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1.
J Environ Sci (China) ; 150: 14-24, 2025 Apr.
Article in English | MEDLINE | ID: mdl-39306391

ABSTRACT

The mass production and widespread use of Pharmaceuticals and Personal Care Products (PPCPs) have posed a serious threat to the water environment and public health. In this work, a green metal-based Metal Organic Framework (MOF) Bi-NH2-BDC was prepared and characterized, and the adsorption characteristics of Bi-NH2-BDC were investigated with typical PPCPs-diclofenac sodium (DCF). It was found that DCF mainly covered the adsorbent surface as a single molecular layer, the adsorption reaction was a spontaneous, entropy-increasing exothermic process and the adsorption mechanisms between Bi-NH2-BDC and DCF were hydrogen bonding, π-π interactions and electrostatic interactions. In addition, Bi-NH2-BDC also had considerable photocatalytic properties, and its application in adsorbent desorption treatment effectively solved the problem of secondary pollution, achieving a green and sustainable adsorption desorption cycle.


Subject(s)
Bismuth , Diclofenac , Metal-Organic Frameworks , Water Pollutants, Chemical , Diclofenac/chemistry , Adsorption , Water Pollutants, Chemical/chemistry , Metal-Organic Frameworks/chemistry , Bismuth/chemistry , Catalysis , Water Purification/methods
2.
Molecules ; 29(18)2024 Sep 21.
Article in English | MEDLINE | ID: mdl-39339484

ABSTRACT

Drug overuse harms the biosphere, leading to disturbances in ecosystems' functioning. Consequently, more and more actions are being taken to minimise the harmful impact of xenopharmaceuticals on the environment. One of the innovative solutions is using biosorbents-natural materials such as cells or biopolymers-to remove environmental pollutants; however, this focuses mainly on the removal of metal ions and colourants. Therefore, this study investigated the biosorption ability of selected pharmaceuticals-paracetamol, diclofenac, and ibuprofen-by the biomass of the cyanobacteria Anabaena sp. and Chroococcidiopsis thermalis, using the LC-MS/MS technique. The viability of the cyanobacteria was assessed by determining photosynthetic pigments in cells using a UV-VIS spectrophotometer. The results indicate that both tested species can be effective biosorbents for paracetamol and diclofenac. At the same time, the tested compounds did not have a toxic effect on the tested cyanobacterial species and, in some cases, stimulated their cell growth. Furthermore, the Anabaena sp. can effectively biotransform DCF into its dimer.


Subject(s)
Anabaena , Anabaena/metabolism , Diclofenac/chemistry , Diclofenac/metabolism , Cyanobacteria/metabolism , Cyanobacteria/chemistry , Biodegradation, Environmental , Tandem Mass Spectrometry , Adsorption , Biomass , Acetaminophen/chemistry , Acetaminophen/metabolism , Pharmaceutical Preparations/metabolism , Pharmaceutical Preparations/chemistry
3.
Environ Sci Pollut Res Int ; 31(43): 55317-55335, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39225928

ABSTRACT

This work involved the preparation of pristine and iron nanoparticle-loaded biochar from a water chestnut shell to remove diclofenac sodium (DCF) containing effluent of pharmaceutical origin. To create suitable forecasting equations for the modelling of the DCF adsorption onto the adsorbent, response surface methodology (RSM) was used. The parameters, e.g. pH, adsorbent mass, DCF concentration and contact time, were used for the modeling of adsorption. The RSM model predicts that for 98.0% DCF removal, the ideal conditions are pH 6, an adsorbent dose of 0.5 g L-1, and a contact time of 60 min with an initial adsorbate concentration of 25 mg L-1 at 303 K. The maximum capacity deduced from the Langmuir model was 75.9 mg g-1 for pristine water chestnut shell biochar (pWCBC) and 122.3 mg g-1 for magnetically modified nano-Fe2O3 biochar (mWCBC). Under equilibrium conditions, the Langmuir model was the best-suited model compared to the Temkin and Freundlich models. The adsorption data in this investigation efficiently fitted the pseudo-second-order model, emphasizing that chemisorption or ion exchange processes may be involved in the process. The WCBC demonstrated recyclability after 10 cycles of repeated adsorption and desorption of DCF. A combined coagulation adsorption process removed COD, NH3-N, NO3-, PO43-, and DCF by 92.50%, 86.41%, 77.57%, 84.54%, and 97.25%, respectively. This study therefore shows that coagulation followed by adsorption onto biochar can be a cost-effective substitute for conventional pharmaceutical wastewater treatment.


Subject(s)
Charcoal , Diclofenac , Water Pollutants, Chemical , Diclofenac/chemistry , Adsorption , Charcoal/chemistry , Water Pollutants, Chemical/chemistry , Water Purification/methods , Kinetics , Ferric Compounds/chemistry
4.
J Environ Manage ; 369: 122393, 2024 Oct.
Article in English | MEDLINE | ID: mdl-39226810

ABSTRACT

Sodium diclofenac (DCF) widely exists in actual water matrices, which can negatively impact ecosystems and aquatic environments even at low-strength. Herein, the adsorption-concentration-mineralization process was innovatively constructed for low-strength DCF elimination by freeze-dried biocarbon and oven-dried biocarbon coupled with cobalt oxide composites derived from the same waste biomass. Surprisingly, low-strength DCF of 0.5 mg/L was adsorbed rapidly and enriched to high-strength DCF under light with a concentration efficiency of 99.67 % by freeze-dried biocarbon. Subsequently, the concentrated DCF was economically mineralized by bifunctional oven-dried biocarbon coupled with cobalt oxide composites for peroxydisulfate (PDS) activation with full PDS activation and 76.11 % mineralization efficiency. Compared with direct low-strength DCF oxidation, adsorption-concentration-mineralization consumed less energy and none PDS residues. Mechanisms confirmed that DCF was adsorbed by freeze-dried biocarbon through hydrogen bonds and π-π stacking interactions, which were switched on due to electron-induced effect by light in DCF desorption-concentration. Furthermore, nonradical pathway (electron transfer) and radical pathway (SO4•-) were involved in efficient PDS activation by oven-dried biocarbon coupled with cobalt oxide composites for concentrated DCF mineralization, and the former was more prominent, in which graphitic carbon, cobalt redox cycle and carboxy groups were the main active sites. Overall, an energy-efficient strategy was proposed for elimination of low-strength DCF in real water matrices.


Subject(s)
Diclofenac , Diclofenac/chemistry , Adsorption , Sulfates/chemistry , Water Pollutants, Chemical/chemistry
5.
Dalton Trans ; 53(36): 15215-15235, 2024 Sep 18.
Article in English | MEDLINE | ID: mdl-39221624

ABSTRACT

Fourteen cobalt(II) complexes with the non-steroidal anti-inflammatory drugs sodium meclofenamate, tolfenamic acid, mefenamic acid, naproxen, sodium diclofenac, and diflunisal were prepared in the presence or absence of a series of nitrogen-donors (namely imidazole, pyridine, 3-aminopyridine, neocuproine, 2,2'-bipyridine, 1,10-phenanthroline and 2,2'-bipyridylamine) as co-ligands and were characterised by spectroscopic and physicochemical techniques. Single-crystal X-ray crystallography was employed to determine the crystal structure of eight complexes. The biological profile of the complexes was investigated regarding their interaction with serum albumins and DNA, and their antioxidant potency. The interaction of the compounds with calf-thymus DNA takes place via intercalation. The ability of the complexes to cleave pBR322 plasmid DNA at the concentration of 500 µM is rather low. The complexes demonstrated tight and reversible binding to human and bovine serum albumins and the binding site of bovine serum albumin was also examined. In order to assess the antioxidant activity of the compounds, the in vitro scavenging activity towards free radicals, namely 1,1-diphenyl-picrylhydrazyl and 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid), and their ability to reduce H2O2 were studied.


Subject(s)
Anti-Inflammatory Agents, Non-Steroidal , Cobalt , Coordination Complexes , DNA , Mefenamic Acid , Anti-Inflammatory Agents, Non-Steroidal/chemistry , Anti-Inflammatory Agents, Non-Steroidal/pharmacology , Cobalt/chemistry , Coordination Complexes/chemistry , Coordination Complexes/pharmacology , Coordination Complexes/chemical synthesis , Humans , DNA/chemistry , DNA/metabolism , Cattle , Animals , Mefenamic Acid/chemistry , Mefenamic Acid/pharmacology , Antioxidants/chemistry , Antioxidants/pharmacology , Diflunisal/chemistry , Diflunisal/pharmacology , Meclofenamic Acid/chemistry , Meclofenamic Acid/pharmacology , Crystallography, X-Ray , Serum Albumin, Bovine/chemistry , Serum Albumin, Bovine/metabolism , Diclofenac/chemistry , Diclofenac/pharmacology , Naproxen/chemistry , Naproxen/pharmacology , ortho-Aminobenzoates/chemistry , ortho-Aminobenzoates/pharmacology
6.
Int J Biol Macromol ; 277(Pt 2): 134246, 2024 Oct.
Article in English | MEDLINE | ID: mdl-39098461

ABSTRACT

A novel nanoparticle screening technique was established to mostly enhance the aqueous solubility and oral bioavailability of aceclofenac using nanoparticle systems. Among the polymers investigated, sodium carboxymethylcellulose (Na-CMC) showed the greatest increase in drug solubility. Utilizing spray-drying technique, the solvent-evaporated solid dispersion (SESD), surface-attached solid dispersion (SASD), and solvent-wetted solid dispersion (SWSD) were prepared using aceclofenac and Na-CMC at a weight ratio of 1:1 in 50 % ethanol, distilled water, and ethanol, respectively. Using Na-CMC as a solid carrier, an aceclofenac-loaded liquid self-emulsifying drug delivery system was spray-dried and fluid-bed granulated together with microcrystalline cellulose, producing a solid self-nanoemulsifying drug delivery system (SNEDDS) and solid self-nanoemulsifying granule system (SNEGS), respectively. Their physicochemical properties and preclinical assessments in rats were performed. All nanoparticles exhibited very different properties, including morphology, crystallinity, and size. As a result, they significantly enhanced the solubility, dissolution, and oral bioavailability in the following order: SNEDDS ≥ SNEGS > SESD ≥ SASD ≥ SWSD. Based on our screening technique, the SNEDDS was selected as the optimal nanoparticle with the highest bioavailability of aceclofenac. Thus, our nanoparticle screening technique should be an excellent guideline for solubilization research to improve the solubility and bioavailability of many poorly water-soluble bioactive materials.


Subject(s)
Biological Availability , Carboxymethylcellulose Sodium , Diclofenac , Nanoparticles , Solubility , Water , Diclofenac/pharmacokinetics , Diclofenac/analogs & derivatives , Diclofenac/chemistry , Diclofenac/administration & dosage , Carboxymethylcellulose Sodium/chemistry , Nanoparticles/chemistry , Animals , Rats , Administration, Oral , Water/chemistry , Male , Emulsions/chemistry , Drug Carriers/chemistry , Particle Size , Rats, Sprague-Dawley
7.
Environ Sci Pollut Res Int ; 31(42): 54695-54712, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39210226

ABSTRACT

The presence of drugs in aquatic environments has been considered a global challenge and several remediation technologies have been proposed, including adsorption. In this study, new diclofenac adsorbents were obtained from the reaction of sodium magadiite (Na-Mag) with surfactants dodecylpyridinium chloride hydrate (C12pyCl) and hexadecylpyridinium chloride monohydrate (C16pyCl)), 1-hexadecyltrimethylammonium bromide (C16Br), and dodecyltrimethylammonium bromide (C12Br). The synthesis was carried out in the microwave at 50 °C for 5 min using surfactant amounts of 100% and 200% in relation to the cation exchange capacity of Na-Mag. The elemental analysis indicated that surfactants with a longer organic chain were more incorporated into Na-Mag, whose values were 1.42 and 1.32 mmol g-1 for C16pyMag200% and C16Mag200%, respectively. X-ray diffraction results suggested formation of intercalated products with basal space in the range of 2.81-4.00 nm. Diclofenac was quickly adsorbed on all organophilic magadiites, at an equilibrium time of 1 min. Drug capacity adsorption was influenced by the arrangement and packing density of organic cations, the basal distance, and the organic contents of the samples at high drug concentrations. Alkylpyridinium magadiites exhibited maximum adsorption capacities higher than alkylammonium magadiites, of 96.4, 100.7, 131.7, and 166.1 mg g-1 for C12pyMag100%, C12pyMag200%, C16pyMag100%, and C16pyMag200%, respectively, at pH 6.0 and 30 °C. Diclofenac removal by samples was not affected by the presence of ibuprofen, which was also removed from binary system by organophilic magadiites reaching removal of 76.5% and 86.9% by C16pyMag100% and C16pyMag200%, respectively. Regeneration studies demonstrated a drug removal percentage of 83-92% for C16pyMag and C16Mag after three cycles of adsorption.


Subject(s)
Diclofenac , Surface-Active Agents , Water Pollutants, Chemical , Diclofenac/chemistry , Surface-Active Agents/chemistry , Adsorption , Water Pollutants, Chemical/chemistry
8.
Int J Biol Macromol ; 278(Pt 3): 134871, 2024 Oct.
Article in English | MEDLINE | ID: mdl-39173807

ABSTRACT

Pharmaceuticals and personal care products and dyes have low biodegradability and high toxicity, seriously threaten the human health and ecological environment. Therefore, seeking effective removal methods has become the focus of research. In this study, silver-based metal-organic framework (Ag-MOF) and chitosan (CS) hybrid adsorbent (Ag-MOF-CS) was synthesized via solvothermal one-pot synthesis to remove diclofenac sodium (DCF) and acid Red 1 (AR1) from water for the first time. The morphology and structure of Ag-MOF-CS were confirmed by various characterizations. The effect on adsorption was investigated by changing the adsorbent dosage, pH and other conditions. The adsorption kinetics, adsorption isotherms and thermodynamics were analyzed. Ag-MOF-CS showed a high adsorption capacity. And the maximum adsorption capacity of Ag-MOF-CS for DCF and AR1 was 351.75 mg/g and 678.83 mg/g, respectively. The adsorbent bound to DCF and AR1 may via electrostatic forces, π-π interactions, hydrogen bonding. Even after four cycles of Ag-MOF-CS, the DCF removal can still be higher than 80 %. The eco-friendly Ag-MOF-CS demonstrated significant potential for utilization in treating wastewater.


Subject(s)
Chitosan , Coloring Agents , Diclofenac , Metal-Organic Frameworks , Silver , Water Pollutants, Chemical , Water Purification , Chitosan/chemistry , Metal-Organic Frameworks/chemistry , Silver/chemistry , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/isolation & purification , Adsorption , Kinetics , Coloring Agents/chemistry , Coloring Agents/isolation & purification , Diclofenac/chemistry , Water Purification/methods , Hydrogen-Ion Concentration , Thermodynamics
9.
Environ Sci Pollut Res Int ; 31(40): 53074-53089, 2024 Aug.
Article in English | MEDLINE | ID: mdl-39172341

ABSTRACT

Herein, we report the efficient photocatalytic degradation of the diclofenac drug using the Zn1-x-yPrxAlyO photocatalyst [x, y] = (0.00, 0.00), (0.03, 0.01), (0.03,0.03) under UV light irradiation. The analysis of the structure reveals that the Pr3+ and Al3+ cations insertion into the ZnO lattice leads to a decrease in the lattice constant (a and c), Zn-O bond length, strain lattice, and crystallite size. These alterations are linked to the high degree of atomic disorder triggered by the dopants, which produce stress and strain in the ZnO structure. The Raman measurements confirmed the structural phase and showed changes in the position and intensity of the E2High mode, associated with oxygen vibrations and material crystallinity. The presence of the dopants reduces the concentration of VZn and VO++ type defects while increasing the levels of VO, VO+, and Oi defects, as observed from the fitting of the Photoluminescence spectra. Furthermore, it was noted that de Pr3+ and Al3+ cations insertion into ZnO increases the optical band gap, which is associated with the Moss-Burstein effect. The micrograph images show that dopants transform the morphology from quasi-spherical particles to irregular cluster structures. The textural analysis indicated that an increase in the concentration of Al3+ in the ZnO lattice led to a higher surface area, likely enhancing photocatalytic activity. The sample containing 3% Pr3+ and 3% Al3+ showed the highest photocatalytic activity and degraded up to 71.42% of diclofenac. In addition, experiments with scavengers revealed that hydroxyl radicals are the main species involved in the drug's photodegradation mechanism. Finally, the Zn1-x-yPrxAlyO compound is highly recyclable and stable.


Subject(s)
Diclofenac , Ultraviolet Rays , Diclofenac/chemistry , Catalysis , Zinc Oxide/chemistry , Zinc/chemistry , Photolysis
10.
Inorg Chem ; 63(33): 15421-15432, 2024 Aug 19.
Article in English | MEDLINE | ID: mdl-39115163

ABSTRACT

The escalating levels of hazardous pharmaceutical contaminants, specifically nonsteroidal anti-inflammatory drugs (NSAIDs), in groundwater reservoir surfaces and surface waterway systems have prompted substantial scientific interest regarding their potential deleterious effects on both aquatic ecosystems and human health. Extraction of those pollutants from wastewater is quite challenging. Hence, the development of economic, sustainable, and scalable techniques for capturing and removing those pollutants is crucial to ensure water safety. Herein, we demonstrate a physicochemically stable, reusable, porous Hf(IV)-based cationic metal-organic framework (MOF), namely, 1'@MeCl for the aqueous phase adsorption-based removal of NSAIDs (diclofenac, naproxen, ibuprofen) from the wastewater environment. The highly positively charged surface of the 1'@MeCl MOF enables it to selectively extract more than 99% of diclofenac, naproxen, and ibuprofen contaminants within less than 30 s. With fast adsorption kinetics, very high adsorption capacities (Qe) were achieved at neutral pH for diclofenac (482.9 mg/g), naproxen (295.9 mg/g), and ibuprofen (219.5 mg/g). Moreover, the influence of changes in pH and coexisting anions on the adsorption property of the 1'@MeCl MOF was studied. Furthermore, the adsorption efficiency of 1'@MeCl in different real water environments was ensured by performing diclofenac, naproxen, and ibuprofen adsorption from tap, river, and lake water. Moreover, a 1'@MeCl-anchored cellulose acetate-chitosan membrane was developed successfully to demonstrate the membrane-based extraction of diclofenac, naproxen, and ibuprofen from contaminated water. Furthermore, a molecular-level mechanistic study was performed through experimental and computational study to propose the plausible adsorption mechanisms for diclofenac, naproxen, and ibuprofen over the surface of 1'@MeCl.


Subject(s)
Anti-Inflammatory Agents, Non-Steroidal , Metal-Organic Frameworks , Water Pollutants, Chemical , Metal-Organic Frameworks/chemistry , Adsorption , Water Pollutants, Chemical/isolation & purification , Water Pollutants, Chemical/chemistry , Hydrogen-Ion Concentration , Anti-Inflammatory Agents, Non-Steroidal/chemistry , Anti-Inflammatory Agents, Non-Steroidal/isolation & purification , Diclofenac/chemistry , Diclofenac/isolation & purification , Naproxen/chemistry , Naproxen/isolation & purification , Ibuprofen/chemistry , Ibuprofen/isolation & purification , Surface Properties , Carboxylic Acids/chemistry , Carboxylic Acids/isolation & purification , Molecular Structure , Density Functional Theory , Cations/chemistry
11.
Sci Rep ; 14(1): 19009, 2024 08 16.
Article in English | MEDLINE | ID: mdl-39152164

ABSTRACT

The contamination of water sources by pharmaceutical pollutants presents significant environmental and health hazards, making the development of effective photocatalytic materials crucial for their removal. This research focuses on the synthesis of a novel Ag/CuS/Fe3O4 nanocomposite and its photocatalytic efficiency against tetracycline (TC) and diclofenac contaminants. The nanocomposite was created through a straightforward and scalable precipitation method, integrating silver nanoparticles (AgNPs) and copper sulfide (CuS) into a magnetite framework. Various analytical techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR),ultraviolet-visible spectrophotometry (UV-Vis) and energy-dispersive X-ray spectroscopy (EDS), were employed to characterize the structural and morphological properties of the synthesized material. The photocatalytic activity was tested by degrading tetracycline and diclofenac under visible light. Results indicated a marked improvement in the photocatalytic performance of the Ag/CuS/Fe3O4 nanocomposite (98%photodegradation of TC 60 ppm in 30 min) compared to both pure magnetite and CuS/Fe3O4. The enhanced photocatalytic efficiency is attributed to the synergistic interaction between AgNPs, CuS, and Fe3O4, which improves light absorption and charge separation, thereby increasing the generation of reactive oxygen species (ROS) and promoting the degradation of the pollutants. The rate constant k of photodegradation was about 0.1 min-1 for catalyst dosages 0.02 g. Also the effect of photocatalyst dose and concentration of TC and pH of solution was tested. The modified photocatalyst was also used for simultaneous photodegradation of TC and diclofenac successfully. This study highlights the potential of the Ag/CuS/Fe3O4 nanocomposite as an efficient and reusable photocatalyst for eliminating pharmaceutical pollutants from water.


Subject(s)
Copper , Diclofenac , Ferrosoferric Oxide , Nanocomposites , Silver , Tetracycline , Water Pollutants, Chemical , Diclofenac/chemistry , Nanocomposites/chemistry , Tetracycline/chemistry , Catalysis , Silver/chemistry , Ferrosoferric Oxide/chemistry , Water Pollutants, Chemical/chemistry , Copper/chemistry , Metal Nanoparticles/chemistry , Photolysis , X-Ray Diffraction , Light
12.
Mol Pharm ; 21(9): 4524-4540, 2024 Sep 02.
Article in English | MEDLINE | ID: mdl-39109552

ABSTRACT

Molecular interactions between active pharmaceutical ingredients (APIs) and xanthine (XAT) derivatives were analyzed using singular value decomposition (SVD). XAT derivatives were mixed with equimolar amounts of ibuprofen (IBP) and diclofenac (DCF), and their dissolution behaviors were measured using high-performance liquid chromatography. The solubility of IBP decreased in mixtures with caffeine (CFN) and theophylline (TPH), whereas that of DCF increased in mixtures with CFN and TPH. No significant differences were observed between the mixtures of theobromine (TBR) or XAT with IBP and DCF. Mixtures with various molar ratios were analyzed using differential scanning calorimetry, X-ray powder diffraction, and Fourier-transform infrared spectroscopy to further explore these interactions. The results were subjected to SVD. This analysis provides valuable insights into the differences in interaction strength and predicted interaction sites between XAT derivatives and APIs based on the combinations that form mixtures. The results also showed the impact of the XAT derivatives on the dissolution behavior of IBP and DCF. Although IBP and DCF were found to form intermolecular interactions with CFN and TPH, these effects resulted in a reduction of the solubility of IBP and an increase in the solubility of DCF. The current approach has the potential to predict various interactions that may occur in different combinations, thereby contributing to a better understanding of the impact of health supplements on pharmaceuticals.


Subject(s)
Caffeine , Calorimetry, Differential Scanning , Ibuprofen , Powders , Solubility , X-Ray Diffraction , Caffeine/chemistry , Spectroscopy, Fourier Transform Infrared/methods , Ibuprofen/chemistry , Calorimetry, Differential Scanning/methods , Powders/chemistry , X-Ray Diffraction/methods , Theophylline/chemistry , Chromatography, High Pressure Liquid/methods , Theobromine/chemistry , Diclofenac/chemistry , Xanthine/chemistry
13.
Environ Sci Pollut Res Int ; 31(38): 50804-50819, 2024 Aug.
Article in English | MEDLINE | ID: mdl-39102135

ABSTRACT

In this study, the adsorption of a mixture of high-consumed drugs onto virgin and aged PET microplastics has been studied for the time ever. The target mixture comprised two anti-inflammatory drugs, diclofenac and ketoprofen, one anti-hypertensive, valsartan, and four common antibiotics, indomethacin, trimethoprim, isoniazid, and metronidazole. Two types of PET MPs (virgin and UV-aged) were used in the experimental procedure. Kinetic studies were conducted, and adsorption isotherms were obtained revealing the possible interactions that take place between adsorbents and adsorbates. Among the studied pharmaceuticals, diclofenac presents the highest uptake due to its hydrophobic nature, while aging appears to induce the adsorption of the drugs in MPs. Factors like pH or the environmental matrix were also evaluated. The results revealed that sorption is pH-dependent, while more complicated matrices like wastewater or seawater exhibit lower uptake than distilled water due to the natural organic matter present or the increased salinity, respectively. Finally, desorption studies were also conducted in three different aqueous solutions examining the pH effect. The desorption of the compounds was higher for diclofenac, followed by valsartan, and ketoprofen. The desorption percentages of antibiotics were quite low.


Subject(s)
Microplastics , Water Pollutants, Chemical , Adsorption , Water Pollutants, Chemical/chemistry , Polyethylene Terephthalates/chemistry , Pharmaceutical Preparations/chemistry , Kinetics , Diclofenac/chemistry
14.
Environ Monit Assess ; 196(9): 802, 2024 Aug 09.
Article in English | MEDLINE | ID: mdl-39120741

ABSTRACT

This study assess how well diclofenac (DCF) can be separated from aqueous solution using potassium permanganate-modified eggshell biosorbent (MEB). The MEB produced was characterised using XRD, FTIR, and SEM. Batch experiments were conducted to examine and assess the impact of contact time, adsorbent dosage, initial concentration, and temperature on the adsorption capacity of the MEB in the DCF sequestration. The best parameters to obtained 95.64% DCF removal from liquid environment were 0.05 g MEB weight, 50 mg/L initial concentration, and 60 min contact time at room temperature. The maximum DCF sequestration capacity was found to be 159.57 mg/g with 0.05 g of MEB at 298 K. The adsorption isotherm data were more accurately predicted by the Freundlich model, indicating a process of heterogeneous multilayer adsorption. The results of the kinetic study indicated that the pseudo-second-order kinetic models best matched the experimental data. The findings revealed that the dynamic of DCF entrapment is largely chemisorption and diffusion controlled. Based on the values of thermodynamic parameters, the process is both spontaneous and endothermic. The primary processes of DCF sorption mechanism onto the MEB were chemical surface complexation, hydrogen bonding, π-π stacking, and electrostatic interactions. The produced MEB showed effective DCF separation from the aqueous solution and continued to have maximal adsorption capability even after five regeneration cycles. These findings suggest that MEB could be highly efficient adsorbent for the removal of DCF from pharmaceutical wastewater.


Subject(s)
Diclofenac , Egg Shell , Potassium Permanganate , Thermodynamics , Water Pollutants, Chemical , Diclofenac/chemistry , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/analysis , Adsorption , Kinetics , Egg Shell/chemistry , Potassium Permanganate/chemistry , Water Purification/methods , Waste Disposal, Fluid/methods , Animals
15.
Environ Res ; 260: 119611, 2024 Nov 01.
Article in English | MEDLINE | ID: mdl-39029726

ABSTRACT

The inclusion of mineral salts in carbon activators are beneficial for advanced oxidation processes (AOPs). Herein, we present the application of ball-milled biochar with phosphate salt for periodate (IO4-) activation and degradation of antibiotics in contaminated water. Physical characterization results showed that the catalyst is infused with Mg3(PO4)2 and ball-milling increased the specific surface area to 216 m2 g-1 from 46 m2 g-1 while reducing the particle size to less than 1.0 µ. The optimized system successfully eliminated >99% of diclofenac while maintaining the pH of the reaction medium to circumneutral levels. Scavenger and ESR experiments revealed the degradation is triggered by O2•-, 1O2 and •OH species within the system. Electrochemical studies confirmed electron transfer during diclofenac degradation. The reported system demonstrated high degradation efficiency under both neutral and acidic pH conditions. Based on the by-product analysis, the degradation pathway of diclofenac was elucidated. Further, the toxicity assessment for the identified intermediates showed minimum toxicity of the degraded products. This mineral-biochar composite exhibited promising performance in eliminating other antibiotic substances. Therefore, the present finding highlights the importance of raw materials selection for producing mineral-biochar composite that provide new insights into IO4- activation for antibiotic removal by maintaining the natural pH.


Subject(s)
Anti-Bacterial Agents , Charcoal , Water Pollutants, Chemical , Hydrogen-Ion Concentration , Water Pollutants, Chemical/chemistry , Anti-Bacterial Agents/chemistry , Charcoal/chemistry , Diclofenac/chemistry , Water Purification/methods , Oxides/chemistry , Minerals/chemistry
16.
Int J Mol Sci ; 25(13)2024 Jul 06.
Article in English | MEDLINE | ID: mdl-39000538

ABSTRACT

Skin penetration of an active pharmaceutical ingredient is key to developing topical drugs. This penetration can be adjusted for greater efficacy and/or safety through the selection of dosage form. Two emerging dosage forms, cream-gel and gel-in-oil emulsion, were tested for their ability to deliver diclofenac into the skin, with the target of maximising skin retention while limiting systemic exposure. Prototypes with varying amounts of solvents and emollients were formulated and evaluated by in vitro penetration testing on human skin. Cream-gel formulas showed better skin penetration than the emulgel benchmark drug even without added solvent, while gel-in-oil emulsions resulted in reduced diffusion of the active into the receptor fluid. Adding propylene glycol and diethylene glycol monoethyl ether as penetration enhancers resulted in different diclofenac penetration profiles depending on the dosage form and whether they were added to the disperse or continuous phase. Rheological characterisation of the prototypes revealed similar profiles of cream-gel and emulgel benchmark, whereas gel-in-oil emulsion demonstrated flow characteristics suitable for massaging product into the skin. This study underlined the potential of cream-gel and gel-in-oil emulsions for adjusting active penetration into the skin, broadening the range of choices available to topical formulation scientists.


Subject(s)
Administration, Cutaneous , Diclofenac , Emulsions , Skin Absorption , Skin , Diclofenac/pharmacokinetics , Diclofenac/administration & dosage , Diclofenac/chemistry , Humans , Skin Absorption/drug effects , Emulsions/chemistry , Skin/metabolism , Skin/drug effects , Rheology , Gels/chemistry , Anti-Inflammatory Agents, Non-Steroidal/pharmacokinetics , Anti-Inflammatory Agents, Non-Steroidal/administration & dosage , Anti-Inflammatory Agents, Non-Steroidal/chemistry , Administration, Topical , Emollients/chemistry , Emollients/pharmacokinetics , Emollients/administration & dosage
17.
An Acad Bras Cienc ; 96(suppl 1): e20231110, 2024.
Article in English | MEDLINE | ID: mdl-39046057

ABSTRACT

The present study modeled the adsorption process of the drug diclofenac sodium on activated charcoal. For this purpose, a mass balance-based model was used considering a fixed bed column. The mass transfer rate in the solid phase was represented by a driving force model proposed in this study, and a gamma exponent with a range of 0 > γ ≤ 2 was assigned to the model. Different isotherms were adopted to represent the equilibrium at the solid/liquid interface: the Langmuir, Freundlich, Sips and Redlich-Peterson isotherms. The modeling was approached from the perspective of Bayesian statistics, and the Markov chain Monte Carlo method was used for parameter estimation. Model validation was performed with experimental data obtained under different operating conditions of initial concentration ($C_{0.


Subject(s)
Bayes Theorem , Charcoal , Diclofenac , Diclofenac/chemistry , Adsorption , Charcoal/chemistry , Monte Carlo Method , Models, Chemical
18.
Environ Sci Pollut Res Int ; 31(35): 48650-48662, 2024 Jul.
Article in English | MEDLINE | ID: mdl-39037628

ABSTRACT

The presence of pharmaceuticals in wastewater resulting from human activities has driven researchers to explore effective treatment methods such as adsorption using activated carbon (AC). While AC shows promise as an adsorbent, further studies are essential to comprehend its entire interaction with pharmaceuticals. This article investigates the adsorption of potassium diclofenac (PD) onto AC using experimental and modeling approaches. Batch adsorption studies coupled with Fourier transform infrared spectroscopy (FTIR) were employed to clarify the adsorption mechanism of PD on AC. Various kinetic and isotherm adsorption models were applied to analyze the adsorbent-adsorbate interaction. The kinetics were best described by Avrami's fractional order (AFO) nonlinear model. Also, the intraparticle diffusion (IP) model reveals a three-stage adsorption process. The experimental equilibrium data fitted well with the three-parameter nonlinear Liu model, indicating a maximum adsorption capacity (Qmax) of 88.45 mg g-1 and suggesting monolayer or multilayer adsorption. Thermodynamic analysis showed favorable adsorption (ΔG° < 0), with an enthalpy change (ΔH° = -30.85 kJ mol-1) characteristic of physisorption involving hydrogen bonds and π-π interactions. The adsorption mechanism was attributed to forming a double layer (adsorbate-adsorbent and adsorbate-adsorbate).


Subject(s)
Charcoal , Diclofenac , Water Pollutants, Chemical , Diclofenac/chemistry , Adsorption , Charcoal/chemistry , Water Pollutants, Chemical/chemistry , Kinetics , Thermodynamics , Spectroscopy, Fourier Transform Infrared , Wastewater/chemistry , Carbon/chemistry
19.
Chemosphere ; 363: 142974, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39084301

ABSTRACT

The prevalent presence of pharmaceuticals in aquatic ecosystems underscores the necessity for developing cost-effective techniques to remove them from water. The utilization of affordable precursors in producing activated carbon, capable of rivaling commercial alternatives, remains a persistent challenge. The adsorption of diclofenac and ciprofloxacin onto a novel pinewood-derived activated carbon (FPWAC) was explored, employing a sequential activation process involving ammonium nitrate (NH4NO3) treatment followed by sodium hydroxide (NaOH) activation. The produced FPWAC was then thoroughly characterized by employing several techniques. The removal of diclofenac and ciprofloxacin in water and real wastewater effluent was examined in batch tests. The optimum removal conditions were an FPWAC dosage of 1 g L-1, pH 6, mixture concentration of 25 mg L-1, and a temperature of 25 °C. The FPWAC was able to remove both pharmaceuticals for up to six cycles, with more than 95% removal for water and 90% for wastewater in the first cycle. The adsorption performance fitted well with the non-linear Freundlich isotherm for both pollutants. The kinetics of adsorption of diclofenac followed a pseudo-first-order model, while ciprofloxacin showed adherence to the pseudo-second-order model. FPWAC proved its potency as a low-cost adsorbent for pharmaceutical removal from wastewater.


Subject(s)
Ciprofloxacin , Diclofenac , Wastewater , Water Pollutants, Chemical , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/analysis , Wastewater/chemistry , Diclofenac/chemistry , Diclofenac/isolation & purification , Diclofenac/analysis , Adsorption , Ciprofloxacin/chemistry , Ciprofloxacin/isolation & purification , Ciprofloxacin/analysis , Water Purification/methods , Waste Disposal, Fluid/methods , Pinus/chemistry , Charcoal/chemistry , Wood/chemistry , Kinetics , Hydrogen-Ion Concentration
20.
J Biomater Sci Polym Ed ; 35(13): 2049-2067, 2024 Sep.
Article in English | MEDLINE | ID: mdl-38994903

ABSTRACT

Cartilage tissue engineering holds great promise for efficient cartilage regeneration. However, early inflammatory reactions to seed cells and/or scaffolds impede this process. Consequently, managing inflammation is of paramount importance. Moreover, due to the body's restricted chondrogenic capacity, inducing cartilage regeneration becomes imperative. Thus, a controlled platform is essential to establish an anti-inflammatory microenvironment before initiating the cartilage regeneration process. In this study, we utilized fifth-generation polyamidoamine dendrimers (G5) as a vehicle for drugs to create composite nanoparticles known as G5-Dic/Sr. These nanoparticles were generated by surface modification with diclofenac (Dic), known for its potent anti-inflammatory effects, and encapsulating strontium (Sr), which effectively induces chondrogenesis, within the core. Our findings indicated that the G5-Dic/Sr nanoparticle exhibited selective Dic release during the initial 9 days and gradual Sr release from days 3 to 15. Subsequently, these nanoparticles were incorporated into a gelatin methacryloyl (GelMA) hydrogel, resulting in GelMA@G5-Dic/Sr. In vitro assessments demonstrated GelMA@G5-Dic/Sr's biocompatibility with bone marrow stem cells (BMSCs). The enclosed nanoparticles effectively mitigated inflammation in lipopolysaccharide-induced RAW264.7 macrophages and significantly augmented chondrogenesis in BMSCs cocultures. Implanting BMSCs-loaded GelMA@G5-Dic/Sr hydrogels in immunocompetent rabbits for 2 and 6 weeks revealed diminished inflammation and enhanced cartilage formation compared to GelMA, GelMA@G5, GelMA@G5-Dic, and GelMA@G5/Sr hydrogels. Collectively, this study introduces an innovative strategy to advance cartilage regeneration by temporally modulating inflammation and chondrogenesis in immunocompetent animals. Through the development of a platform addressing the temporal modulation of inflammation and the limited chondrogenic capacity, we offer valuable insights to the field of cartilage tissue engineering.


Subject(s)
Chondrogenesis , Dendrimers , Diclofenac , Inflammation , Nanoparticles , Strontium , Chondrogenesis/drug effects , Strontium/chemistry , Strontium/pharmacology , Animals , Diclofenac/pharmacology , Diclofenac/chemistry , Dendrimers/chemistry , Dendrimers/pharmacology , Nanoparticles/chemistry , Inflammation/drug therapy , Rabbits , Mice , Mesenchymal Stem Cells/drug effects , Mesenchymal Stem Cells/cytology , Hydrogels/chemistry , Hydrogels/pharmacology , Surface Properties , Gelatin/chemistry , Cartilage/drug effects , Cartilage/physiology , Drug Liberation , Tissue Engineering , Drug Carriers/chemistry
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