{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,12,5]],"date-time":"2025-12-05T18:12:13Z","timestamp":1764958333310,"version":"3.46.0"},"reference-count":40,"publisher":"MDPI AG","issue":"12","license":[{"start":{"date-parts":[[2025,12,4]],"date-time":"2025-12-04T00:00:00Z","timestamp":1764806400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia, I.P.\/MCTES through national funds: LSRE-LCM","doi-asserted-by":"publisher","award":["UID\/50020\/2025","LA\/P\/0045\/2020"],"award-info":[{"award-number":["UID\/50020\/2025","LA\/P\/0045\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"name":"the Brazilian National Council for Scientific and Technological Development"},{"DOI":"10.13039\/501100003593","name":"the Coordination for the Improvement of Higher Education Personnel","doi-asserted-by":"publisher","award":["001"],"award-info":[{"award-number":["001"]}],"id":[{"id":"10.13039\/501100003593","id-type":"DOI","asserted-by":"publisher"}]},{"name":"6th edition of FCT Individual Call to Scientific Employment Stimulus\u2014\u201cO-MIX\u2014Mixing Principles in Modulated Flow Reactors\u201d"},{"DOI":"10.13039\/501100004837","name":"activities of the project","doi-asserted-by":"publisher","award":["TED2021-130147B-C21"],"award-info":[{"award-number":["TED2021-130147B-C21"]}],"id":[{"id":"10.13039\/501100004837","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100004837","name":"MCI, Spain","doi-asserted-by":"publisher","award":["PID2022-9136816OB-I00"],"award-info":[{"award-number":["PID2022-9136816OB-I00"]}],"id":[{"id":"10.13039\/501100004837","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100004837","name":"MICIU, Spain","doi-asserted-by":"publisher","award":["PID2023-147456OB-C22"],"award-info":[{"award-number":["PID2023-147456OB-C22"]}],"id":[{"id":"10.13039\/501100004837","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["J. Compos. Sci."],"abstract":"<jats:p>The high use and improper disposal of chloroquine (CQ) during the COVID-19 pandemic have significantly increased its presence in water bodies, representing an environmental risk. Adsorption is one of the most-used treatments to remove recalcitrant compounds, although there is still a lack of efficient biosorbents. This work aimed to develop an efficient biosorbent using additive manufacturing (AM) to synthesize bionanocomposite hydrogels based on cellulose fibers, sodium alginate (SA), and graphene oxide (GO) for CQ adsorption. The hydrogels were characterized by mechanical, morphological, and physicochemical techniques. Results show that increasing GO content and reducing water contributed to higher yield stress, which is important for maintaining shape fidelity during the printing. SEM images evidenced thin GO layers interacting with the polymer matrix and cellulose fibers, resulting in 3D disordered porous microstructures. The adsorption capacity of the 3D-printed hydrogel samples for aqueous CQ was analyzed by evaluating the pH effect, contact time, and the adsorption equilibrium isotherms, showing notorious potential for CQ removal, with maximum adsorption capacity of ~25 mg\u2219g\u22121 at 25 \u00b0C. Results show that the tested formulations were stable for producing hydrogels and efficient on chloroquine adsorption, revealing their potential as novel adsorbents for removing emerging organic pollutants from water.<\/jats:p>","DOI":"10.3390\/jcs9120673","type":"journal-article","created":{"date-parts":[[2025,12,5]],"date-time":"2025-12-05T17:35:17Z","timestamp":1764956117000},"page":"673","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Additive Manufacturing of Graphene Oxide\/Sodium Alginate\u2013Cotton Microfiber Composite Hydrogels: Structure, Properties, and Adsorption Performance"],"prefix":"10.3390","volume":"9","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4187-392X","authenticated-orcid":false,"given":"Nickolly B. V.","family":"Serafim","sequence":"first","affiliation":[{"name":"Chemical Engineering Department, Federal University of Pernambuco, Recife 50670-901, Brazil"},{"name":"LSRE-LCM, ALiCE, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5336-1390","authenticated-orcid":false,"given":"Caroline M. B.","family":"de Araujo","sequence":"additional","affiliation":[{"name":"Campus de Gualtar, University of Minho, R. da Universidade, 4710-057 Braga, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1134-1743","authenticated-orcid":false,"given":"Margarida S. C. A.","family":"Brito","sequence":"additional","affiliation":[{"name":"LSRE-LCM, ALiCE, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal"}]},{"given":"Yaidelin A.","family":"Manrique","sequence":"additional","affiliation":[{"name":"LSRE-LCM, ALiCE, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6469-4871","authenticated-orcid":false,"given":"Cl\u00e1udia G.","family":"Silva","sequence":"additional","affiliation":[{"name":"LSRE-LCM, ALiCE, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7415-7260","authenticated-orcid":false,"given":"Marcos G.","family":"Ghislandi","sequence":"additional","affiliation":[{"name":"Engineering Campus, Federal Rural University of Pernambuco, R. Cento e Sessenta e Tr\u00eas, 300, Cabo de Santo Agostinho 54518-430, Brazil"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1729-3386","authenticated-orcid":false,"given":"Jose L.","family":"Sanchez-Salvador","sequence":"additional","affiliation":[{"name":"Chemical Engineering and Materials Department, Universidad Complutense de Madrid (UCM), Avda. Complutense s\/n, 28040 Madrid, Spain"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6820-7698","authenticated-orcid":false,"given":"Angeles","family":"Blanco","sequence":"additional","affiliation":[{"name":"Chemical Engineering and Materials Department, Universidad Complutense de Madrid (UCM), Avda. Complutense s\/n, 28040 Madrid, Spain"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8006-1556","authenticated-orcid":false,"given":"Jorge V. F. L.","family":"Cavalcanti","sequence":"additional","affiliation":[{"name":"Chemical Engineering Department, Federal University of Pernambuco, Recife 50670-901, Brazil"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2638-9096","authenticated-orcid":false,"given":"Maur\u00edcio A.","family":"da Motta Sobrinho","sequence":"additional","affiliation":[{"name":"Chemical Engineering Department, Federal University of Pernambuco, Recife 50670-901, Brazil"}]},{"given":"Alexandre F. P.","family":"Ferreira","sequence":"additional","affiliation":[{"name":"LSRE-LCM, ALiCE, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2025,12,4]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"50847","DOI":"10.1002\/app.50847","article-title":"3D printing of shape memory polymers","volume":"138","author":"Ehrmann","year":"2021","journal-title":"J. Appl. Polym. Sci."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"1309","DOI":"10.1016\/j.matpr.2021.11.059","article-title":"A comprehensive review of emerging additive manufacturing (3D printing technology): Methods, materials, applications, challenges, trends and future potential","volume":"52","author":"Praveena","year":"2022","journal-title":"Mater. Today Proc."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"9656938","DOI":"10.1155\/2019\/9656938","article-title":"Additive Manufacturing Technologies: An Overview about 3D Printing Methods and Future Prospects","volume":"2019","author":"Romero","year":"2019","journal-title":"Complexity"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"4275","DOI":"10.1007\/s10570-018-1888-y","article-title":"3D printing with cellulose materials","volume":"25","author":"Wang","year":"2018","journal-title":"Cellulose"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"447","DOI":"10.1016\/j.carbon.2018.11.006","article-title":"Alginate-graphene oxide hydrogels with enhanced ionic tunability and chemomechanical stability for light-directed 3D printing","volume":"143","author":"Valentin","year":"2019","journal-title":"Carbon"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"699","DOI":"10.1021\/acsapm.0c01002","article-title":"Direct Ink Writing of Hierarchically Porous Cellulose\/Alginate Monolithic Hydrogel as a Highly Effective Adsorbent for Environmental Applications","volume":"3","author":"Yuan","year":"2021","journal-title":"ACS Appl. Polym. Mater."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"3191","DOI":"10.1007\/s11947-023-03296-7","article-title":"Development of O\/W Pickering Emulsions Stabilized with Leek Leaf Trimmings Using Batch and Continuous Modes","volume":"17","author":"Marques","year":"2024","journal-title":"Food Bioprocess Technol."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"128357","DOI":"10.1016\/j.colsurfa.2022.128357","article-title":"Wastewater treatment using recyclable agar-graphene oxide biocomposite hydrogel in batch and fixed-bed adsorption column: Bench experiments and modeling for the selective removal of organics","volume":"639","author":"Ghislandi","year":"2022","journal-title":"Colloids Surf. A Physicochem. Eng. Asp."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"17358","DOI":"10.1007\/s11356-021-16943-3","article-title":"Synthesis and application of graphene oxide as a nanoadsorbent to remove Cd (II) and Pb (II) from water: Adsorption equilibrium, kinetics, and regeneration","volume":"29","author":"Gomes","year":"2022","journal-title":"Environ. Sci. Pollut. Res."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"114425","DOI":"10.1016\/j.envres.2022.114425","article-title":"Continuous removal of pharmaceutical drug chloroquine and Safranin-O dye from water using agar-graphene oxide hydrogel: Selective adsorption in batch and fixed-bed experiments","volume":"216","author":"Wernke","year":"2023","journal-title":"Environ. Res."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"9181","DOI":"10.1007\/s13399-021-01828-9","article-title":"Novel plantain peel activated carbon\u2013supported zinc oxide nanocomposites (PPAC-ZnO-NC) for adsorption of chloroquine synthetic pharmaceutical used for COVID-19 treatment","volume":"13","author":"Dada","year":"2023","journal-title":"Biomass Convers. Biorefinery"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"133213","DOI":"10.1016\/j.chemosphere.2021.133213","article-title":"Application of activated carbon functionalized with graphene oxide for efficient removal of COVID-19 treatment-related pharmaceuticals from water","volume":"289","author":"Fachina","year":"2022","journal-title":"Chemosphere"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"1339","DOI":"10.1021\/ja01539a017","article-title":"Preparation of Graphitic Oxide","volume":"80","author":"Hummers","year":"1958","journal-title":"J. Am. Chem. Soc."},{"key":"ref_14","doi-asserted-by":"crossref","unstructured":"Sauerwein, M., Zlopasa, J., Doubrovski, Z., Bakker, C., and Balkenende, R. (2020). Reprintable Paste-Based Materials for Additive Manufacturing in a Circular Economy. Sustainability, 12.","DOI":"10.3390\/su12198032"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"1361","DOI":"10.1021\/ja02242a004","article-title":"The Adsorption of Gases on Plane Surfaces of Glass, Mica and Platinum","volume":"40","author":"Langmuir","year":"1918","journal-title":"J. Am. Chem. Soc."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"884","DOI":"10.1080\/01496395.2023.2167662","article-title":"The Sips isotherm equation: Often used and sometimes misused","volume":"58","author":"Hashim","year":"2023","journal-title":"Sep. Sci. Technol."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"118079","DOI":"10.1016\/j.seppur.2020.118079","article-title":"Fitting a little-known isotherm equation to S-shaped adsorption equilibrium data","volume":"259","author":"Chu","year":"2021","journal-title":"Sep. Purif. Technol."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"345","DOI":"10.1016\/j.carbpol.2016.08.047","article-title":"High performance agar\/graphene oxide composite aerogel for methylene blue removal","volume":"155","author":"Chen","year":"2017","journal-title":"Carbohydr. Polym."},{"key":"ref_19","doi-asserted-by":"crossref","unstructured":"Belattmania, Z., Kaidi, S., El Atouani, S., Katif, C., Bentiss, F., Jama, C., Reani, A., Sabour, B., and Vasconcelos, V. (2020). Isolation and FTIR-ATR and 1H NMR Characterization of Alginates from the Main Alginophyte Species of the Atlantic Coast of Morocco. Molecules, 25.","DOI":"10.3390\/molecules25184335"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1475","DOI":"10.1039\/D3SM01053H","article-title":"Separation of the heme protein cytochrome C using a 3D structured graphene oxide bionanocomposite as an adsorbent","volume":"20","author":"Rios","year":"2024","journal-title":"Soft Matter"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"1313","DOI":"10.1007\/s00216-020-03094-6","article-title":"Micro-FTIR combined with curve fitting method to study cellulose crystallinity of developing cotton fibers","volume":"413","author":"Zhang","year":"2021","journal-title":"Anal. Bioanal. Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"133034","DOI":"10.1016\/j.colsurfa.2023.133034","article-title":"Multi-crosslinked robust alginate\/polyethyleneimine modified graphene aerogel for efficient organic dye removal","volume":"683","author":"Liu","year":"2024","journal-title":"Colloids Surf. A Physicochem. Eng. Asp."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"128240","DOI":"10.1016\/j.chemosphere.2020.128240","article-title":"Crucial roles of graphene oxide in preparing alginate\/nanofibrillated cellulose double network composites hydrogels","volume":"263","author":"Liu","year":"2021","journal-title":"Chemosphere"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"41473","DOI":"10.1021\/acsami.7b13534","article-title":"A 3D Printable and Mechanically Robust Hydrogel Based on Alginate and Graphene Oxide","volume":"9","author":"Liu","year":"2017","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"4343","DOI":"10.1021\/acsami.9b22062","article-title":"Chondroinductive Alginate-Based Hydrogels Having Graphene Oxide for 3D Printed Scaffold Fabrication","volume":"12","author":"Arens","year":"2020","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_26","doi-asserted-by":"crossref","unstructured":"Flores-Hern\u00e1ndez, C.G., Cornejo-Villegas, M.d.l.A., Moreno-Martell, A., and Del Real, A. (2021). Synthesis of a Biodegradable Polymer of Poly (Sodium Alginate\/Ethyl Acrylate). Polymers, 13.","DOI":"10.3390\/polym13040504"},{"key":"ref_27","doi-asserted-by":"crossref","unstructured":"Kowalonek, J., \u0141ukomska, B., and Szyd\u0142owska-Czerniak, A. (2025). Color, Structure, and Thermal Stability of Alginate Films with Raspberry and\/or Black Currant Seed Oils. Molecules, 30.","DOI":"10.3390\/molecules30020245"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"3374","DOI":"10.1021\/acs.biomac.0c00805","article-title":"Thermal Degradation of Cellulose Filaments and Nanocrystals","volume":"21","author":"Hamad","year":"2020","journal-title":"Biomacromolecules"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"146","DOI":"10.1016\/j.mee.2016.03.030","article-title":"Low-temperature thermal reduction of graphene oxide films in ambient atmosphere: Infra-red spectroscopic studies and gas sensing applications","volume":"159","author":"Tegou","year":"2016","journal-title":"Microelectron. Eng."},{"key":"ref_30","doi-asserted-by":"crossref","unstructured":"Akinyi, C., Longun, J., Chen, S., and Iroh, J.O. (2021). Decomposition and Flammability of Polyimide Graphene Composites. Minerals, 11.","DOI":"10.3390\/min11020168"},{"key":"ref_31","doi-asserted-by":"crossref","unstructured":"Zhao, W., Qi, Y., Wang, Y., Xue, Y., Xu, P., Li, Z., and Li, Q. (2018). Morphology and Thermal Properties of Calcium Alginate\/Reduced Graphene Oxide Composites. Polymers, 10.","DOI":"10.3390\/polym10090990"},{"key":"ref_32","first-page":"100133","article-title":"Development and physical characterization of novel bio-nanocomposite films based on reduced graphene oxide, agar and melipona honey","volume":"2","author":"Lemus","year":"2021","journal-title":"Carbohydr. Polym. Technol. Appl."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"684","DOI":"10.22146\/ijc.38168","article-title":"Alginate-Graphene Oxide Biocomposite Sorbent for Rapid and Selective Extraction of Non-Steroidal Anti-Inflammatory Drugs Using Micro-Solid Phase Extraction","volume":"19","author":"Tabish","year":"2019","journal-title":"Indones. J. Chem."},{"key":"ref_34","doi-asserted-by":"crossref","unstructured":"Kumar, N., Kumar, B., Gupta, H., and Kumar, A. (2023). Development and Evaluation of Cellulose\/Graphene-Oxide Based Composite for Removing Phenol from Aqueous Solutions. Polymers, 15.","DOI":"10.3390\/polym15030572"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"122517","DOI":"10.1016\/j.seppur.2022.122517","article-title":"Nitrogen-rich based conjugated microporous polymers for highly efficient adsorption and removal of COVID-19 antiviral drug chloroquine phosphate from environmental waters","volume":"305","author":"Wang","year":"2023","journal-title":"Sep. Purif. Technol."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"3538","DOI":"10.1016\/j.matpr.2022.06.099","article-title":"Synthesis, physiochemical and spectroscopic characterization of palm kernel shell activated carbon doped AgNPs (PKSAC@AgNPs) for adsorption of chloroquine pharmaceutical waste","volume":"65","author":"Atunwa","year":"2022","journal-title":"Mater. Today Proc."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"85344","DOI":"10.1007\/s11356-023-28242-0","article-title":"Adsorption of chloroquine, propranolol, and metformin in aqueous solutions using magnetic graphene oxide nanocomposite","volume":"30","author":"Nascimento","year":"2023","journal-title":"Environ. Sci. Pollut. Res."},{"key":"ref_38","first-page":"1","article-title":"Removal of Aspirin and Chloroquine from Aqueous Solution Using Organo-Clay Derived from Kaolinite","volume":"9","author":"Nkwoada","year":"2022","journal-title":"J. Phys. Chem. Mater."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"122162","DOI":"10.1016\/j.molliq.2023.122162","article-title":"Removal of chloroquine from the aqueous solution by adsorption onto a\u00e7a\u00ed-based biochars: Kinetics, thermodynamics, and phytotoxicity","volume":"383","author":"Santos","year":"2023","journal-title":"J. Mol. Liq."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"58156","DOI":"10.1007\/s11356-023-26669-z","article-title":"An eco-friendly cellulose support functionalized with tin titanate nanoparticles for the fast removal of clonazepam drug from the drinking water: Adsorption mechanisms","volume":"30","author":"Oliva","year":"2023","journal-title":"Environ. Sci. Pollut. Res."}],"container-title":["Journal of Composites Science"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2504-477X\/9\/12\/673\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,12,5]],"date-time":"2025-12-05T18:09:02Z","timestamp":1764958142000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2504-477X\/9\/12\/673"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,12,4]]},"references-count":40,"journal-issue":{"issue":"12","published-online":{"date-parts":[[2025,12]]}},"alternative-id":["jcs9120673"],"URL":"https:\/\/doi.org\/10.3390\/jcs9120673","relation":{},"ISSN":["2504-477X"],"issn-type":[{"value":"2504-477X","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,12,4]]}}}