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1.
Int J Biol Macromol ; 263(Pt 1): 130224, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38387636

RESUMO

Treating wastewater polluted with organic dyestuffs is still a challenge. In that vein, facile synthesis of a structurally simple composite of chitosan with montmorillonite (CS-MMT) using glutaraldehyde as a crosslinker and the magnetized analogue (MAG@CS-MMT) was proposed as versatile adsorbents for the cationic dye, basic Fuchsin (FUS). Statistical modeling of the adsorption process was mediated using Box-Behnken (BB) design and by varying the composite dose, pH, [FUS], and contact time. Characterization of both composites showed an enhancement of surface features upon magnetization, substantiating a better FUS removal of the MAG@CS-MMT (%R = 98.43 %) compared to CS-MMT (%R = 68.02 %). The surface area analysis demonstrates that MAG@CS-MMT possesses a higher surface area, measuring 41.54 m2/g, and the surface analysis of the magnetized nanocomposite, conducted using FT-IR and Raman spectroscopies, proved the presence of FeO peaks. In the same context, adsorption of FUS onto MAG@CS-MMT fitted-well to the Langmuir isotherm model and the maximum adsorption capacities (qm) were 53.11 mg/g for CS-MMT and 88.34 mg/g for MAG@CS-MMT. Kinetics investigation shows that experimental data fitted well to the pseudo-second order (PSO) model. Regeneration study reveals that MAG@CS-MMT can be recovered effectively for repeated use with a high adsorption efficiency for FUS.


Assuntos
Quitosana , Corantes de Rosanilina , Poluentes Químicos da Água , Bentonita/química , Águas Residuárias , Quitosana/química , Espectroscopia de Infravermelho com Transformada de Fourier , Adsorção , Cinética , Poluentes Químicos da Água/química , Concentração de Íons de Hidrogênio
2.
Environ Sci Pollut Res Int ; 30(56): 118764-118781, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37919500

RESUMO

The existence of methylene blue (MB) in wastewater even as traces is raising environmental concerns. In this regard, the performances of four adsorbents, avocado stone biochar (AVS-BC), montmorillonite (MMT), and their magnetite Fe3O4-derived counterparts, were compared. Results showed the superior performance of Fe3O4@AVS-BC and Fe3O4@MMT nanocomposites with removal percentages (%R) of 95.59% and 88%. The morphological features of AVS-BC as revealed by SEM analysis showed a highly porous surface compared to a plane and smooth surface in the case of MMT. Surface analysis using FT-IR and Raman spectroscopies corroborated the existence of the Fe-O peaks upon loading with magnetite. The XRD analysis confirmed the formation of cubic magnetite nanoparticles. The adsorption process in the batch mode was optimized using central composite design (CCD). Equilibrium and kinetic isotherms showed that the adsorption of MB onto Fe3O4@AVS-BC fitted well with the Langmuir isotherm and the pseudo-second-order (PSO) model. The maximum adsorption capacity (qm) was 118.9 mg/g (Fe3O4@AVS-BC) and 72.39 mg/g (Fe3O4@MMT). The Fe3O4@AVS-BC showed a higher selectivity toward MB compared to other organic contaminants. The MB-laden adsorbent was successfully used for the remediation of Cr (III), Ni (II), and Cd (II) with removal efficiencies hitting 100% following thermal activation.


Assuntos
Nanocompostos , Persea , Poluentes Químicos da Água , Adsorção , Bentonita , Óxido Ferroso-Férrico , Cinética , Azul de Metileno , Espectroscopia de Infravermelho com Transformada de Fourier , Poluentes Químicos da Água/análise , Recuperação e Remediação Ambiental
3.
Environ Sci Pollut Res Int ; 30(34): 82387-82405, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37326738

RESUMO

This research aims to remove two phenothiazines, promazine (PRO) and promethazine (PMT), from their individual and binary mixtures using olive tree pruning biochar (BC-OTPR). The impact of individual and combinatory effects of operational variables was evaluated for the first time using central composite design (CCD). Simultaneous removal of both drugs was maximized utilizing the composite desirability function. At low concentrations, the uptake of PRO and PMT from their individual solutions was achieved with high efficiency of 98.64%, 47.20 mg/g and 95.87%, 38.16 mg/g, respectively. No major differences in the removal capacity were observed for the binary mixtures. Characterization of BC-OTPR confirmed successful adsorption and showed that the OTPR surface was predominantly mesoporous. Equilibrium investigations revealed that the Langmuir isotherm model best describes the sorption of PRO/PMT from their individual solutions with maximum adsorption capacities of 640.7 and 346.95 mg/g, respectively. The sorption of PRO/PMT conforms to the pseudo-second-order kinetic model. Regeneration of the adsorbent surface was successfully done with desorption efficiencies of 94.06% and 98.54% for PRO and PMT, respectively, for six cycles.


Assuntos
Olea , Poluentes Químicos da Água , Águas Residuárias , Prometazina , Promazina , Cinética , Adsorção , Carvão Vegetal , Poluentes Químicos da Água/análise , Concentração de Íons de Hidrogênio
4.
Heliyon ; 9(5): e15802, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-37180896

RESUMO

Pharmaceutically active compounds (PhACs) represent an emerging class of contaminants. With a potential to negatively impact human health and the ecosystem, existence of pharmaceuticals in the aquatic systems is becoming a worrying concern. Antibiotics is a major class of PhACs and their existence in wastewater signifies a health risk on the long run. With the purpose of competently removing antibiotics from wastewater, cost-effective, and copiously available waste-derived adsorbents were structured. In this study, mango seeds kernel (MSK), both as a pristine biochar (Py-MSK) and as a nano-ceria-laden (Ce-Py-MSK) were applied for the remediation of rifampicin (RIFM) and tigecycline (TIGC). To save time and resources, adsorption experiments were managed using a multivariate-based scheme executing the fractional factorial design (FrFD). Percentage removal (%R) of both antibiotics was exploited in terms of four variables: pH, adsorbent dosage, initial drug concentration, and contact time. Preliminary experiments showed that Ce-Py-MSK has higher adsorption efficiency for both RIFM and TIGC compared to Py-MSK. The %R was 92.36% for RIFM compared to 90.13% for TIGC. With the purpose of comprehending the adsorption process, structural elucidation of both sorbents was performed using FT-IR, SEM, TEM, EDX, and XRD analyses which confirmed the decoration of the adsorbent surface with the nano-ceria. BET analysis revealed that Ce-Py-MSK has a higher surface area (33.83 m2/g) contrasted to the Py-MSK (24.72 m2/g). Isotherm parameters revealed that Freundlich model best fit Ce-Py-MSK-drug interactions. A maximum adsorption capacity (qm) of 102.25 and 49.28 mg/g was attained for RIFM and TIGC, respectively. Adsorption kinetics for both drugs conformed well with both pseudo-second order (PSO) and Elovich models. This study, therefore, has established the suitability of Ce-Py-MSK as a green, sustainable, cost-effective, selective, and efficient adsorbent for the treatment of pharmaceutical wastewater.

5.
Nanomaterials (Basel) ; 13(9)2023 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-37176989

RESUMO

Drugs and pharmaceuticals are an emergent class of aquatic contaminants. The existence of these pollutants in aquatic bodies is currently raising escalating concerns because of their negative impact on the ecosystem. This study investigated the efficacy of two sorbents derived from orange peels (OP) biochar (OPBC) for the removal of the antineoplastic drug daunorubicin (DNB) from pharmaceutical wastewater. The adsorbents included pristine (OPBC) and magnetite (Fe3O4)-impregnated (MAG-OPBC) biochars. Waste-derived materials offer a sustainable and cost-effective solution to wastewater bioremediation. The results showed that impregnation with Fe3O4 altered the crystallization degree and increased the surface area from 6.99 m2/g in OPBC to 60.76 m2/g in the case of MAG-OPBC. Placket-Burman Design (PBD) was employed to conduct batch adsorption experiments. The removal efficiency of MAG-OPBC (98.51%) was higher compared to OPBC (86.46%). DNB adsorption onto OPBC followed the D-R isotherm, compared to the Langmuir isotherm in the case of MAG-OPBC. The maximum adsorption capacity (qmax) was 172.43 mg/g for MAG-OPBC and 83.75 mg/g for OPBC. The adsorption kinetics for both sorbents fitted well with the pseudo-second-order (PSO) model. The results indicate that MAG-OPBC is a promising adsorbent for treating pharmaceutical wastewater.

6.
Environ Sci Pollut Res Int ; 30(28): 71554-71573, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-33829381

RESUMO

In the current investigation, watermelon rinds (WMR) have been utilized as an eco-friendly and cost-efficient adsorbent for acridine orange (AO) from contaminated water samples. Adsorption of AO onto raw (RWM) and thermally treated rinds (TTWM250 and TTWM500) has been studied. The adsorption efficiency of the three adsorbents was evaluated by measuring the % removal (%R) of AO and the adsorption capacity (qe, mg/g). Dependent variables (%R and qe) were optimized as a function of four factors: pH, sorbent dosage (AD), the concentration of AO (DC), and contact time (ST). Box-Behnken (BB) design has been utilized to obtain the optimum adsorption conditions. Prepared adsorbents have been characterized using scanning electron microscopy (SEM), Fourier-transform infrared (FT-IR), and Raman spectroscopies. The surface area of RWM, TTWM250, and TTWM500, as per the Brunauer-Emmett-Teller (BET) analysis, was 2.66, 2.93, and 5.03 m2/g, respectively. Equilibrium investigations suggest that Freundlich model was perfectly fit for adsorption of AO onto TTWM500. Maximum adsorption capacity (qmax) of 69.44 mg/g was obtained using the Langmuir equation. Adsorption kinetics could be best described by the pseudo-second-order (PSO) model. The multi-cycle sorption-desorption study showed that TTWM500 could be regenerated with the adsorption efficiency being preserved up to 87% after six cycles.


Assuntos
Laranja de Acridina , Poluentes Químicos da Água , Laranja de Acridina/análise , Laranja de Acridina/química , Espectroscopia de Infravermelho com Transformada de Fourier , Poluentes Químicos da Água/análise , Cinética , Adsorção
7.
Pharmaceuticals (Basel) ; 15(7)2022 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-35890186

RESUMO

Tigecycline (TIGC) reacts with 7,7,8,8-tetracyanoquinodimethane (TCNQ) to form a bright green charge transfer complex (CTC). The spectrum of the CTC showed multiple charge transfer bands with a major peak at 843 nm. The Plackett-Burman design (PBD) was used to investigate the process variables with the objective being set to obtaining the maximum absorbance and thus sensitivity. Four variables, three of which were numerical (temperature-Temp; reagent volume-RV; reaction time-RT) and one non-numerical (diluting solvent-DS), were studied. The maximum absorbance was achieved using a factorial blend of Temp: 25 °C, RV: 0.50 mL, RT: 60 min, and acetonitrile (ACN) as a DS. The molecular composition that was investigated using Job's method showed a 1:1 CTC. The method's validation was performed following the International Conference of Harmonization (ICH) guidelines. The linearity was achieved over a range of 0.5-10 µg mL-1 with the limits of detection (LOD) and quantification (LOQ) of 166 and 504 ng mL-1, respectively. The method was applicable to TIGC per se and in formulations without interferences from common additives. The application of the Benesi-Hildebrand equation revealed the formation of a stable complex with a standard Gibbs free energy change (∆G°) value of -26.42 to -27.95 kJ/mol. A study of the reaction kinetics revealed that the CTC formation could be best described using a pseudo-first-order reaction.

8.
Nanomaterials (Basel) ; 12(3)2022 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-35159724

RESUMO

Cobalt oxide (Co3O4) nanoparticles supported on olive stone biochar (OSBC) was used as an efficient sorbent for rifampicin (RIFM) and tigecycline (TIGC) from wastewater. Thermal stabilities, morphologies, textures, and surface functionalities of two adsorbents; OSBC and Co-OSBC were compared. BET analysis indicated that Co-OSBC possesses a larger surface area (39.85 m2/g) and higher pore-volume compared to the pristine OSBC. FT-IR analysis showed the presence of critical functional groups on the surface of both adsorbents. SEM and EDX analyses showed the presence of both meso- and macropores and confirmed the presence of Co3O4 nanoparticles on the adsorbent surface. Batch adsorption studies were controlled using a two-level full-factorial design (2k-FFD). Adsorption efficiency of Co-OSBC was evaluated in terms of the % removal (%R) and the sorption capacity (qe, mg/g) as a function of four variables: pH, adsorbent dose (AD), drug concentration, and contact time (CT). A %R of 95.18% and 75.48% could be achieved for RIFM and TIGC, respectively. Equilibrium studies revealed that Langmuir model perfectly fit the adsorption of RIFM compared to Freundlich model for TIGC. Maximum adsorption capacity (qmax) for RIFM and TIGC was 61.10 and 25.94 mg/g, respectively. Adsorption kinetics of both drugs could be best represented using the pseudo-second order (PSO) model.

9.
Molecules ; 26(20)2021 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-34684719

RESUMO

Adsorptive removal of methylene blue (MB) from contaminated water samples was achieved using green tea waste (GTW). Adsorption of MB onto raw (RGTW) and thermally treated waste (TTGTW250-TTGTW500) was explored. The performance of the tested adsorbents was assessed in terms of percentage removal of MB (%R) and adsorption capacity (qe, mg/g). A full factorial design (FFD) was employed to optimize the adsorption of MB onto both RGTW and TTGTW500. Four factors were studied: pH, adsorbent dose (AD), dye concentration (DC), and contact time (CT). Value for %R of 96.58% and 98.07% were obtained using RGTW and TTGTW500, respectively. FT-IR and Raman analyses were used to study the surfaces of the prepared adsorbents, and the IR spectrum showed the existence of a variety of functionalities on the surfaces of both the RGTW and thermally treated samples. BET analysis showed the presence of mesopores and macropores in the case of RGTW and micropores in the case of thermally processed adsorbents. Equilibrium studies indicated that the Freundlich isotherm best described the adsorption of MB onto both adsorbents. The maximum adsorption capacity (qmax) was found to be 68.28 and 69.01 mg/g for RGTW and TTGTW500, respectively, implying the superior capacity of TTGTW500 in removing MB. Adsorption of MB was found to proceed via chemisorption (RGTW) and physisorption (TTGTW500), as indicated by the Dubinin-Radushkevich (D-R) isotherm. A pseudo-second order (PSO) model best demonstrated the kinetics of the MB adsorption onto both adsorbents.

10.
Nanomaterials (Basel) ; 11(4)2021 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-33918728

RESUMO

Olive stone biochars (OSBC), both pristine and following magnetization (MAG-OSBC), were utilized as eco-friendly and cost-effective sorbents for the antituberculosis, clofazimine (CLOF). Morphologies, textures, surface functionalities, and thermal stabilities of both adsorbents were explored using SEM, EDX, TEM, BET, FT-IR, Raman, XRD and TGA analyses. SEM analysis showed meso- and macroporous surfaces. BET data showed that the MAG-OSBC possesses a larger surface area (33.82 m2/g) and pore volume. Batch adsorption studies were conducted following the experimental scenario of Box-Behnken (BB) design. The adsorption efficiency of both adsorbents was evaluated in terms of the % removal (%R) and the sorption capacity (qe, mg/g). Dependent variables (%R and qe) were maximized as a function of four factors: pH, sorbent dose (AD), the concentration of CLOF ([CLOF]), and contact time (CT). A %R of 98.10% and 98.61% could be obtained using OSBC and MAG-OSBC, respectively. Equilibrium studies indicated that both Langmuir and Freundlich models were perfectly fit for adsorption of CLOF. Maximum adsorption capacity (qmax) of 174.03 mg/g was obtained using MAG-OSBC. Adsorption kinetics could be best illustrated using the pseudo-second-order (PSO) model. The adsorption-desorption studies showed that both adsorbents could be restored with the adsorption efficiency being conserved up to 92% after the sixth cycles.

11.
Molecules ; 26(8)2021 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-33921054

RESUMO

Biochars (BC) of spent coffee grounds, both pristine (SCBC) and impregnated with titanium oxide (TiO2@SCBC) were exploited as environmentally friendly and economical sorbents for the fluroquinolone antibiotic balofloxacin (BALX). Surface morphology, functional moieties, and thermal stabilities of both adsorbents were scrutinized using SEM, EDS, TEM, BET, FTIR, Raman, and TG/dT analyses. BET analysis indicated that the impregnation with TiO2 has increased the surface area (50.54 m2/g) and decreased the pore size and volume. Batch adsorption experiments were completed in lights of the experimental set-up of Plackett-Burman design (PBD). Two responses were maximized; the % removal (%R) and the adsorption capacity (qe, mg/g) as a function of four variables: pH, adsorbent dosage (AD), BALX concentration ([BALX]), and contact time (CT). %R of 68.34% and 91.78% were accomplished using the pristine and TiO2@SCBC, respectively. Equilibrium isotherms indicated that Freundlich model was of a perfect fit for adsorption of BALX onto both adsorbents. Maximum adsorption capacity (qmax) of 142.55 mg/g for SCBC and 196.73 mg/g for the TiO2@SCBC. Kinetics of the adsorption process were best demonstrated using the pseudo-second order (PSO) model. The adsorption-desorption studies showed that both adsorbents could be restored with the adsorption efficiency being conserved up to 66.32% after the fifth cycles.


Assuntos
Carvão Vegetal/química , Café , Fluoroquinolonas/química , Poluentes Químicos da Água/química , Adsorção , Titânio/química
12.
Nanomaterials (Basel) ; 11(1)2020 Dec 24.
Artigo em Inglês | MEDLINE | ID: mdl-33374367

RESUMO

Non-magnetic and magnetic low-cost biochar (BC) from date pits (DP) were applied to remove tigecycline (TIGC) from TIGC-artificially contaminated water samples. Pristine biochar from DP (BCDP) and magnetite-decorated biochar (MBC-DP) were therefore prepared. Morphologies and surface chemistries of BCDP and MBC-DP were explored using FT-IR, Raman, SEM, EDX, TEM, and BET analyses. The obtained IR and Raman spectra confirmed the presence of magnetite on the surface of the MBC-DP. SEM results showed mesoporous surface for both adsorbents. BET analysis indicated higher amount of mesopores in MBC-DP. Box-Behnken (BB) design was utilized to optimize the treatment variables (pH, dose of the adsorbent (AD), concentration of TIGC [TIGC], and the contact time (CT)) and maximize the adsorptive power of both adsorbents. Higher % removal (%R), hitting 99.91%, was observed using MBC-DP compared to BCDP (77.31%). Maximum removal of TIGC (99.91%) was obtained using 120 mg/15 mL of MBC-DP for 10 min at pH 10. Equilibrium studies showed that Langmuir and Freundlich isotherms could best describe the adsorption of TIGC onto BCDP and MBC-DP, respectively, with a maximum adsorption capacity (qmax) of 57.14 mg/g using MBC-DP. Kinetics investigation showed that adsorption of TIGC onto both adsorbents could be best-fitted to a pseudo-second-order (PSO) model.

13.
Molecules ; 25(22)2020 Nov 19.
Artigo em Inglês | MEDLINE | ID: mdl-33228258

RESUMO

In the current study, eco-structured and efficient removal of the veterinary fluoroquinolone antibiotic sarafloxacin (SARA) from wastewater has been explored. The adsorptive power of four agro-wastes (AWs) derived from pistachio nutshells (PNS) and Aloe vera leaves (AV) as well as the multi-walled carbon nanotubes (MWCNTs) has been assessed. Adsorbent derived from raw pistachio nutshells (RPNS) was the most efficient among the four tested AWs (%removal '%R' = 82.39%), while MWCNTs showed the best adsorptive power amongst the five adsorbents (%R = 96.20%). Plackett-Burman design (PBD) was used to optimize the adsorption process. Two responses ('%R' and adsorption capacity 'qe') were optimized as a function of four variables (pH, adsorbent dose 'AD' (dose of RPNS and MWCNTs), adsorbate concentration [SARA] and contact time 'CT'). The effect of pH was similar for both RPNS and MWCNTs. Morphological and textural characterization of the tested adsorbents was carried out using FT-IR spectroscopy, SEM and BET analyses. Conversion of waste-derived materials into carbonaceous material was investigated by Raman spectroscopy. Equilibrium studies showed that Freundlich isotherm is the most suitable isotherm to describe the adsorption of SARA onto RPNS. Kinetics' investigation shows that the adsorption of SARA onto RPNS follows a pseudo-second order (PSO) model.


Assuntos
Agricultura , Ciprofloxacina/análogos & derivados , Nanotubos de Carbono/química , Águas Residuárias/química , Poluentes Químicos da Água/isolamento & purificação , Adsorção , Análise de Variância , Ciprofloxacina/química , Ciprofloxacina/isolamento & purificação , Concentração de Íons de Hidrogênio , Cinética , Nanotubos de Carbono/ultraestrutura , Pistacia/química , Espectroscopia de Infravermelho com Transformada de Fourier , Análise Espectral Raman , Termogravimetria
14.
Molecules ; 25(16)2020 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-32824634

RESUMO

Adsorptive removal of rose bengal (RB) from contaminated water samples was approached using pineapple leaves (PAL). Three adsorbents were utilized for that purpose; raw pineapple leaves (RPAL) and the thermally activated bio-waste leaves at 250 and 500 °C. Two measures were executed to evaluate the functionality of exploited biomasses; percentage removal (%R) and adsorption capacity (qe). Face-centered central composite design (FCCCD) was conducted to experiment the influence of variables on the %R. Dose of PAL as adsorbent (AD), concentration of RB (DC), pH and contact time (CT), were the inspected factors. Existence of functional groups and formation of activated carbon was instigated employing Fourier-transform infrared (FT-IR) and Raman spectroscopies. Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) analyses were used to explore surface features. Thermal behavior of adsorbents was studied using thermogravimetric analysis (TGA). The surface area and other surface structural properties were established using the Brunauer Emmett-Teller (BET) analysis. An amount of 92.53% of RB could be removed with an adsorption capacity of 58.8 mg/g using a combination of pH 5.00 ± 0.20, RPAL dose of 0.05 mg/50 mL, and 10-ppm RB for 180 min. Equilibrium studies divulge a favorable adsorption that follows the Freundlich isotherm. Pseudo-second-order model explains the observed adsorption kinetics.


Assuntos
Ananas/química , Folhas de Planta/química , Rosa Bengala/análise , Rosa Bengala/isolamento & purificação , Águas Residuárias/química , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/isolamento & purificação , Adsorção , Espectroscopia de Infravermelho com Transformada de Fourier , Termodinâmica
15.
Front Chem ; 7: 552, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31457003

RESUMO

Date pits (DPs) have been recycled into a low-cost adsorbent for removing of selected heavy metals (HMs) from artificially contaminated aqueous solutions. Adsorption of targeted HMs, both by raw date pits (RDP) and burnt date pits (BDP) was tested. Results showed that BDP is more efficient as an adsorbent and mostly adsorbing Cu(II). A novel approach; fractional factorial design (2 k-p - FrFD) was used to build the experimental pattern of this study. The effects of four factors on the maximum percentage (%) of removal (Y) were considered; pH, adsorbent dose (AD), heavy metal concentration (HMC), and contact time (CT). Statistically significant variables were detected using Pareto chart of standardized effects, normal and half-normal plots together with analysis of variance (ANOVA) at 95.0 confidence intervals (CI). Optimizing (maximizing) the percentage (%) removal of Cu(II) by BDP, was performed using optimization plots. Results showed that the factors: pH and adsorbent dose (AD) affect the response positively. Scanning electron microscopy (SEM) was used to study the surface morphology of both adsorbents while fourier-transform infrared spectroscopy (FTIR) was employed to get an idea on the functional groups on the surface and hence the adsorption mechanism. Raman spectroscopy was used to characterize the prepared adsorbents before and after adsorption of Cu(II). Equilibrium studies show that the adsorption behavior differs according to the equilibrium concentration. In general, it follows Langmuir isotherm up to 155 ppm, then Freundlich isotherm. Free energy of adsorption (ΔG ad) is -28.07 kJ/mole, when equilibrium concentration is below 155 ppm, so the adsorption process is spontaneous, while (ΔG ad) equals +17.89 kJ/mole above 155 ppm, implying that the process is non-spontaneous. Furthermore, the adsorption process is a mixture of physisorption and chemisorption processes, which could be endothermic or exothermic reactions. The adsorption kinetics were described using a second order model.

16.
RSC Adv ; 9(43): 24722-24732, 2019 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-35528693

RESUMO

Herein, a spectrochemical approach was adopted to study the charge-transfer (CT) complexation of sparfloxacin (SFX) with tetracyanoethylene (TCNE). In this study, a three-level design of experiments (DOE) involving a definitive screening design (DSD) was implemented. This is the first effort to operate this new category of design to determine a pharmaceutical compound in its pure form and in formulations. The proposed design allowed the establishment of a regression model that described the relation between the factorial input and the response surface. Moreover, two charge-transfer states (CTSs) were observed at 390 and 464 nm. The DFT calculations conducted using B3LYP/6-31+G showed that SFX had several donation sites (donor, D), whereas TCNE had two acceptor (A) sites. The two states were influenced differently by the experimental conditions as per the findings of the DSD analysis. In general, the diluting solvent had the largest impact. Probability plots, histograms, individual value plots, residual plots as well as analysis of variance (ANOVA) were delineated at the 95.0% confidence interval (CI). A Job's plot showed that a 1 : 1 complex was formed. The results were further confirmed using Benesi-Hildebrand plots. The proposed approach was proved to be linear in the range of 10-90 µg mL-1 SFX when the absorbance was measured at 464 nm. Different set-ups were adopted for studying the reaction kinetics. Analytical method performance was assessed following the ICH guiding principles, and the results obtained were found to be satisfactory. Complex formation was found to be an exothermic reaction.

17.
RSC Adv ; 9(38): 22106-22115, 2019 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-35518865

RESUMO

A simple and highly sensitive univariate calibration strategy based on ultraviolet-visible (UV-Vis) absorption spectroscopy and assisted by multivariate screening and optimization was utilized for the determination of l-ornithine (l-ORN) as such and in the alimentary supplements. l-ORN, an OTC marketed amino acid, is widely used for bodybuilding and might be abused by athletes. A nucleophilic substitution reaction using 7-chloro-4-nitrobenzo-2-oxa-1,3-diazole (NBD-Cl) was the basis of the current investigation. Plackett-Burman design (PBD) and a response surface optimizer as screening and fine-tuning strategies, respectively, were instigated. Four numerical variables, reaction time (RT), temperature (Temp), pH and reagent volume (RV), and one categorical variable, the diluting solvent (DS), were considered. Absorbance of the yellow-colored adduct at 469 nm was the response studied. Pareto analysis, along with analysis of variance (ANOVA) were used to ascertain the significant variables (screening phase) and their domains (optimization phase). Response transformation and stepwise analysis were employed when necessary. Probability, cube and individual value plots were used to get an insight into the statistical impact of the variables tested. Multiple responses' optimization was performed using Derringer's function. Calibration curves were linear in the range of 5-50 µg mL-1. Job's technique of continuous variation showed that the stoichiometric ratio is 2 : 1 (NBD-Cl : l-ORN). The proposed technique was successfully applied to the dietary supplements of l-ORN, inferring no interference from adjuvants and excipients. Analytical performance of this technique was validated conforming to the ICH standards.

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