Abstract
In the present study, a novel pH-sensitive hydrogel composite of pectin-grafted-poly (acrylic acid-co-itaconic acid)/MWCNTs-COOH was prepared by using graft copolymerization of acrylic acid and itaconic acid on pectin backbone with incorporation of MWCNTS-COOH. The prepared hydrogel composite has been employed for the adsorption and controlled release of the diclofenac sodium (DS) drug. The hydrogel composite was characterized by the analysis methods: FTIR, XRD, SEM, and TGA to analyze structural characteristics before and after DS drug adsorption. The swelling ratio of the hydrogel composite was investigated at different pH values from pH 1.2 to 10. According to the results, the swelling ratio of the hydrogel composite was found 4195% at pH 7.4. Adsorption process parameters such as pH, contact time, adsorbent dose, and temperature were investigated and found to have a significant influence on DS drug adsorption. The maximum DS drug loading through adsorption of 91% was obtained at pH 3, adsorbent dose of 0.05 g, contact time of 150 min, and temperature of 15 °C. The adsorption isotherm and kinetic results were well-fitted to Freundlich and second-order models. Thermodynamic parameters including changes in Gibb’s free energy, enthalpy, and entropy suggested that the adsorption of DS drug onto hydrogel composite was a spontaneous and exothermic process. The in vitro drug release experiment showed that the cumulative release of DS drug from hydrogel composite after 35 h was significantly higher in simulated intestinal fluid at pH 7.4 than in simulated gastric fluid at pH 1.2.
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References
Adepu S, Ramakrishna S (2021) Controlled drug delivery systems: current status and future directions. Molecules 26(19):5905
Wang Q, Xie X, Zhang X, Zhang J, Wang A (2010) Preparation and swelling properties of pH-sensitive composite hydrogel beads based on chitosan-g-poly (acrylic acid)/vermiculite and sodium alginate for diclofenac controlled release. Int J Biol Macromol 46(3):356–362
Ameli H, Alizadeh N (2022) Targeted delivery of capecitabine to colon cancer cells using nano polymeric micelles based on beta cyclodextrin. RSC Adv 12(8):4681–4691
Prajapati VD, Jani GK, Kapadia JR (2015) Current knowledge on biodegradable microspheres in drug delivery. Expert Opin Drug Deliv 12(8):1283–1299
Gulen B, Demircivi P (2020) Synthesis and characterization of montmorillonite/ciprofloxacin/TiO2 porous structure for controlled drug release of ciprofloxacin tablet with oral administration. Appl Clay Sci 197:105768
Gu L, He X, Wu Z (2014) Mesoporous hydroxyapatite: Preparation, drug adsorption, and release properties. Mater Chem Phys 148(1–2):153–158
Chudoba D, Jażdżewska M, Łudzik K, Wołoszczuk S, Juszyńska-Gałązka E, Kościński M (2021) Description of release process of doxorubicin from modified carbon nanotubes. Int J Mol Sci 22(21):12003
Li X, Xue X, Jia J, Zou X, Guan Y, Zhu L, Wang Z (2023) Nonsteroidal anti-inflammatory drug diclofenac accelerates the emergence of antibiotic resistance via mutagenesis. Environ Pollut 326:121457
Khan SA, Siddiqui MF, Khan TA (2020) Synthesis of poly(methacrylic acid)/montmorillonite hydrogel nano- composite for efficient adsorption of amoxicillin and diclofenac from aqueous environment: kinetic, isotherm, reusability, and thermodynamic investigations. ACS Omega 5(6):2843–2855
Li L, Zheng X, Pan C, Pan H, Guo Z, Liu B, Liu Y (2021) A pH-sensitive and sustained-release oral drug delivery system: the synthesis, characterization, adsorption and release of the xanthan gum-graft-poly (acrylic acid)/GO–DCFP composite hydrogel. RSC Adv 11(42):26229–26240
Abasalizadeh F, Moghaddam SV, Alizadeh E, Akbari E, Kashani E, Fazljou SMB, Torbati M, Akbarzadeh A (2020) Alginate-based hydrogels as drug delivery vehicles in cancer treatment and their applications in wound dressing and 3D bioprinting. J Biol Eng 14:1–22
Che Nan NF, Zainuddin N, Ahmad M (2019) Preparation and swelling study of CMC hydrogel as potential superabsorbent. Pertanika J Sci Technol 27(1):489–498
Jiang J, Bai S, Yang M, Zou J, Li N, Peng J, Wang H, Xiang K, Liu S, Zhai T (2022) Strategic design and fabrication of MXenes-Ti3CNCl2@ CoS2 core-shell nanostructure for high-efficiency hydrogen evolution. Nano Res 15(7):5977–5986
Kaur P, Agrawal R, Pfeffer FM, Williams R, Bohidar HB (2023) Hydrogels in agriculture: prospects and challenges. J Polym Environ 31:3701–3718
Li Y, Yang HY, Lee DS (2021) Advances in biodegradable and injectable hydrogels for biomedical applications. J Control Release 330:151–160
Martínez-Ibarra DM, Sánchez-Machado DI, López-Cervantes J, Campas-Baypoli ON, Sanches-Silva A, Madera-Santana TJ (2019) Hydrogel wound dressings based on chitosan and xyloglucan: development and characterization. J Appl Polym Sci 136(12):47342
Roshanbinfar K, Mohammadi Z, Mesgar AS-M, Dehghan MM, Oommen OP, Hilborn J, Engel FB (2019) Carbon nanotube doped pericardial matrix derived electroconductive biohybrid hydrogel for cardiac tissue engineering. Biomater Sci 7(9):3906–3917
Gholamali I, Asnaashariisfahani M, Alipour E (2020) Silver nanoparticles incorporated in pH-sensitive nano- composite hydrogels based on carboxymethyl chitosan-poly (vinyl alcohol) for use in a drug delivery system. Regen Eng Transl Med 6:138–153
Ahmad S, Tanweer MS, Mir TA, Alam M, Ikram S, Sheikh JN (2023) Antimicrobial gum based hydrogels as adsorbents for the removal of organic and inorganic pollutants. J Water Process Eng 51:103377
Sun X-F, Wang H-h, Jing Z-x, Mohanathas R (2013) Hemicellulose-based pH-sensitive and biodegradable hydrogel for controlled drug delivery. Carbohydr Polym 92(2):1357–1366
Zou J, Wu S, Liu Y, Sun Y, Cao Y, Hsu J-P, Wee ATS, Jiang J (2018) An ultra-sensitive electrochemical sensor based on 2D g-C3N4/CuO nanocomposites for dopamine detection. Carbon 130:652–663
Wang J, Qin Q, Li F, Anjarsari Y, Sun W, Azzahiidah R, Zou J, Xiang K, Ma H, Jiang J (2023) Recent advances of MXenes Mo2C-based materials for efficient photocatalytic hydrogen evolution reaction. Carbon Lett 33(5):1381–1394
Makhado E, Hato MJ (2021) Preparation and characterization of sodium alginate-based oxidized multi-walled carbon nanotubes hydrogel nanocomposite and its adsorption behaviour for methylene blue dye. Front Chem 9:576913
Yang M, Chen Y, Wang H, Zou Y, Wu P, Zou J, Jiang J (2022) Solvothermal preparation of CeO2 nano- particles–graphene nanocomposites as an electrochemical sensor for sensitive detecting pentachlorophenol. Carbon Lett 32(5):1277–1285
Makhado E, Pandey S, Nomngongo PN, Ramontja J (2018) Preparation and characterization of xanthan gum-cl-poly (acrylic acid)/o-MWCNTs hydrogel nanocomposite as highly effective re-usable adsorbent for removal of methylene blue from aqueous solutions. J Colloid Interface Sci 513:700–714
Chen Y, Tu C, Liu Y, Liu P, Gong P, Wu G, Huang X, Chen J, Liu T, Jiang J (2023) Microstructure and mechanical properties of carbon graphite composites reinforced by carbon nanofibers. Carbon Lett 33(2):561–571
Zhu W, Huang H, Dong Y, Han C, Sui X, Jian B (2019) Multi-walled carbon nanotube-based systems for improving the controlled release of insoluble drug dipyridamole. Exp Ther Med 17(6):4610–4616
Jiang J, Xiong Z, Wang H, Liao G, Bai S, Zou J, Wu P, Zhang P, Li X (2022) Sulfur-doped g-C3N4/g-C3N4 isotype step-scheme heterojunction for photocatalytic H2 evolution. J Mater Sci Technol 118:15–24
Malek SK, Gabris MA, Jume BH, Baradaran R, Aziz M, Karim KJBA, Nodeh HR (2019) Adsorption and in vitro release study of curcumin form polyethyleneglycol functionalized multi walled carbon nanotube: kinetic and isotherm study. DARU J Pharm Sci 27:9–20
Li F, Anjarsari Y, Wang J, Azzahiidah R, Jiang J, Zou J, Xiang K, Ma H, Arramel, (2023) Modulation of the lattice structure of 2D carbon-based materials for improving photo/electric properties. Carbon Lett 33(5):1321–1331
Yadollahi M, Farhoudian S, Barkhordari S, Gholamali I, Farhadnejad H, Motasadizadeh H (2016) Facile synthesis of chitosan/ZnO bio-nanocomposite hydrogel beads as drug delivery systems. Int J Biol Macromol 82:273–278
Zou J, Liao G, Jiang J, Xiong Z, Bai S, Wang H, Wu P, Zhang P, Li X (2022) In-situ construction of sulfur-doped g-C3N4/defective g-C3N4 isotype step-scheme heterojunction for boosting photocatalytic H2 evolution. Chin J Struct Chem 41(1):2201025–2201033
El Nemr A, Serag E, El-Maghraby A, Fathy SA, Abdel Hamid FF (2019) Manufacturing of pH sensitive PVA /PVP/MWCNT and PVA/PEG/MWCNT nanocomposites: an approach for significant drug release. J Macromol Sci A 56(8):781–793
Mok CF, Ching YC, Osman NAA, Muhamad F, Hai ND, Choo J, Hassan CR (2020) Adsorbents for removal of cationic dye: nanocellulose reinforced biopolymer composites. J Polym Res 27:1–15
Adeola AO, de Lange J, Forbes PB (2021) Adsorption of antiretroviral drugs, efavirenz and nevirapine from aqueous solution by graphene wool: kinetic, equilibrium, thermodynamic and computational studies. Appl Surf Sci Adv 6:100157
Alwan SH, Salem KH, Alshamsi HA (2022) Visible light-driven photocatalytic degradation of rhodamine B dye onto TiO2/rGO nanocomposites. Mater Today Commun 33:104558
Tan TL, Nakajima H, Rashid SA (2020) Adsorptive, kinetics and regeneration studies of fluoride removal from water using zirconium-based metal organic frameworks. RSC Adv 10(32):18740–18752
Wang Y, Yang S-T, Wang Y, Liu Y, Wang H (2012) Adsorption and desorption of doxorubicin on oxidized carbon nanotubes. Colloids Surf B 97:62–69
Mohammadi M, Vadi M, Bagehri N, Shekoohi K, Younessi F (2021) Kinetics and thermodynamics adsorption of Oxazepam drug on the multi-walled carbon nanotube. J Chin Chem Soc 68(5):799–805
Edet UA, Ifelebuegu AO (2020) Kinetics, isotherms, and thermodynamic modeling of the adsorption of phosphates from model wastewater using recycled brick waste. Processes 8(6):665
Alwan SH, Alshamsi HA (2022) In situ synthesis NiO/F-MWCNTs nanocomposite for adsorption of malachite green dye from polluted water. Carbon Lett 32(4):1073–1084
Bera A, Kumar T, Ojha K, Mandal A (2013) Adsorption of surfactants on sand surface in enhanced oil recovery: isotherms, kinetics and thermodynamic studies. Appl Surf Sci 284:87–99
Hiew BYZ, Lee LY, Lai KC, Gan S, Thangalazhy-Gopakumar S, Pan G-T, Yang TC-K (2019) Adsorptive decontamination of diclofenac by three-dimensional graphene-based adsorbent: response surface methodology, adsorption equilibrium, kinetic and thermodynamic studies. Environ Res 168:241–253
Hanna DH, Saad GR (2019) Encapsulation of ciprofloxacin within modified xanthan gum-chitosan based hydrogel for drug delivery. Bioorg Chem 84:115–124
Gull N, Khan SM, Butt OM, Islam A, Shah A, Jabeen S, Khan SU, Khan A, Khan RU, Butt MTZ (2020) Inflammation targeted chitosan-based hydrogel for controlled release of diclofenac sodium. Int J Biol Macromol 162:175–187
Ajaz N, Khan IU, Khalid I, Khan RU, Khan HA, Asghar S, Khalid SH, Shahzad Y, Yousaf AM, Hussain T (2020) In vitro and toxicological assessment of dexamethasone sodium phosphate loaded pH sensitive Pectin-g-poly (AA)/PVP semi interpenetrating network. Mater Today Commun 25:101325
Hu X, Wei W, Qi X, Yu H, Feng L, Li J, Wang S, Zhang J, Dong W (2015) Preparation and characterization of a novel pH-sensitive Salecan-g-poly (acrylic acid) hydrogel for controlled release of doxorubicin. J Mater Chem B 3(13):2685–2697
Tahermansouri H, Ahi RM, Kiani F (2014) Kinetic, equilibrium and isotherm studies of cadmium removal from aqueous solutions by oxidized multi-walled carbon nanotubes and the functionalized ones with thio-semicarbazide and their toxicity investigations: a comparison. J Chin Chem Soc 61(11):1188–1198
Dai H, Zhang Y, Ma L, Zhang H, Huang H (2019) Synthesis and response of pineapple peel carboxymethyl cellulose-g-poly (acrylic acid-co-acrylamide)/graphene oxide hydrogels. Carbohydr Polym 215:366–376
Suhail M, Wu P-C, Minhas MU (2021) Development and characterization of pH-sensitive chondroitin sulfate -co-poly (acrylic acid) hydrogels for controlled release of diclofenac sodium. J Saudi Chem Soc 25(4):101212
Mahmoud GA, Ali AE-H, Raafat AI, Badawy NA, Elshahawy MF (2018) Development of (acrylic acid/polyethylene glycol)-zinc oxide mucoadhesive nanocomposites for buccal administration of propranolol HCl. Radiat Phys Chem 147:18–26
Kodoth AK, Badalamoole V (2019) Pectin based graft copolymer–ZnO hybrid nanocomposite for the adsorp- tive removal of crystal violet. J Polym Environ 27:2040–2053
Hu X, Feng L, Xie A, Wei W, Wang S, Zhang J, Dong W (2014) Synthesis and characterization of a novel hydrogel: salecan/polyacrylamide semi-IPN hydrogel with a desirable pore structure. J Mater Chem B 2(23):3646–3658
Wen F, Li S, Chen R, He Y, Li L, Cheng L, Ma J, Mu J (2022) Improved thermal and electromagnetic shielding of PEEK composites by hydroxylating PEK-C grafted MWCNTs. Polymers 14(7):1328
Anirudhan T, Mohan AM (2014) Novel pH switchable gelatin based hydrogel for the controlled delivery of the anti cancer drug 5-fluorouracil. RSC Adv 4(24):12109–12118
Date P, Tanwar A, Ladage P, Kodam KM, Ottoor D (2020) Carbon dots-incorporated pH-responsive agarose- PVA hydrogel nanocomposites for the controlled release of norfloxacin drug. Polym Bull 77:5323–5344
Wang Z, Ning A, Xie P, Gao G, Xie L, Li X, Song A (2017) Synthesis and swelling behaviors of carboxy-methyl cellulose-based superabsorbent resin hybridized with graphene oxide. Carbohydr Polym 157:48–56
Mahmoodi H, Fattahi M, Motevassel M (2021) Graphene oxide–chitosan hydrogel for adsorptive removal of diclofenac from aqueous solution: preparation, characterization, kinetic and thermodynamic modelling. RSC Adv 11(57):36289–36304
El Naga AOA, El Saied M, Shaban SA, El Kady FY (2019) Fast removal of diclofenac sodium from aqueous solution using sugar cane bagasse-derived activated carbon. J Mol Liq 285:9–19
Avcu T, Üner O, Geçgel Ü (2021) Adsorptive removal of diclofenac sodium from aqueous solution onto sycamore ball activated carbon–isotherms, kinetics, and thermodynamic study. Surf Interfaces 24:101097
Bhadra BN, Seo PW, Jhung SH (2016) Adsorption of diclofenac sodium from water using oxidized activated carbon. Chem Eng J 301:27–34
Akl ZF, Zaki EG, ElSaeed SM (2021) Green hydrogel-biochar composite for enhanced adsorption of uranium. ACS Omega 6(50):34193–34205
Acelas N, Lopera SM, Porras J, Torres-Palma RA (2021) Evaluating the removal of the antibiotic cephalexin from aqueous solutions using an adsorbent obtained from palm oil fiber. Molecules 26(11):3340
Kausar A, Naeem K, Hussain T, Bhatti HN, Jubeen F, Nazir A, Iqbal M (2019) Preparation and characterization of chitosan/clay composite for direct Rose FRN dye removal from aqueous media: comparison of linear and non-linear regression methods. J Mater Res Technol 8(1):1161–1174
Verma A, Thakur S, Mamba G, Gupta RK, Thakur P, Thakur VK (2020) Graphite modified sodium alginate hydrogel composite for efficient removal of malachite green dye. Int J Biol Macromol 148:1130–1139
Seera SDK, Kundu D, Gami P, Naik PK, Banerjee T (2021) Synthesis and characterization of xylan-gelatin cross-linked reusable hydrogel for the adsorption of methylene blue. Carbohydr Polym 256:117520
Cuerda-Correa EM, Domínguez-Vargas JR, Olivares-Marín FJ, de Heredia JB (2010) On the use of carbon blacks as potential low-cost adsorbents for the removal of non-steroidal anti-inflammatory drugs from river water. J Hazard Mater 177(1–3):1046–1053
Bensalah H, Younssi SA, Ouammou M, Gurlo A, Bekheet MF (2020) Azo dye adsorption on an industrial waste-transformed hydroxyapatite adsorbent: kinetics, isotherms, mechanism and regeneration studies. J Environ Chem Eng 8(3):103807
Ning F, Zhang J, Kang M, Ma C, Li H, Qiu Z (2021) Hydroxyethyl cellulose hydrogel modified with tannic acid as methylene blue adsorbent. J Appl Polym Sci 138(8):49880
Rigueto CVT, Rosseto M, Nazari MT, Ostwald BEP, Alessandretti I, Manera C, Piccin JS, Dettmer A (2021) Adsorption of diclofenac sodium by composite beads prepared from tannery wastes-derived gelatin and carbon nanotubes. J Environ Chem Eng 9(1):105030
Rehman TU, Bibi S, Khan M, Ali I, Shah LA, Khan A, Ateeq M (2019) Fabrication of stable superabsorbent hydrogels for successful removal of crystal violet from waste water. RSC Adv 9(68):40051–40061
Jawad AH, Mallah SH, Mastuli MS (2018) Adsorption behavior of methylene blue on acid-treated rubber (Hevea brasiliensis) leaf. Desalin Water Treat 124:297–307
Rasoulzadeh H, Mohseni-Bandpei A, Hosseini M, Safari M (2019) Mechanistic investigation of ciprofloxacin recovery by magnetite–imprinted chitosan nanocomposite: isotherm, kinetic, thermodynamic and reus- ability studies. Int J Biol Macromol 133:712–721
Yadav S, Asthana A, Singh AK, Chakraborty R, Sree Vidya S, Singh A, Carabineiro SA (2021) Methionine-functionalized graphene oxide/sodium alginate bio-polymer nanocomposite hydrogel beads: synthesis, isotherm and kinetic studies for an adsorptive removal of fluoroquinolone antibiotics. Nanomaterials 11(3):568
Lv Y, Liang Z, Li Y, Chen Y, Liu K, Yang G, Liu Y, Lin C, Ye X, Shi Y (2021) Efficient adsorption of diclofenac sodium in water by a novel functionalized cellulose aerogel. Environ Res 194:110652
Lonappan L, Rouissi T, Brar SK, Verma M, Surampalli RY (2018) An insight into the adsorption of diclofenac on different biochars: Mechanisms, surface chemistry, and thermodynamics. Bioresour Technol 249:386–394
Saxena R, Saxena M, Lochab A (2020) Recent progress in nanomaterials for adsorptive removal of organic contaminants from wastewater. Chem Select 5(1):335–353
Thi Minh Tam N, Liu Y, Bashir H, Yin Z, He Y, Zhou X (2020) Efficient removal of diclofenac from aqueous solution by potassium ferrate-activated porous graphitic biochar: ambient condition influences and adsorption mechanism. Int J Environ Res Public Health 17(1):291
Alharby NF, Almutairi RS, Mohamed NA (2021) Adsorption behavior of methylene blue dye by novel cross linked O-CM-Chitosan hydrogel in aqueous solution: kinetics, isotherm and thermodynamics. Polymers 13(21):3659
Wang Q, Zhang J, Wang A (2009) Preparation and characterization of a novel pH-sensitive chitosan-g-poly (acrylic acid)/attapulgite/sodium alginate composite hydrogel bead for controlled release of diclofenac sodium. Carbohydr Polym 78(4):731–737
Hua S, Ma H, Li X, Yang H, Wang A (2010) pH-sensitive sodium alginate/poly (vinyl alcohol) hydrogel beads prepared by combined Ca2+ crosslinking and freeze-thawing cycles for controlled release of diclofenac sodium. Int J Biol Macromol 46(5):517–523
Suhail M, Khan A, Rosenholm JM, Minhas MU, Wu P-C (2021) Fabrication and characterization of diclofenac sodium loaded hydrogels of sodium alginate as sustained release carrier. Gels 7(1):10
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The authors are thankful to the University of Al-Qadisiyah in Iraq for providing the necessary support and facilities for the completion of the study.
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All authors contributed to the design and conduct of the study. Materials preparation, experiments, data collection, analysis, and writing were performed by Wissam L. Penyan and Layth S Jasim. All authors commented on previous versions of the manuscript. Finally, all authors read and approved the final manuscript.
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Penyan, W.L., Jasim, L.S. Preparation and characterization of a novel pH-sensitive pectin-grafted-poly (acrylic acid-co-itaconic acid)/MWCNTs-COOH hydrogel composite for adsorption and controlled release of diclofenac sodium. Carbon Lett. (2024). https://doi.org/10.1007/s42823-024-00702-8
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DOI: https://doi.org/10.1007/s42823-024-00702-8