M. Morais, T.L. Rocha, J. Blasco, M.J. Bebianno, activated coke by thiol-functionalization, Chem. Eng. J. 228 (2013) 925–934, Toxic effects of cisplatin cytostatic drug in mussel Mytilus galloprovincialis, Mar. https://doi.org/10.1016/j.cej.2013.05.063. Environ. Res. 119 (2016) 12–21, https://doi.org/10.1016/j. [34] B. Parambath Kanoth, M. Claudino, M. Johansson, L.A. Berglund, Q. Zhou, marenvres.2016.05.004. Biocomposites from natural rubber: synergistic effects of functionalized cellulose [10] T.G. Fonseca, M.B. Morais, T. Rocha, D.M.S. Abessa, M. Aureliano, M.J. Bebianno, nanocrystals as both reinforcing and cross-linking agents via free-radical thiol-ene Ecotoxicological assessment of the anticancer drug cisplatin in the polychaete chemistry, ACS Appl. Mater. Interfaces. 7 (2015) 16303–16310, https://doi.org/ Nereis diversicolor, Sci. Total Environ. 575 (2017) 162–172, https://doi.org/ 10.1021/acsami.5b03115. 10.1016/j.scitotenv.2016.09.185. [35] S.Y. Park, J.W. Chung, R.D. Priestley, S.Y. Kwak, Covalent assembly of metal [11] T.G. da Fonseca, D.M.S. Abessa, M.J. Bebianno, Effects of mixtures of anticancer nanoparticles on cellulose fabric and its antimicrobial activity, Cellul. 19 (2012) drugs in the benthic polychaete Nereis diversicolor, Environ. Pollut. 252 (2019) 2141–2151, https://doi.org/10.1007/s10570-012-9773-6. 1180–1192, https://doi.org/10.1016/j.envpol.2019.05.095. [36] D. Mohan, A. Sarswat, V.K. Singh, M. Alexandre-Franco, C.U. Pittman, [12] M. Jureczko, J. Kalka, Cytostatic pharmaceuticals as water contaminants, Eur. J. Development of magnetic activated carbon from almond shells for trinitrophenol Pharmacol. 866 (2020), 172816, https://doi.org/10.1016/j.ejphar.2019.172816. removal from water, Chem. Eng. J. 172 (2-3) (2011) 1111–1125. [13] T. Farías, S. Hajizadeh, L. Ye, Cryogels with high cisplatin adsorption capacity: [37] L. Simonelli, C. Marini, W. Olszewski, M. Ávila Pérez, N. Ramanan, G. Guilera, Towards removal of cytotoxic drugs from wastewater, Sep. Purif. Technol. 235 V. Cuartero, K. Klementiev, Clæss,, The hard X-ray absorption beamline of the (2020), 116203, https://doi.org/10.1016/j.seppur.2019.116203. ALBA CELLS synchrotron, Cogent Phys. 3 (2016), https://doi.org/10.1080/ [14] F. Ogata, K. Inoue, H. Tominaga, Y. Iwata, A. Ueda, Y. Tanaka, N. Kawasaki, Use of 23311940.2016.1231987. calcined gibbsite to remove cisplatin from aqueous solutions, J. Water Environ. [38] C. Marini, R. Boada, J. Prieto Burgos, N. Ramanan, I. García Domínguez, J. Zhao, T. Technol. 12 (2014) 13–23, https://doi.org/10.2965/jwet.2014.13. T. Xiao, L. Simonelli, Low-cost vacuum compatible liquid cell for hard X-ray [15] K. Lenz, S. Hann, G. Koellensperger, Z. Stefanka, G. Stingeder, N. Weissenbacher, S. absorption spectroscopy, Nucl. Instruments Methods Phys. Res. Sect. A Accel. N. Mahnik, M. Fuerhacker, Presence of cancerostatic platinum compounds in Spectrometers, Detect. Assoc. Equip. 908 (2018) 333–337, https://doi.org/ hospital wastewater and possible elimination by adsorption to activated sludge, 10.1016/j.nima.2018.08.036. Sci. Total Environ. 345 (2005) 141–152, https://doi.org/10.1016/j. [39] B. Ravel, M. Newville, Athena, Artemis, Hephaestus: data analysis for X-ray scitotenv.2004.11.007. absorption spectroscopy using IFEFFIT, J. Synchrotron Radiat. 12 (2005) 537–541, [16] K. Folens, A. Abebe, J. Tang, F. Ronsse, G. Du Laing, Biosorption of residual https://doi.org/10.1107/S0909049505012719. cisplatin, carboplatin and oxaliplatin antineoplastic drugs in urine after [40] W. Guo, Q. Zhou, Y. Jia, J. Xu, Cluster and factor analysis of elements in serum and chemotherapy treatment, Environ. Chem. 15 (2018) 506–512, https://doi.org/ urine of diabetic patients with peripheral neuropathy and healthy people, Biol. 10.1071/EN18115. Trace Elem. Res. 194 (2020) 48–57, https://doi.org/10.1007/s12011-019-01747- [17] J. Dobrzyńska, M. Dąbrowska, R. Olchowski, E. Zięba, R. Dobrowolski, x. Development of a method for removal of platinum from hospital wastewater by [41] Y. Gao, N. Yang, X. Yan, W. Hang, J. Xing, J. Zheng, E. Zhu, B. Huang, Early novel ion-imprinted mesoporous organosilica, J. Environ. Chem. Eng. 9 (4) (2021) diagnosis of urinary lithiasis via elementary profile of serum samples, Anal. 105302. Methods. 4 (2012) 693–698, https://doi.org/10.1039/c2ay05705k. [18] K. Lenz, G. Koellensperger, S. Hann, N. Weissenbacher, S.N. Mahnik, [42] X.-Y. Lou, R. Boada, V. Verdugo, L. Simonelli, G. Pérez, M. Valiente, Decoupling the M. Fuerhacker, Fate of cancerostatic platinum compounds in biological wastewater adsorption mechanisms of arsenate at molecular level on modified cube-shaped treatment of hospital effluents, Chemosphere 69 (2007) 1765–1774, https://doi. sponge loaded superparamagnetic iron oxide nanoparticles, J. Environ. Sci. 121 org/10.1016/j.chemosphere.2007.05.062. (2022) 1–12, https://doi.org/10.1016/j.jes.2021.09.001. [19] K. Lenz, S.N. Mahnik, N. Weissenbacher, R.M. Mader, P. Krenn, S. Hann, [43] A. Politzer, J.C. H Teng, T.T. Singh, T.J.C. H, T.T. Singh, The method of producing G. Koellensperger, M. Uhl, S. Knasmüller, F. Ferk, W. Bursch, M. Fuerhacker, a regenerated cellulose sponge, 1963. https://lens.org/073-184-824-742-697. Monitoring, removal and risk assessment of cytostatic drugs in hospital [44] P.E.L. Kyle, T.B. P, Ion exchange polymers on improved porous substrates, 1982. wastewater, Water Sci. Technol. 56 (2007) 141–149, https://doi.org/10.2166/ https://lens.org/080-517-023-858-186. wst.2007.828. [45] X.Y. Lou, R. Boada, L. Simonelli, M. Valiente, Enhanced arsenite removal by [20] C. Hernández, Y. Ramos, L.A. Fernández, O. Ledea, M. Bataller, E. Véliz, V. Besada, superparamagnetic iron oxide nanoparticles in-situ synthesized on a commercial A. Rosado, Ozonation of cisplatin in aqueous solution at pH 9, Ozone Sci. Eng. 30 cube-shape sponge: adsorption-oxidation mechanism, J. Colloid Interface Sci. 614 (2008) 189–196, https://doi.org/10.1080/01919510801907722. (2022) 460–467, https://doi.org/10.1016/j.jcis.2022.01.119. [21] T. Kobayashi, J. Hirose, K. Sano, N. Hiro, Y. Ijiri, H. Takiuchi, H. Tamai, [46] N.B. Rainer, R.N. B, Polymer product for the selective absorption of dissolved ions, H. Takenaka, K. Tanaka, T. Nakano, Evaluation of an electrolysis apparatus for 1992. https://lens.org/018-286-240-697-194. inactivating antineoplastics in clinical wastewater, Chemosphere 72 (2008) [47] J.A. Muñoz, A. Gonzalo, M. Valiente, J. O S E Ä A N T O N I O M U ÑO Z, A N N A 659–665, https://doi.org/10.1016/j.chemosphere.2008.02.020. G O N Z A L O, A N D M A N U E L V A L I E N T E, J.A. Muñoz, A. Gonzalo, M. [22] J. Hirose, F. Kondo, T. Nakano, T. Kobayashi, N. Hiro, Y. Ando, H. Takenaka, Valiente, Arsenic Adsorption by Fe(III)-Loaded Open-Celled Cellulose Sponge. K. Sano, Inactivation of antineoplastics in clinical wastewater by electrolysis, Thermodynamic and Selectivity Aspects, Environ. Sci. Technol. 36 (2002) Chemosphere 60 (2005) 1018–1024, https://doi.org/10.1016/j. 3405–3411. https://doi.org/10.1021/es020017c. chemosphere.2005.01.024. [48] J. Li, L.P. Zhang, F. Peng, J. Bian, T.Q. Yuan, F. Xu, R.C. Sun, Microwave-assisted [23] K.D. Lee, Y. Il Jeong, D.H. Kim, G.T. Lim, K.C. Choi, Cisplatin-incorporated solvent-free acetylation of cellulose with acetic anhydride in the presence of iodine nanoparticles of poly(acrylic acid-co-methyl methacrylate) copolymer, Int. J. as a catalyst, Molecules 14 (2009) 3551–3566, https://doi.org/10.3390/ Nanomedicine. 8 (2013) 2835–2845, https://doi.org/10.2147/IJN.S48367. molecules14093551. [24] B. Singh, N. Chauhan, V. Sharma, Design of molecular imprinted hydrogels for [49] T. Burks, M. Avila, F. Akhtar, M. Göthelid, P.C. Lansåker, M.S. Toprak, controlled release of cisplatin: evaluation of network density of hydrogels, Ind. M. Muhammed, A. Uheida, Studies on the adsorption of chromium(VI) onto 3- Eng. Chem. Res. 50 (2011) 13742–13751, https://doi.org/10.1021/ie200758b. Mercaptopropionic acid coated superparamagnetic iron oxide nanoparticles, [25] R. Lombana Fraguela, J.A. Ricardo Garcia, M.E. Villanueva Tagle, M.S. Pomares J. Colloid Interface Sci. 425 (2014) 36–43, https://doi.org/10.1016/j. Alfonso, M. Cracchiolo, A. Kovačević, M. Tolazzi, A. Melchior, M. Sanadar, jcis.2014.03.025. Evaluation of Dithiocarbamate-Modified Silica for Cisplatin Removal from Water, [50] C. Han, K. Xu, Q. Liu, X. Liu, J. Li, Colorimetric sensing of cysteine using label-free Processes. 11 (2023) 472. https://doi.org/10.3390/pr11020472. silver nanoparticles, Sensors Actuators, B Chem. 202 (2014) 574–582, https://doi. [26] D. Han, M. López-Mesas, M. Luaces, Y. Enamorado, M. Sanadar, A. Melchior, org/10.1016/j.snb.2014.05.139. M. Valiente, Comparative study on removal of platinum cytostatic drugs at trace [51] K.H. Glover, H. Tsubomura, Compounds with zinc (II), cadmium (II), mercury (II), level by cysteine, diethylenetriamino functionalized Si-gels and polyethyleneimine J. Am. Chem. Soc. 87 (1965) 1904–1909. functionalized sponge: adsorption performance and mechanisms, Sci. Total [52] S. Aryal, B.K.C. Remant, N. Dharmaraj, N. Bhattarai, C.H. Kim, H.Y. Kim, Environ. 891 (2023), 164385, https://doi.org/10.1016/j.scitotenv.2023.164385. Spectroscopic identification of SAu interaction in cysteine capped gold 12 D. Han et al. Chemical Engineering Journal 472 (2023) 144894 nanoparticles, Spectrochim. Acta - Part A Mol. Biomol. Spectrosc. 63 (2006) [74] D. Han, X. Li, Z. Gong, L. Jiang, Z. Wang, P. Liu, Hierarchical porous catalytic 160–163, https://doi.org/10.1016/j.saa.2005.04.048. pyrolysis char derived from oily sludge for enhanced adsorption, ACS Omega 6 [53] A. Ihs, B. Liedberg, Chemisorption of l-cysteine and 3-mercaptopropionic acid on (2021) 20549–20559, https://doi.org/10.1021/acsomega.1c02575. gold and copper surfaces: an infrared reflection-absorption study, J. Colloid [75] V.D. Chinh, L.X. Hung, L. Di Palma, V.T.H. Hanh, G. Vilardi, Effect of carbon Interface Sci. 144 (1991) 282–292, https://doi.org/10.1016/0021-9797(91) nanotubes and carbon nanotubes/gold nanoparticles composite on the 90259-B. photocatalytic activity of TiO2 and TiO2-SiO2, Chem. Eng. Technol. 42 (2019) [54] R. Alimohammadzadeh, A.A. Rafi, L. Goclik, C.W. Tai, A. Cordova, Direct 308–315, https://doi.org/10.1002/ceat.201800265. organocatalytic thioglycolic acid esterification of cellulose nanocrystals: a simple [76] G. Los, M.J.H. Van Vugt, L. Den Engelse, H.M. Pinedo, Effects of temperature on entry to click chemistry on the surface of nanocellulose, Carbohydr. Polym. the interaction of cisplatin and carboplatin with cellular DNA, Biochem. Technol. Appl. 3 (2022), 100205, https://doi.org/10.1016/j.carpta.2022.100205. Pharmacol. 46 (1993) 1229–1237, https://doi.org/10.1016/0006-2952(93)90472- [55] H.Y. Choi, J.H. Bae, Y. Hasegawa, S. An, I.S. Kim, H. Lee, M. Kim, Thiol- 9. functionalized cellulose nanofiber membranes for the effective adsorption of heavy [77] M.A. Allsopp, G.J. Sewell, C.G. Rowland, C.M. Riley, R.L. Schowen, The metal ions in water, Carbohydr. Polym. 234 (2020), 115881, https://doi.org/ degradation of carboplatin in aqueous solutions containing chloride or other 10.1016/j.carbpol.2020.115881. selected nucleophiles, Int. J. Pharm. 69 (1991) 197–210, https://doi.org/10.1016/ [56] K. Pramanik, P. Sarkar, D. Bhattacharyay, 3-Mercapto-propanoic acid modified 0378-5173(91)90362-R. cellulose filter paper for quick removal of arsenate from drinking water, Int. J. Biol. [78] J. Wang, X. Guo, Adsorption isotherm models: classification, physical meaning, Macromol. 122 (2019) 185–194, https://doi.org/10.1016/j.ijbiomac.2018.10.065. application and solving method, Chemosphere 258 (2020), 127279, https://doi. [57] G.H. Gao, M.J. Park, Y. Li, G.H. Im, J.H. Kim, H.N. Kim, J.W. Lee, P. Jeon, O. org/10.1016/j.chemosphere.2020.127279. Y. Bang, J.H. Lee, D.S. Lee, The use of pH-sensitive positively charged polymeric [79] R.D. Hancock, A.E. Martell, Ligand design for selective complexation of metal ions micelles for protein delivery, Biomaterials 33 (2012) 9157–9164, https://doi.org/ in aqueous solution, Chem. Rev. 89 (1989) 1875–1914, https://doi.org/10.1021/ 10.1016/j.biomaterials.2012.09.016. cr00098a011. [58] M. Pavelka, M.F.A. Lucas, N. Russo, On the hydrolysis mechanism of the second- [80] A. Alfarra, E. Frackowiak, F. Béguin, The HSAB concept as a means to interpret the generation anticancer drug carboplatin, Chem. - A Eur. J. 13 (2007) 10108–10116, adsorption of metal ions onto activated carbons, Appl. Surf. Sci. 228 (2004) 84–92, https://doi.org/10.1002/chem.200700887. https://doi.org/10.1016/j.apsusc.2003.12.033. [59] M. Sooriyaarachchi, A. Narendran, J. Gailer, Comparative hydrolysis and plasma [81] P. Pourhakkak, A. Taghizadeh, M. Taghizadeh, M. Ghaedi, S. Haghdoust, protein binding of cis-platin and carboplatin in human plasma in vitro, Metallomics Fundamentals of adsorption technology, 1st ed., Elsevier Ltd., 2021. https://doi. 3 (2011) 49–55, https://doi.org/10.1039/c0mt00058b. org/10.1016/B978-0-12-818805-7.00001-1. [60] X.L. Yang, A.H.J. Wang, Structural studies of atom-specific anticancer drugs acting [82] M. Sun, Y. Yang, M. Huang, S. Fu, Y. Hao, S. Hu, D. Lai, L. Zhao, Adsorption on, DNA (1999), https://doi.org/10.1016/S0163-7258(99)00020-0. behaviors and mechanisms of antibiotic norfloxacin on degradable and [61] W.J.F. van der Vijgh, Clinical pharmacokinetics of carboplatin, Clin. nondegradable microplastics, Sci. Total Environ. 807 (2022), 151042, https://doi. Pharmacokinet. 21 (1991) 242–261, https://doi.org/10.2165/00003088- org/10.1016/j.scitotenv.2021.151042. 199121040-00002. [83] R.M. Schneider, C.F. Cavalin, M.A.S.D. Barros, C.R.G. Tavares, Adsorption of [62] A.J. Di Pasqua, J. Goodisman, J.C. Dabrowiak, Understanding how the platinum chromium ions in activated carbon, Chem. Eng. J. 132 (2007) 355–362, https:// anticancer drug carboplatin works: from the bottle to the cell, Inorganica Chim. doi.org/10.1016/j.cej.2007.01.031. Acta. 389 (2012) 29–35, https://doi.org/10.1016/j.ica.2012.01.028. [84] S. Guo, M. Gao, T. Shen, Y. Xiang, G. Cao, Effective adsorption of sulfamethoxazole [63] J. Wang, J. Tao, S. Jia, M. Wang, H. Jiang, Z. Du, The protein-binding behavior of by novel organo-Vts and their mechanistic insights, Microporous Mesoporous platinum anticancer drugs in blood revealed by mass spectrometry, Mater. 286 (2019) 36–44, https://doi.org/10.1016/j.micromeso.2019.05.032. Pharmaceuticals. 14 (2021) 1–17, https://doi.org/10.3390/ph14020104. [85] Z. Gu, M. Gao, Z. Luo, L. Lu, Y. Ye, Y. Liu, Bis-pyridinium dibromides modified [64] D. Wang, S.J. Lippard, Cellular processing of platinum anticancer drugs, Nat. Rev. organo-bentonite for the removal of aniline from wastewater: a positive role of π-π Drug Discov. 4 (2005) 307–320, https://doi.org/10.1038/nrd1691. Polar interaction, Appl. Surf. Sci. 290 (2014) 107–115, https://doi.org/10.1016/j. [65] K.U. Maheswari, T. Ramachandran, D. Rajaji, Interaction of cisplatin with planar apsusc.2013.11.008. model membranes - dose dependent change in electrical characteristics, Biochim. [86] S.F. Soares, J. Nogueira, T. Trindade, A.L. Daniel-da-Silva, Towards efficient Biophys. Acta - Biomembr. 1463 (2000) 230–240, https://doi.org/10.1016/S0005- ciprofloxacin adsorption using magnetic hybrid nanoparticles prepared with κ-, ι-, 2736(99)00189-3. and λ-carrageenan, J. Nanostructure Chem. 13 (2022) 283–302, https://doi.org/ [66] G. Speelmans, W.H.H.M. Sips, R.J.H. Grisel, R.W.H.M. Staffhorst, A.M. 10.1007/s40097-022-00498-x. J. Fichtinger-Schepman, J. Reedijk, B. De Kruijff, The interaction of the anti-cancer [87] S. Kishani, T. Benselfelt, L. Wågberg, J. Wohlert, Entropy drives the adsorption of drug cisplatin with phospholipids is specific for negatively charged phospholipids xyloglucan to cellulose surfaces – a molecular dynamics study, J. Colloid Interface and takes place at low chloride ion concentration, Biochim. Biophys. Acta - Sci. 588 (2021) 485–493, https://doi.org/10.1016/j.jcis.2020.12.113. Biomembr. 1283 (1996) 60–66, https://doi.org/10.1016/0005-2736(96)00080-6. [88] G.D. Değermenci, N. Değermenci, V. Ayvaoğlu, E. Durmaz, D. Çakır, E. Akan, [67] T. Zimmermann, F. Šebesta, J.V. Burda, A new grand-canonical potential for the Adsorption of reactive dyes on lignocellulosic waste; characterization, equilibrium, thermodynamic description of the reactions in solutions with constant pH, J. Mol. kinetic and thermodynamic studies, J. Clean. Prod. 225 (2019) 1220–1229, Liq. 335 (2021) 115979. https://doi.org/10.1016/j.jclepro.2019.03.260. [68] J.R. Yachnin, I. Wallin, R. Lewensohn, F. Sirzén, H. Ehrsson, The kinetics and [89] T. Yoshinaga, Y. Iso, T. Isobe, Optimizing the microwave-assisted hydrothermal cytotoxicity of cisplatin and its monohydrated complex, Cancer Lett. 132 (1998) synthesis of blue-emitting L-cysteine-derived carbon dots, J. Lumin. 213 (2019) 175–180, https://doi.org/10.1016/S0304-3835(98)00175-X. 6–14, https://doi.org/10.1016/j.jlumin.2019.05.003. [69] E. Curis, K. Provost, D. Bouvet, I. Nicolis, S. De Crauste-Manciet, D. De Brossard, [90] V. Sharma, P. Ilaiyaraja, A.C. Dakshinamurthy, C. Sudakar, One step thermolysis of S. Bénazeth, Carboplatin and oxaliplatin decomposition in chloride medium, Sb-Mercaptopropionic acid complex in ambient air atmosphere for growing Sb2S3 monitored by XAS, J. Synchrotron Radiat. 8 (2001) 716–718, https://doi.org/ thin films with controlled microstructure, Mater. Sci. Semicond. Process. 121 10.1107/S0909049500017775. (2021), 105330, https://doi.org/10.1016/j.mssp.2020.105330. [70] G. Feiqiang, L. Xiaolei, J. Xiaochen, Z. Xingmin, G. Chenglong, R. Zhonghao, [91] M. Mrad, T. Ben Chaabane, H. Rinnert, B. Lavinia, J. Jasniewski, G. Medjahdi, Characteristics and toxic dye adsorption of magnetic activated carbon prepared R. Schneider, Aqueous synthesis for highly emissive 3-mercaptopropionic acid- from biomass waste by modified one-step synthesis, Colloids Surfaces A capped AIZS quantum dots, Inorg. Chem. 59 (2020) 6220–6231, https://doi.org/ Physicochem. Eng. Asp. 555 (2018) 43–54, https://doi.org/10.1016/j. 10.1021/acs.inorgchem.0c00347. colsurfa.2018.06.061. [92] W. Jian, S. Liu, J. Li, W. Yang, Decomposition reaction of Zn-MPA(3- [71] S. Sen Gupta, K.G. Bhattacharyya, Kinetics of adsorption of metal ions on inorganic mercaptopropionic acid) complex under microwave irradiation, Chem. Res. materials: a review, Adv. Colloid Interface Sci. 162 (2011) 39–58, https://doi.org/ Chinese Univ. 24 (3) (2008) 353–356. 10.1016/j.cis.2010.12.004. [93] R. Micanovic, K. Lafavers, P.S. Garimella, X.R. Wu, T.M. El-Achkar, Uromodulin [72] J. Wang, X. Guo, Adsorption kinetic models: physical meanings, applications, and (Tamm-Horsfall protein): guardian of urinary and systemic homeostasis, Nephrol. solving methods, J. Hazard. Mater. 390 (2020), 122156, https://doi.org/10.1016/ Dial. Transplant. 35 (2020) 33–43, https://doi.org/10.1093/ndt/gfy394. j.jhazmat.2020.122156. [94] S. Aitekenov, A. Gaipov, R. Bukasov, Review: detection and quantification of [73] M. Mourabet, H. El Boujaady, A. El Rhilassi, H. Ramdane, M. Bennani-Ziatni, R. El proteins in human urine, Talanta 223 (2021), 121718, https://doi.org/10.1016/j. Hamri, A. Taitai, Defluoridation of water using brushite: equilibrium, kinetic and talanta.2020.121718. thermodynamic studies, Desalination 278 (2011) 1–9, https://doi.org/10.1016/j. [95] L. Curtis, A. Turner, N. Vyas, G. Sewell, Speciation and reactivity of cisplatin in desal.2011.05.068. river water and seawater, Environ. Sci. Technol. 44 (2010) 3345–3350, https:// doi.org/10.1021/es903620z. 13