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This research investigated the adsorption of propranolol (PROP) by functionalized green carbon nanotubes (MWCNT-B), assessing the influence of pH, in addition to kinetic, equilibrium, and thermodynamic studies and reuse of the material. For this purpose, speciation of PROP and the point of zero charge (pH PZC ) of MWCNT-B were performed, indicating a pKa of 9.67 and pH PZC of 3.31. The adsorption tests at different pH values revealed that in the range of pH 3 to 9, there is no significant variation in PROP uptake, despite this, at pH 11, the removal decreases. Regarding PROP adsorption, the equilibrium time ranged from 30 to 90 min, and the PFO model best represented the kinetic data. The Langmuir model was more predictive in representing isotherms (R 2  > 0.95), and the adsorption process was spontaneous and favorable (ΔG <  - 20 kJ mol -1 ) and indicated exothermic behavior (ΔH =  - 33 kJ mol -1 ) for PROP removal. In addition, the material showed satisfactory thermal regeneration results and can be reused for four cycles. The results suggest that MWCNT-B is an attractive adsorbent and exhibits effective removal of propranolol from aqueous matrices., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Critical metals such as rare earths are essential for important industrial applications and for producing high-tech materials. Currently, the development of alternative and non-conventional biomaterials has gained significant interest. This work investigated the use of crosslinked sericin-alginate-based natural polymeric particles for the removal of rare earths from water. Affinity tests showed that sericin-alginate/polyethylene glycol diglycidyl ether had the highest potential for capturing europium (0.258 mmol/g and 94.33%) and erbium (0.259 mmol/g and 94.55%). Next, erbium was selected based on the affinity with sericin-alginate/polyethylene glycol diglycidyl to investigate the effect of dose/pH, biosorption kinetics, isothermal equilibrium, desorption/reuse, and selectivity. The effect of dose and pH showed that 8.0 g/L (95.91%) and pH 5.0 (97.53%) were more efficient in capturing erbium. The biosorption kinetics showed that the equilibration time was reached within 210 min. The PSO and EMTR models effectively represented the kinetics data. The isothermal equilibrium revealed that the maximum uptake capacity for erbium was 0.641 mmol/g. The isothermal curves better fit the Dubinin-Radushkevich (55 °C) and Langmuir (25 and 40 °C) models. Thermodynamic quantitates indicated that erbium uptake was spontaneous, governed by entropic changes, and endothermic. The recovery of Er 3+ was greater than 98% and the reuse of the eluent in the cycles enriched the Er 3+ load 10-times (1.0 to 9.91 mmol/L). The beads also showed better performance for capturing Er 3+ and Eu 3+ with other coexisting ions. Characterization analyzes revealed the ion exchange mechanism between Ca 2+ /Er 3+ prevailed in the Er 3+ removal. Thus, the results pointed out that crosslinked sericin-alginate can be used as an alternative and promising biosorbent to remove and recover rare earths., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

In this study, four Brazilian clays (Bofe, Verde-lodo, commercial Fluidgel, and expanded commercial vermiculite) were evaluated for their adsorptive capacity and removal percentage in relation to different toxic metals (Ni 2+ , Cd 2+ , Zn 2+ , and Cu 2+ ). The best results were obtained by expanded vermiculite, with cadmium removal reaching values of 95%. The most promising clay was modified by the sodification process, and the metal cadmium was used to evaluate the ion exchange process. The clays expanded vermiculite (EV) and VNa-sodified vermiculite were evaluated by equilibrium study at 25, 35, and 45 °C. At 25 °C, EV obtained a maximum adsorption capacity of 0.368 mmol/g and sodified vermiculite 0.480 mmol/g, which represents an improvement of 30.4% in modified clay capacity. At 45 °C, the sodified vermiculite reached 0.970 mmol/g adsorption capacity. The Langmuir, Redlich-Peterson Freundlich, and Dubinin-Raduskevich models were adjusted to the results. Langmuir provided the best fit among the models. The thermodynamic quantities (ΔS, ΔH, and ΔG) demonstrated that the process is spontaneous and endothermic and the metal is captured by physisorption and chemisorption in the studied temperature range. For the ion exchange equilibrium, the binary Langmuir and binary Langmuir-Freundlich models were adjusted to the expanded vermiculite and sodified vermiculite isotherms, respectively. Both models were predictive. Thermal analysis indicated good heat resistance even after material modification. The apparent and real densities demonstrated that after each treatment or contamination, the clayey material undergoes contraction in its structure. An improved efficiency of the adsorbent was found after sodification., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The presence of emerging contaminants in wastewater poses a global environmental challenge, requiring the development of innovative materials or methods for their treatment. This study focused on the production of green functionalized carbon nanotubes (CNTs) and using them in the adsorption of the pharmaceuticals Losartan (LOS) and Diclofenac (DIC). The efficiency of the methodology was verified by characterization techniques. Elemental composition analysis indicated a significant increase in the iron content after the green functionalization, proving the effectiveness of the method. Thermogravimetric analysis showed similar thermal degradation profiles for pristine CNTs and functionalized CNTs, indicating better post-functionalization thermal stability. BET analysis revealed mesoporous characteristics of CNTs, with increased surface area and pore volumes after functionalization. X-Ray diffraction confirmed the preservation of the lattice structure of the CNTs post-functionalization and post-adsorption, with changes in peak broadening suggesting surface modifications. LOS and DIC adsorption were evaluated via kinetic studies at four different concentrations (0.1-0.4 mmol/L) that were best represented by the pseudo-second order model, suggesting chemisorption mechanisms, with faster and higher uptakes for DIC (0.084-0.261 mmol/g; t eq  = 5 min) when compared to LOS (0.058-0.235 mmol/g; t eq  = 20 min). The curves were also studied via artificial neural networks (ANN) and revealed that the best ANN architecture for representing the experimental data is a network with [3 5 5 2] neurons trained using the Bayesian-Regularization algorithm and the Log-sigmoid (hidden layers) and Linear (output layer) transfer functions. The desorption study showed that CaCl 2 had better performance in CNT regeneration, reaching its removal capacity above 50% up to 3 cycles, for both pharmaceuticals. These findings reveal the potential of the developed material as a promising adsorbent for targeted removal of pollutants, contributing to advances in the remediation of emerging contaminants and the application of artificial intelligence in adsorption research., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Oral drug administration, especially when composed of mucoadhesive delivery systems, has been a research trend due to increased residence time and contact with the mucosa, potentially increasing drug bioavailability and stability. In this context, this study aimed to develop self-assembly mucoadhesive beads composed of blends of κ-carrageenan and sericin (κ-Car/Ser) loaded with the anti-inflammatory drug indomethacin (IND). We investigated the swelling, adhesion behaviour, and mechanical/physical properties of the beads, assessing their effects on cell viability, safety and permeation characteristics in both 2D and triple-culture model. The swelling ratio of the beads indicated pH-responsiveness, with maximum water absorption at pH 6.8, and strong mucoadhesion, increasing primarily with higher polymer concentrations. The beads exhibited thermal stability and no chemical interaction with IND, showing improved mechanical properties. Furthermore, the beads remained stable during accelerated and long-term storage studies. The beads were found to be biocompatible, and IND encapsulation improved cell viability (>70 % in both models, 79 % in VN) and modified IND permeation through the models (6.3 % for F5 formulation (κ-Car 0.90 % w/v | Ser 1.2 % w/v| IND 3.0 g); 10.9 % for free IND, p < 0.05). Accordingly, κ-Car/Ser/IND beads were demonstrated to be a promising IND drug carrier to improve oral administration while mitigating the side effects of non-steroidal anti-inflammatories., Competing Interests: Declaration of competing interest The authors of this study declare no conflict of interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

This study investigated the single and multicomponent adsorption of three emerging pollutants, the basic dyes Rhodamine 6G (R6G), Auramine-O (AO), and Brilliant Green (BG) by using hydroxyapatite synthesized from Pirarucu scales as adsorbent (HAP). The adsorption process was studied using seven different systems: AO-single, R6G-single, BG-single, R6G + AO, BG + AO, BG + R6G, and R6G + AO + BG. For kinetics, the initial concentration of each adsorbate per system was 50 mg/L, the results showed that the singular adsorption of these dyes was best-represented by the pseudo-second-order model (q AO  = 62.54 mg/g, q R6G  = 7.91 mg/g, q BG  = 62.40 mg/g), however, the multicomponent adsorption was well-fitted by a pseudo-first-order model (ternary system: q AO  = 56.21 mg/g, q R6G  = 14.95 mg/g, q BG  = 60.62 mg/g). For equilibrium, the initial concentration of each adsorbate per system was 10-300 mg/L, and the single adsorption systems were best represented by the Langmuir model. Nonetheless, the results displayed in the multicomponent mixture showed the presence of inflection points of AO and R6G whenever BG was present in solution with C 0  > 150 mg/L, thus indicating that BG has greater affinity with HAP. The presence of inflection points in the curves represented a limitation for applying traditional equilibrium models, thus, an artificial neural network (ANN) was applied to non-linear curve fit this process and satisfactorily predicted the kinetics and equilibrium data. Finally, the analysis of thermodynamics for the ternary mixture revealed that the adsorption process is spontaneous (ΔG < 0), endothermic (ΔH > 0), and increases to a disorganized state as the temperature rises (ΔS > 0)., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

This study explores the utilization of adsorption and advanced oxidation processes for the degradation of ofloxacin (OFL) and ciprofloxacin (CIP) using a green functionalized carbon nanotube (MWCNT-OH/COOH-E) as adsorbent and catalyst material. The stability and catalytic activity of the solid material were proved by FT-IR and TG/DTG, which also helped to elucidate the reaction mechanisms. In adsorption kinetic studies, both antibiotics showed similar behavior, with an equilibrium at 30 min and 60% removal. The adsorption kinetic data of both antibiotics were well described by the pseudo-first-order (PFO) model. Different advanced oxidation processes (AOPs) were used, and the photolytic degradation was not satisfactory, whereas heterogeneous photocatalysis showed high degradation (⁓ 70%), both processes with 30 min of reaction. Nevertheless, ozonation and catalytic ozonation have resulted in the highest efficiencies, 90%, and 70%, respectively, after 30-min reaction. For AOP data modeling, the first-order model better described CIP and OFL in photocatalytic and ozonation process. Intermediates were detected by MS-MS analysis, such as P313, P330, and P277 for ciprofloxacin and P391 and P332 for ofloxacin. The toxicity test demonstrated that a lower acute toxicity was observed for the photocatalysis method samples, with only 3.1 and 1.5 TU for CIP and OFL, respectively, thus being a promising method for its degradation, due to its lower risk of inducing the proliferation of bacterial resistance in an aquatic environment. Ultimately, the analysis of MWCNT reusability showed good performance for 2 cycles and regeneration of MWCNT with ozone confirmed its effectiveness up to 3 cycles., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The crosslinking of the polymer matrix with compatible macromolecules results in a three-dimensional network structure that offers an enhancement in the controlled release properties of the material. In this sense, this work aimed to improve the release profile of mefenamic acid (MAC) through crosslinking strategies. κ-Carrageenan/sericin crosslinked blend was obtained by covalent and thermal crosslinking and the different formulations were characterized. The gastroresistant potential and release profile were evaluated in the dissolution assay. The effect and characterization of the particles were investigated. Multiple units presented high entrapment efficiency (94.11-104.25), high drug loading (36.50-47.50 %) and adequate particle size (1.34-1.57 mm) with rough surface and visually spherical shape. The Weibull model showed that drug release occurred by relaxation, erosion and Fickian diffusion. Material stability and absence of MAC -polymer interactions were demonstrated by FTIR and thermogravimetric analysis. DSC showed a stable character of MAC in the drug-loaded beads. Moreover, the application studies of κ-Car/Ser/carboxymethylcellulose in the in vitro intestine mode showed that the crosslinked blend increased cell viability (>85 %), while free MAC exhibited a cytotoxic effect. Finally, the crosslinked k-Car/Ser blend MAC -loaded showed promising properties of a sustained release form of anti-inflammatory drug., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The oil industry faces the challenge of reducing its high polluting potential, due to the presence of aromatic pollutants, such as polycyclic aromatic hydrocarbons (PAHs). Efforts have been made to mitigate the impact of PAHs in industry through the development of detection technologies and the implementation of mitigation strategies. This study presents the adsorption of fluoranthene, through a magnetic composite of graphene oxide and chitosan as a method of remediation of produced water. The efficiency of the process was evaluated through kinetic, equilibrium, thermodynamic, and characterization analyses. The nanocomposite was able to remove 90.9% of FLT after 60 min and showed a maximum adsorption capacity of 28.22 mg/g, demonstrating that they can be implemented to remove fluoranthene. Kinetic and equilibrium experimental data showed that physisorption is the predominant adsorptive mechanism; however, the process is also influenced by chemisorption, which occurs through electrostatic interactions between the surface of the material and the adsorbate. The thermodynamic study showed that fluoranthene and graphene composite have high affinity, and that the adsorption is exothermic and spontaneous. The results presented in this paper indicate that the magnetic composite is a potential and sustainable adsorbent for fluoranthene remediation., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

This paper investigated the uptake of CIP and OFL in single and multicomponent adsorptive systems using modified carbon nanotubes (CNTs) as adsorbent material. The characterization analyses of the pre- and post-process material by XPS, TG/DTG, FT-IR, SEM/EDS, and XRD helped in the elucidation of the mechanisms, indicating greater involvement of n-n and π -π interactions. In the kinetic studies, the simple systems with CIP and OFL were similar, both showed equilibrium time around 20/30 min and increased adsorptive capacity with increasing initial drug concentration. In the multicomponent system, different fractions of CIP and OFL were tested and the time to reach equilibrium also varied between 20 and 30 min. In general, the adsorption capacity of CIP is slightly lower than that of OFL under the conditions tested. The selectivity analysis of the system showed that the selectivity's of the two drugs are identical in equimolar fractions. The mathematical modeling of the kinetic data indicated that in monocomponent systems, the model of pseudo-second order (PSO) adequately described both CIP and OFL kinetics. Furthermore, with the implementation of Artificial Neural Networks (ANN), it was possible to obtain a more assertive prediction of the behavior of single and binary systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Modified release of multiparticulate pharmaceutical forms is a key therapeutic strategy to reduce side effects and toxicity caused by high and repeated doses of immediate-release oral drugs. This research focused on the encapsulation of indomethacin (IND) in the crosslinked k-Car/Ser polymeric matrix by covalent and thermal methods to evaluate drug delivery modulation and properties of the crosslinked blend. Therefore, the entrapment efficiency (EE %), drug loading (DL %) and physicochemical properties of the particles were investigated. The particles presented a spherical shape and a rough surface with a mean diameter of 1.38-2.15 mm (CCA) and 1.56-1.86 mm (thermal crosslink). FTIR investigation indicated the presence of IDM in the particles and X-ray pattern showed the maintenance of crystallinity of IDM. The in vitro release in acidic medium (pH 1.2) and phosphate buffer saline solution (pH 6.8) was 1.23-6.81 % and 81-100 %, respectively. Considering the results, the formulations remained stable after 6 months. The Weibull equation was adequately fitted for all formulations and a diffusion mechanism, swelling and relaxation of chain were observed. IDM-loaded k-carrageenan/sericin/CMC increases cell viability (> 75 % for neutral red and > 81 % for MTT). Finally, all formulations present gastro-resistance, pH response and altered release and have the potential to be used as drug delivery careers., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: We do not have other relationship or activities as a conflict of interest., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Cerium is an essential element for several applications in industry, therefore, recovering it from secondary sources is a promising strategy from an economic and environmental perspective. For this purpose, biosorption is a low-cost and effective alternative. The present work evaluated the recovery of Ce 3+ from aqueous solutions using alginate/vermiculite-based particles (ALEV) functionalized by ionic imprinting. From the kinetic assays, it was verified that the uptake of Ce 3+ followed the pseudo-second-order model and was mainly controlled by external diffusion. The Langmuir model better described the equilibrium data, and a maximum biosorption capacity of 0.671 mmol/g at 45 °C was attained. The evaluation of the thermodynamic quantities revealed that the process occurs spontaneously and endothermically. The particles reuse and Ce 3+ recovery were achieved using 0.1 mol/L HCl or 1.0 mol/L CaCl 2 solutions for up to four cycles of biosorption/desorption. The biosorbent was characterized before and posted Ce 3+ biosorption to investigate the morphology, textural properties, crystallinity, thermal resistance, composition, and functional groups of the biosorbent., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Declarations., (Copyright © 2023 Elsevier B.V. All rights reserved.)

A clay-based adsorbent (CBA) was purified from a sustainable precursor (raw clay, RC), which was obtained from the Amazon region in Brazil. The CBA was characterized using X-ray diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR), Brunauer-Emmet-Teller surface area (S BET , RC = 23.386 m 2 .g -1 , CBA = 33.020 m 2 .g -1 ), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), thermogravimetric analysis (TGA), cation exchange capacity (CEC, CBA = 44.75 cmol/kg), and point of zero charge analyses (pH PZC , CBA = 2.20). Subsequently, CBA was used to adsorb basic yellow 2 (BY2) dye from aqueous solutions. A CBA dosage (1 g/L), initial concentration of dye (C 0  = 15 mg/L), and pH (5.6) were ideal conditions for the BY2 dye removal of ~ 98%. The BY2 kinetics was better represented by the pseudo-first-order (PFO) model while the BY2 equilibrium was well represented by the Sips model, with a maximum adsorption capacity of q ms  = 18.04 mg/g at 28 °C. The negative values of ΔG° and ΔH° showed that the studied process is spontaneous and exothermic, while the values of isosteric heat (∆H st , -16 to -20 kJ/mol) suggest a predominance of physical interactions. The molecular chemical reactivity of BY2 was investigated using quantum chemical descriptors calculated based on Density Functional Theory (DFT) optimization of the dye molecule, and the results revealed a large energy gap value (4.3900 eV) and considerable chemical hardness (η = 2.1950 eV). Therefore, the correlation between DFT and experimental results consistently sustains that BY2 dye tends to be adsorbed on the CBA surface by electrostatic interactions, thus, this is the possible adsorption mechanism of this process., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Removal of emerging contaminants, such as antibiotics, from wastewater by adsorption is a simple, low-cost, and high-performance process; however, regeneration and reuse of the exhausted adsorbent are necessary to make the process economically viable. This study aimed to investigate the possibility of electrochemical-based regeneration of clay-type materials. For this, the calcined Verde-lodo (CVL) clay was saturated with the antibiotics ofloxacin (OFL) and ciprofloxacin (CIP) in one-component systems by an adsorption process and then subjected to photo-assisted electrochemical oxidation (0.45 A, 0.05 mol/L NaCl, UV-254 nm, and 60 min), which promotes both pollutant degradation and adsorbent regeneration. The external surface of the CVL clay was investigated by X-ray photoelectron spectroscopy before and after the adsorption process. The influence of regeneration time was evaluated for the CVL clay/OFL and CVL clay/CIP systems, and the results demonstrate high regeneration efficiencies after 1 h of photo-assisted electrochemical oxidation. Clay stability during regeneration was investigated by four successive cycles in different aqueous matrices (ultrapure water, synthetic urine, and river water). The results indicated that the CVL clay is relatively stable under the photo-assisted electrochemical regeneration process. Furthermore, CVL clay was able to remove antibiotics even in the presence of natural interfering agents. The hybrid adsorption/oxidation process applied here demonstrated the electrochemical-based regeneration potential of CVL clay for the treatment of emerging contaminants, since it can be operated quickly (1h of treatment) and with lower consumption of energy (3.93 kWh kg -1 ) than the traditional method of thermal regeneration (10 kWh kg -1 )., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

This study aimed to develop a natural and multiparticulate carrier of k-carrageenan (k-Car) and sericin (Ser) for encapsulation of indomethacin (IND) in order to minimize gastrointestinal effects caused by immediate-release. Increasing the amount of IND in the formulations subtly reduced the entrapment efficiency (EE) and drug loading (DL) due to matrix saturation. Sericin was essential to improve EE and DL when compared to pure k-Car (EE > 90 % and DL > 47 %) with suitable particle sizes (1.3461 ± 0.1891-1.7213 ± 0.1586 mm). The incorporation and integrity of IND in the particles were confirmed by analytical techniques of HPLC, XRD, FTIR, and SEM. Additionally, the k-Car/Ser matrix was pH-responsive with low IND release at pH 1.2 and extended-release at pH 6.8. The Weibull model had an adequate fit to the experimental data with R 2 aju 0.950.99 and AIC 82.4-24.9, with curves in parabolic profile (b < 1) and indicative of a controlled drug-release mechanism by diffusion. Besides, k-Car/Ser/IND and placebo were not cytotoxic (cell viability > 85 % at 150-600 μM) for the Caco-2 cell line. Therefore, the polymeric matrix is gastro-resistant, stable, and biocompatible to carry indomethacin and deliver it to the intestinal environment., Competing Interests: Declaration of competing interest No conflicts of interest were declared by the authors of this study., (Copyright © 2023 Elsevier B.V. All rights reserved.)

A green magnetic composite mCS/GO was synthesized using water hyacinth extract, as a reducing agent, and proanthocyanidin, as a crosslinking agent, for the adsorption of naphthalene from effluents. The green composite was evaluated using different characterization techniques to determine its thermal (TG/DTG), structural (BET, XPS and FTIR), crystallographic (XRD), and textural (SEM) properties in natura and post-adsorption. The results obtained through a central composite design (CCD) experiment indicated that the initial concentration of NAP and the adsorbent dosage are significant for the adsorption capacity. The adsorption assays indicated that physisorption, through π-π and hydrophobic interactions, were the main mechanism involved in the NAP adsorption. However, the adjustment to the PSO and Freundlich models, obtained through kinetic and equilibrium studies, indicated that chemisorption also influences the adsorptive process. The thermodynamic study indicated physisorption as the mechanism responsible for the NAP adsorption. Also, the adsorbent has high affinity for the adsorbate and the process is spontaneous and endothermic. The maximum adsorption capacity (q max ) of the green mCS/GO was 334.37 mg g -1 at 20 °C. Furthermore, the green mCS/GO was effectively regenerated with methanol and reused for five consecutive cycles, the percentage of NAP recovery went from approximately 91 to 75% after the fifth cycle. The green composite was also applied in the adsorption of NAP from river water samples, aiming to evaluate the feasibility of the method in real applications. The adsorption efficiency was approximately 70%. From what we know, this it is the first time that a green adsorbent was recycled after the polycyclic aromatic hydrocarbon (PAHs) adsorption process., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Currently, the world faces difficulties related to the quantity and quality of water because of industrial expansion, population growth, and urbanization intensification. Biosorption is considered a promising technology that can be applied to remove toxic metals (TMs) and rare-earth metals (REMs) in wastewater at low concentrations, due to its efficiency and low cost. In this work, we investigated different non-conventional biosorbents to remove metallic ions (TMs and REMs) in biosorptive affinity tests. Metallic affinity assays among lanthanum and different biosorbents showed that greater affinities were found for sericin-alginate beads crosslinked with polyvinyl alcohol (SAPVA) (0.280 mmol/g) and polyethylene glycol diglycidyl ether (SAPEG) (0.277 mmol/g), expanded vermiculite (0.281 mmol/g), Sargassum filipendula seaweed (0.287 mmol/g), and seaweed biomass waste (0.289 mmol/g). Among the biosorbents evaluated, SAPVA and SAPEG beads, besides to sericin-alginate beads crosslinked with proanthocyanidins (SAPAs) were selected for affinity assays with other REMs and TMs. Compared to other particles, SAPVA beads showed higher potential for biosorption by REMs with the following order of affinity: Yb 3+ > Dy 3+ > Nd 3+ > Ce 3+ > La 3+ . Additionally, the biosorptive affinity of TMs by SAPVA beads followed the order: Al 3+ > Cr 3+ > Pb 2+ > Cu 2+ > Cd 2+ > Zn 2+ > Ni 2+ ., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The use of mineral clays as alternative adsorbent has received attention due to their physicochemical characteristics, superficial negative charge, abundance of vermiculite (especially in Brazil), low cost, and chemical composition, which allows the material modification to increase the adsorptive capacity. This manuscript evaluated the use of expanded vermiculite (EV) and sodium-modified vermiculite (VNa) in the adsorption and ion exchange of Cd 2+ ions. The sodification was successfully carried out making the ion exchange capacity greater in the modified clay, confirmed by EDX, cation exchange capacity (CEC), DRX, and FTIR analysis. The CEC was 210 and 233 mEq/100 g for the EV and VNa, respectively, with 97.8% exchangeable ion (Na + ) in the VNa. FTIR spectra showed small variations in the groups related to ion exchange and XRD analysis indicated changes in the distance of the layers with loss of crystallinity after clay modification, which was recovered after cadmium adsorption. The kinetics became faster with an equilibrium time of 10 min for VNa and 45 min for EV. Cd 2+ removal by vermiculite above 99% was achieved. Pseudo-second order model best described the kinetics, in which the resistance to mass transfer in external film is the limiting step of the process and, once this resistance is overcome, the ion exchange happens quickly. Despite the decrease in surface area after sodification, the adsorptive capacity increased 158% in the sodified adsorbent, from 0.107 mmol/g for EV to 0.276 mmol/g for VNa, under the evaluated conditions., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Cefazolin (CFZ) is a ubiquitous antibiotic in hospital settings and has been recognized as an emerging contaminant due to its ecotoxicity. Despite the growing concern around this compound, the literature addressing feasible advanced techniques for CFZ uptake from aqueous matrices is still scarce. Thus, the objective of this work was to evaluate the adsorption of cefazolin on Spectrogel® organoclay in a batch system as an efficient remediation method. The optimization of experimental conditions was determined by a central composite rotational design. A pH study, as well as equilibrium, kinetic, and thermodynamic assays, was performed to assess the adsorption of CFZ on Spectrogel®. The kinetic and equilibrium models that best described the system were the external mass transfer resistance and Sips models, respectively. A removal efficiency above 80% was achieved, and the maximum adsorption capacity at 25 °C was 398.6 mg g -1 . The post-process contaminated organoclay was thermally regenerated. The outcomes of this work indicate that Spectrogel® is an environmentally friendly adsorbent for the removal of cefazolin from wastewater., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Cefazolin (CFZ) is an antibiotic widely used in veterinary and human medicine that has been detected in high residual levels in the environment and is therefore considered an emerging contaminant. This work evaluated the adsorption of this contaminant by Spectrogel® type C organoclay, in continuous mode using a fixed-bed column. The fluid dynamics and the effect of the CFZ concentration were evaluated. In addition, prior and post-process organoclay were characterized. The continuous system under the conditions of C 0  = 0.3 mmol/L and Q = 0.1 mL/min presented lower values of mass transfer zone (5.88 cm), whereas the system with C 0  = 0.5 mmol/L and Q = 0.1 mL/min achieved higher CFZ adsorption capacity (20 µmol/g). Phenomenological and mass-transfer models were applied to the experimental data. The dual-site diffusion (DualSD) model better described the breakthrough (BTC) data. Furthermore, density functional theory (DFT) calculation was performed at the molecular level to provide a better comprehension of CFZ adsorption., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The recovery of rare-earth from secondary sources is essential for cleaner production. The development of natural biocomposites is promising for this purpose. Sericin is a waste protein from silk manufacturing. The highly polar groups on the surface of sericin facilitate blending and crosslinking with other polymers to produce biocomposites with improved properties. In this work, we investigate ytterbium recovery onto a natural biocomposite based on sericin/alginate/poly(vinyl alcohol) (SAPVA) in packed-bed column, aiming to establish a profitable application for sericin. Effects of flow rate and ytterbium inlet concentration showed that the highest exhaustion biosorption capacity (128.39 mg/g) and lowest mass transfer zone (4.13 cm) were reached under the operating conditions of 0.03 L/h and 87.95 mg/L. Four reusability cycles were performed under the optimum operating conditions using 0.3 mol/L HNO 3 . Ytterbium recovery was highly successful; desorption efficiency was higher than 97% and a final ytterbium-rich concentrate (3870 mg/L) was 44 times higher than input concentration. Regenerated beads characterization showed that the cation exchange mechanism plays a major function in continuous biosorption of ytterbium. SAPVA beads also showed higher biosorption/desorption performance for ytterbium than other competing ions. These results suggest the application of SAPVA may be an alternative for large-scale ytterbium recovery., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The residue derived from the alginate extraction from S. filipendula was applied for the biosorption of aluminum from aqueous medium. The adsorptive capacity of the residue (RES) was completely evaluated in batch mode. The effect of pH, contact time, initial concentration, and temperature was assessed through kinetic, equilibrium, and thermodynamic studies. The biosorbent was characterized prior and post-Al biosorption by N 2 physisorption, Hg porosimetry, He pycnometry, and thermogravimetry analyses. Equilibrium was achieved in 60 min. Kinetics obeys pseudo-second-order model at aluminum higher concentrations. Isotherms followed Freundlich model at low temperature (293.15 K) and D-R or Langmuir model at higher temperatures (303 and 313 K). Data modeling indicated the occurrence of both chemical and physical interactions in the aluminum adsorption mechanism using RES. The maximum adsorption capacity obtained was 1.431 mmol/g at 293 K. The biosorption showed a spontaneous, favorable, and exotherm character. A simplified batch design was performed, indicating that the residue is a viable biosorbent, achieving high percentages of removal using low biomass dosage., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

In a scenario of high demand, low availability, and high economic value, the recovery of rare-earth metals from wastewater is economically and environmentally attractive. Bioadsorption is a promising method as it offers simple design and operation. The aim of this study was to investigate lanthanum bioadsorption using a polymeric bioadsorbent of sericin/alginate/poly(vinyl alcohol)-based biocomposite. Batch system assays were performed to evaluate the equilibrium, thermodynamics, regeneration, and selectivity of bioadsorption. The maximum capture amount of lanthanum at equilibrium was 0.644 mmol/g at 328 K. The experimental equilibrium data were better fitted by Langmuir and Dubinin-Radushkevich isotherms. Ion exchange mechanism between calcium and lanthanum (2:3 ratio) was confirmed by bioadsorption isotherms. Thermodynamic quantities showed that the process of lanthanum bioadsorption was spontaneous (-17.586, -19.244, and -20.902 kJ/mol), endothermic (+15.372 kJ/mol), and governed by entropic changes (+110.543 J/mol·K). The reusability of particles was achieved using 0.1 mol/L HNO 3 /Ca(NO 3 ) 2 solution for up to five regeneration cycles. The bioadsorbent selectivity followed the order of lanthanum > cadmium > zinc > nickel. Additionally, characterization of the biocomposite prior to and post lanthanum bioadsorption showed low porosity (9.95 and 12.35%), low specific surface area (0.054 and 0.019 m 2 /g), amorphous character, and thermal stability at temperatures up to 473 K. This study shows that sericin/ alginate/poly(vinyl alcohol)-based biocomposites are effective in the removal and recovery of lanthanum from water.

Different polymer matrix compositions based on sericin and alginate blend (using or not the covalent crosslinking agents dibasic sodium phosphate, polyvinyl alcohol and polyethylene glycol) were evaluated to entrap naproxen. Sericin has been shown to be essential for improving incorporation efficiency. Comparing the formulations with and without crosslinking agent, the best results were obtained for that composed only of sericin and alginate, with satisfactory values of entrapment efficiency (>80%) and drug loading capacity (>20%). In this case, delayed release (<10% in acid medium) and prolonged release (~360 min) were achieved, with a complex release mechanism involving swelling and polymer chain relaxation. The incorporation of the drug could be confirmed by the techniques of characterization of X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR), as well as drug compatibility with the polymer matrix. In addition, particles of suitable size for multiparticulate systems were obtained and with higher thermal stability when compared to the pure drug., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Sericin is a soluble globular protein, present in Bombyx mori silkworm cocoons. Sericin's properties can be improved to expand its application by producing blends with other substances, such as alginate polysaccharide and crosslinking agent poly(vinyl alcohol). This study evaluates the use of alginate and sericin particles chemically crosslinked with poly(vinyl alcohol) (SAPVA) for batch bioadsorption of rare-earth element ytterbium from aqueous medium. The equilibrium study showed that the maximum bioadsorption capacity for ytterbium was 0.642 mmol/g at 55 °C. Equilibrium data fit both Langmuir and Dubinin-Radushkevich models. The estimation of thermodynamic parameters showed that there was an increase in the entropy change, and that the bioadsorption process is endothermic and spontaneous. Characterization analyzes revealed that SAPVA particles, even after ytterbium bioadsorption, showed spherical shape, homogeneous composition, amorphous structure, low surface area, macropores, and low porosity. After the first regeneration cycle, the amount of captured ytterbium ions showed a slight increase (about 0.01 mmol/g) and calcium ions were completely released by SAPVA particles. Bioadsorbent particles separated selectively ytterbium from synthetic effluent containing different toxic metal ions. These results show that the SAPVA particles can be used as an effective bioabsorbent to remove and recover ytterbium from wastewater., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Propranolol hydrochloride is a popular anti-hypertensive and pollutant of emerging concern because of potential ecological risks to aquatic environment. In this study, biosorption is presented as an advanced approach for propranolol uptake from aqueous media. The remaining biomass of alginate extraction from brown seaweed (RSF) was tested as biosorbent owing to its key binding sites, namely carboxyl and hydroxyl functional groups. The high 93% removal efficiency achieved consolidates RSF as effective biosorbent for propranolol environmental remediation and values this waste material, which has been largely discarded in industry after alginate extraction. RSF had morphology, porosity, chemical composition, and thermal behavior characterized prior and post to application in propranolol biosorption. Molecular sieving effects were excluded by assessing the molecular geometry of propranolol. The kinetics was inspected by both rate laws and mass transfer models. Langmuir, Freundlich, and Dubinin-Radushkevich equations were tested for experimental isotherms. Propranolol biosorption onto RSF was further inspected by thermodynamic parameters, including isosteric heat.

This work investigated the use of acidified dealginated residue from Sargassum filipendula algae for biosorption of silver in fixed bed column. This biosorbent was esterified for carboxyl and sulfonate groups to investigate the influence of these groups on silver removal percentage. Potentiometric titration was also evaluated on acidified and esterified biosorbents. Porosity and specific weight were determined by helium picnometry and mercury porosimetry techniques. The results showed that carboxyl and sulfonate groups were significant on silver biosorption. Potentiometric titration showed that esterified and acidified biosorbents presented different acid groups. The porosity of the acidified biosorbent was around 40%. Fixed bed assays were conducted to evaluate the influence of inlet concentration and feed flow rate of silver. Higher percentage removal of silver was obtained at 1.0 mmol · L -1 and 0.5 mL · min -1 . Modified dose-response model obtained the best prediction of experimental data among breakthrough curve models.

In this study, two novel low water-soluble sericin and alginate-based biosorbents were successfully developed for precious metal removal from wastewater: sericin and alginate particles chemically crosslinked by proantocyanidins (SAPAs) and sericin, alginate and polyvinyl alcohol particles (SAPVA). The proportions of proantocynidins (PAs) or polyvinyl alcohol (PVA) added to sericin (2.5% w/v) and alginate (2.0% w/v) blend were 0.5, 1.5, 2.5 and 3.5% w/v. Among these concentrations, particles produced with 0.5% w/v of PVA or 2.5% w/v of PAs presented the lowest water solubility percentages (3.74 ± 0.05 and 3.56 ± 0.21%, respectively) and the following metallic affinity order: AuCl 4 -  > PdCl 4 2-  > PtCl 6 2-  > Ag + . Then, gold biosorption kinetics by SAPAs was evaluated at three gold initial concentrations (72.88, 187.12, and 273.79 mg/L), and its performance was compared to activated carbon adsorbent uptake. The data modeling revealed that the process follows pseudo-first-order kinetics and is mainly controlled by external diffusion. SAPAs before and after gold biosorption (SAPAs-gold) were characterized by scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, optical microscopy, helium pycnometry, mercury porosimetry, N 2 physisorption, and Fourier-transform infrared spectroscopy.

The adsorption characteristics of C.I. basic blue 26 (BB26) from aqueous solutions onto H 3 PO 4 -activated carbons (ACs) produced from açai stones (Euterpe oleracea Martius) and Brazil nut shells (Bertholletia excelsa H. B. K) were investigated in a batch system. The ACs were characterized by XRD, FT-IR, N 2 adsorption at 77 K, mercury porosimetry, and acidity/basicity analysis. The pseudo-first-order, pseudo-second-order kinetic models and intraparticle diffusion model were used for the kinetic interpretations. The adsorption processes follow the pseudo-second-order kinetic model. The Boyd plots revealed that the adsorption processes were mainly controlled by film diffusion. Equilibrium data were analyzed by the Langmuir and Freundlich models, at different temperatures. The equilibrium data were best represented by the Langmuir isotherm. The adsorption processes were found to be favorable, exothermic, and spontaneous. The açai stones and Brazil nut shells-based ACs were shown to be effective adsorbents for removal of BB26 from aqueous solutions.

The alginate extraction residue (RES) from the Brazilian Sargassum filipendula was successfully employed as biosorbent in this binary equilibrium study, revealing a greater affinity and selectivity for Cr(III) than for Zn(II). Experimental results also revealed that the process is of endothermic nature and well adjusted by Langmuir-Freundlich binary model. The X-ray photoelectron spectroscopy (XPS) analysis revealed that coordination with hydroxyl groups of RES prevailed in Cr removal, followed by carboxyl-metal complexation. As far as Zn(II) is concerned, ion exchange with carboxylate groups of RES was the largest contributor. Nevertheless, scanning electron microscopy coupled with Fourier transform infrared spectroscopy indicated the participation of sulfate functions in a minor degree.

The application of biosorption operation has gained attention in the removal and retrieval of toxic metal ions from water bodies. Wastewater from industrial activity generally presents great complexity due to the coadsorption of cations to the inactive biomass binding sites. In this work, the competitive biosorption of Cu(II) and Ag(I) ions was studied in batch systems. A kinetic study applying a non-acidified and acidified waste of Sargassum filipendula in equimolar and non-equimolar metal samples was carried out and the acidified biosorbent was selected due to higher removal rates and selectivity of silver ions. The assays were performed with 2 g L -1 of biosorbent concentration at 25 °C for 12 h and pH was controlled at around 5.0. Copper presented higher affinity for the biosorbent and a fast biosorption kinetic profile, while silver equilibrium times exhibited dependence on the copper concentration. External diffusion is the rate-limiting step in Cu(II) ion removal and it might also limit the kinetic rates of Ag(I) ions with intraparticle diffusion, depending on the initial concentration of metal cations. The ion-exchange mechanism is evidenced and complexation and electrostatic attraction mechanisms might be suggested, explained by simultaneous chemisorption and physisorption processes during the operation. Calcium and sodium were released in considerable amounts by the ion-exchange mechanism. Characterization analyses confirmed the role of several functional groups in the competitive biosorption accompanied by a homogenous covering of both metal ions on the surface of the particles. Particle porosity analyses revealed that the material is macroporous and an appreciable amount of macropores are filled with metal cations after biosorption.

In last decades, the biosorption process has become one of the main alternative treatment technologies for the removal of pollutants from dilute aqueous solution. Among these pollutants, toxic metals have drawn attention due to their negative effects in human body and food chain. Even though biosorption is considered a cost-effective and eco-friendly technology to remove toxic metals from dilute wastewaters, there are still obstacles that restrain its commercialization. For this reason, various scientific articles and patents have been published each year to make more effective and economical this technology. This review reports an overview of past achievements, current research of biosorption studies, and future trends for the development of the biosorption as sustainable cleaner technology. Mechanisms of metal uptake, recovery and biosorbent regeneration, process design, commercial application of biosorbents, and patents registered are presented. Finally, future aspects in biosorption research and suggestions for its application will be discussed.

The aim of this work was an experimental and theoretical investigation of the influence of electrolyte (NaCl) and surfactant (SP), as textile auxiliary agents (TAAs), onto reactive blue 5G (RB5G) dye removal by applying untreated fish scales (FS) in batch system. Kinetic and equilibrium studies were performed, aiming at the comprehension of the mass transfer mechanisms through phenomenological modeling. The biosorbent was texturally characterized, to investigate the adsorbent's characteristics and to support the models' assumptions. Hence, a 'physically meaningful' modeling to assess different systems containing dye-TAA mixtures was employed. The experimental results indicated that despite the FS nonporous characteristics, it showed remarkable adsorption capacities (≈291 mg g-1), which may be ascribed to the adsorbent-adsorbate affinity and to dye-aggregates adsorption onto the FS surface. Those results evidence a potential use of FS as an alternative biosorbent material. The mathematical model was able to identify the rate-limiting step of the process; to predict the adsorption kinetics and equilibrium condition, comprising the description of aggregates formation; and to successfully predict kinetic behavior of independent data in simulated real effluent. Those results indicate that the model can be used to simulate operating conditions and, therefore, support the design, optimization, and scale-up of adsorption processes.

In this study, particles produced from sericin-alginate blend were used as non-conventional bioadsorbent for removing Cr(III) and Cr(VI) from aqueous solutions. Besides chromium mitigation, the use of sericin-alginate particles as bioadsorbent aims to offer an environmental solution of added value for sericin, which is a by-product from silk industry. Sericin-alginate particles in natura and loaded with Cr(III) and Cr(VI) were characterized using N 2 physical adsorption analysis, optical microcopy, mercury porosimetry, helium pycnometry, scanning electron microscope coupled with energy dispersive X-ray spectrometer, Fourier transform infrared spectrometer, and X-ray diffraction. Kinetic studies on the removal of Cr(III) (at pH = 3.5) and Cr(VI) (at pH = 2) indicate the ion exchange mechanism with Ca(II) and the predominance of external mass transfer resistance. Cr(VI) uptake occurs through an adsorption-coupled reduction process, and bioadsorption equilibrium is reached after ~ 1000 min. Cr(III) bioadsorption occurs faster (~ 210 min). The Cr(VI) bioadsorption is endothermic, as bioadsorption capacity increases with temperature: 0.0783 mmol/g (20 °C), 0.1960 mmol/g (30 °C), 0.4570 mmol/g (40 °C), and 0.7577 mmol/g (55 °C). The three-parameter isotherm model of Tóth best represents the equilibrium data of total chromium. From Langmuir isotherm model, the maximum bioadsorption capacity is higher for total chromium, 0.25 mmol/g (30 °C), than for trivalent chromium, 0.023 mmol/g (30 °C). The comparison of bioadsorption capacities with different biomaterials confirms sericin-alginate particles as potential bioadsorbent of chromium.

Several beneficial effects on the skin have been reported for coumestrol (COU), such as protection against photoaging and improvement of skin elasticity and thickness in postmenopausal women. However no reports on the effect of COU on wound healing were found. Nevertheless, COU has low aqueous solubility, which is a crucial limitation for biological tests. The present study was designed as a two-step experiment to evaluate the wound healing effect of COU. First, we used fibroblasts and the experimental in vitro artificial wound model, scratch assay, to compare the effects of COU free, dissolved in dimethyl sulfoxide (DMSO) or Dulbecco's modified Eagle's medium (DMEM), or associated with hydroxypropyl-β-cyclodextrin (HPβCD). The 50 μM (66.1%) and 10 μM (56.3%) COU/HPβCD association induced cell proliferation and migration in inflicted wounds. Subsequently, the in vivo wound healing experimental model (Wistar rats) revealed that COU/HPβCD incorporated into hypromellose (HPMC) hydrogel had similar efficacy in wound healing in comparison to the positive control (Dersani®), with the advantage that 50% wound healing was achieved within a shorter period. In summary, the results successfully demonstrated, for the first time, the wound healing effect of COU/HPβCD incorporated into HPMC hydrogel and describe the feasibility of the biological tests with the use of HPβCD instead DMSO., (Copyright © 2018 Elsevier B.V. All rights reserved.)