{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T00:41:17Z","timestamp":1760229677271,"version":"build-2065373602"},"reference-count":50,"publisher":"MDPI AG","issue":"13","license":[{"start":{"date-parts":[[2022,6,21]],"date-time":"2022-06-21T00:00:00Z","timestamp":1655769600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"COMPETE 2020\u2014Programa Operacional Fatores de Competitividade\u2014Portugal 2020","award":["POCI-01-0247-FEDER-024533","UIDB\/00285\/2020"],"award-info":[{"award-number":["POCI-01-0247-FEDER-024533","UIDB\/00285\/2020"]}]},{"name":"FCT\u2014Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","award":["POCI-01-0247-FEDER-024533","UIDB\/00285\/2020"],"award-info":[{"award-number":["POCI-01-0247-FEDER-024533","UIDB\/00285\/2020"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Polymers"],"abstract":"<jats:p>This work studied the influence of hydrogel\u2019s physical properties (geometry and hierarchical roughness) on the in vitro sorption\/release profiles of molecules. To achieve this goal, chitosan (CS) solutions were cast in 3D-printed (3DP) molds presenting intricate shapes (cubic and half-spherical with\/without macro surface roughness) and further immersed in alkaline solutions of NaOH and NaCl. The resulting physically crosslinked hydrogels were mechanically stable in aqueous environments and successfully presented the shapes and geometries imparted by the 3DP molds. Sorption and release profiles were evaluated using methyl orange (MO) and paracetamol (PMOL) as model molecules, respectively. Results revealed that distinct MO sorption\/PMOL release profiles were obtained according to the sample\u2019s shape and presence\/absence of hierarchical roughness. MO sorption capacity of CS samples presented both dependencies of hierarchical surface and geometry parameters. Hence, cubic samples without a hierarchical surface presented the highest (up to 1.2 \u00d7 greater) dye removal capacity. Moreover, PMOL release measurements were more dependent on the surface area of hydrogels, where semi-spherical samples with hierarchical roughness presented the fastest (~1.13 \u00d7 faster) drug delivery profiles. This work demonstrates that indirect 3DP (via fused filament fabrication (FFF) technology) could be a simple strategy to obtain hydrogels with distinct sorption\/release profiles.<\/jats:p>","DOI":"10.3390\/polym14132530","type":"journal-article","created":{"date-parts":[[2022,6,22]],"date-time":"2022-06-22T04:12:01Z","timestamp":1655871121000},"page":"2530","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Indirect Additive Manufacturing: A Valid Approach to Modulate Sorption\/Release Profile of Molecules from Chitosan Hydrogels"],"prefix":"10.3390","volume":"14","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2297-508X","authenticated-orcid":false,"given":"Mariana F.","family":"Moreira","sequence":"first","affiliation":[{"name":"CEMMPRE-Department of Mechanical Engineering, University of Coimbra, 3030-788 Coimbra, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3851-0319","authenticated-orcid":false,"given":"Akel F.","family":"Kanaan","sequence":"additional","affiliation":[{"name":"CEMMPRE-Department of Mechanical Engineering, University of Coimbra, 3030-788 Coimbra, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1588-0640","authenticated-orcid":false,"given":"Ana P.","family":"Piedade","sequence":"additional","affiliation":[{"name":"CEMMPRE-Department of Mechanical Engineering, University of Coimbra, 3030-788 Coimbra, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2022,6,21]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1930001","DOI":"10.1142\/S2424862219300011","article-title":"Additive Manufacturing Applications in Industry 4.0: A Review","volume":"04","author":"Haleem","year":"2019","journal-title":"J. Ind. Integr. Manag."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"426","DOI":"10.1016\/j.wasman.2020.09.003","article-title":"3D printing goes greener: Study of the properties of post-consumer recycled polymers for the manufacturing of engineering components","volume":"118","author":"Pinho","year":"2020","journal-title":"Waste Manag."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"170","DOI":"10.1080\/17543266.2016.1223355","article-title":"The application of 3D printing technology in the fashion industry","volume":"10","author":"Vanderploeg","year":"2017","journal-title":"Int. J. Fash. Des. Technol. Educ."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"83","DOI":"10.1016\/j.tifs.2017.08.018","article-title":"3D printing: Printing precision and application in food sector","volume":"69","author":"Liu","year":"2017","journal-title":"Trends Food Sci. Technol."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"108","DOI":"10.1016\/j.ihj.2016.01.009","article-title":"Application of 3D printing in medicine","volume":"68","author":"Mishra","year":"2016","journal-title":"Indian Heart J."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"18","DOI":"10.1109\/MPOT.2016.2540098","article-title":"An Overview of 3-D Printing in Manufacturing, Aerospace, and Automotive Industries","volume":"35","author":"Lim","year":"2016","journal-title":"IEEE Potentials"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"119245","DOI":"10.1016\/j.ijpharm.2020.119245","article-title":"Additive Manufacturing Technologies for Drug Delivery Applications","volume":"580","author":"Mohammed","year":"2020","journal-title":"Int. J. Pharm."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"119820","DOI":"10.1016\/j.ijpharm.2020.119820","article-title":"Additive manufacturing in drug delivery applications: A review","volume":"589","author":"Sharma","year":"2020","journal-title":"Int. J. Pharm."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"173","DOI":"10.1016\/j.coche.2020.08.002","article-title":"A review of 3D printing techniques for environmental applications","volume":"28","author":"Nadagouda","year":"2020","journal-title":"Curr. Opin. Chem. Eng."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"132311","DOI":"10.1016\/j.cej.2021.132311","article-title":"Recent Advances in Polymer-based 3D Printing for Wastewater Treatment Application: An Overview","volume":"429","author":"Phang","year":"2022","journal-title":"Chem. Eng. J."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"269","DOI":"10.1002\/pi.1995.210380309","article-title":"Behaviour of catalase immobilised on poly(acrylonitrile)-g.co-hydroxyethyl methacrylate when used in a continuous system","volume":"38","author":"Piedade","year":"1995","journal-title":"Polym. Int."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"105","DOI":"10.1016\/0302-4598(92)80006-3","article-title":"An electrochemical bienzyme membrane sensor for free cholesterol","volume":"28","author":"Gil","year":"1992","journal-title":"Bioelectrochem. Bioenerg."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"269","DOI":"10.1002\/pola.1991.080290215","article-title":"Immobilization of catalase on membranes of poly(ethylene)-g-co-acrylic acid and poly(tetrafluoroethylene)-g-co-acrylic acid and their application in hydrogen peroxide electrochemical sensors","volume":"29","author":"Gil","year":"1991","journal-title":"J. Polym. Sci. Part A Polym. Chem."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"360","DOI":"10.1016\/j.jddst.2015.07.016","article-title":"3D printing by fused deposition modeling (FDM) of a swellable\/erodible capsular device for oral pulsatile release of drugs","volume":"30","author":"Melocchi","year":"2015","journal-title":"J. Drug Deliv. Sci. Technol."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"621","DOI":"10.1021\/acsestwater.0c00131","article-title":"Additive Manufacturing for Contaminants: Ammonia Removal Using 3D Printed Polymer-Zeolite Composites","volume":"1","author":"Kennedy","year":"2021","journal-title":"ACS ES&T Water"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"126383","DOI":"10.1016\/j.jhazmat.2021.126383","article-title":"Quantifying instant water cleaning efficiency using zinc oxide decorated complex 3D printed porous architectures","volume":"418","author":"Kumbhakar","year":"2021","journal-title":"J. Hazard. Mater."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"657","DOI":"10.1016\/j.ijpharm.2015.04.069","article-title":"Effect of geometry on drug release from 3D printed tablets","volume":"494","author":"Goyanes","year":"2015","journal-title":"Int. J. Pharm."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"157","DOI":"10.1016\/j.ejpb.2014.12.003","article-title":"3D printing of modified-release aminosalicylate (4-ASA and 5-ASA) tablets","volume":"89","author":"Goyanes","year":"2015","journal-title":"Eur. J. Pharm. Biopharm."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"414","DOI":"10.1016\/j.ijpharm.2015.10.039","article-title":"Fabrication of controlled-release budesonide tablets via desktop (FDM) 3D printing","volume":"496","author":"Goyanes","year":"2015","journal-title":"Int. J. Pharm."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"11","DOI":"10.1016\/j.ejps.2014.11.009","article-title":"Fabrication of extended-release patient-tailored prednisolone tablets via fused deposition modelling (FDM) 3D printing","volume":"68","author":"Skowyra","year":"2015","journal-title":"Eur. J. Pharm. Sci."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"269","DOI":"10.1016\/j.cej.2018.05.089","article-title":"3D printed polyvinyl alcohol ferrate(VI) capsules: Effective means for the removal of pharmaceuticals and illicit drugs from wastewater","volume":"349","author":"Filip","year":"2018","journal-title":"Chem. Eng. J."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"121418","DOI":"10.1016\/j.jhazmat.2019.121418","article-title":"3D-Printed metal-organic frameworks within biocompatible polymers as excellent adsorbents for organic dyes removal","volume":"384","author":"Pei","year":"2020","journal-title":"J. Hazard. Mater."},{"key":"ref_23","doi-asserted-by":"crossref","unstructured":"Zamboulis, A., Michailidou, G., Koumentakou, I., and Bikiaris, D.N. (2022). Polysaccharide 3D Printing for Drug Delivery Applications. Pharmaceutics, 14.","DOI":"10.3390\/pharmaceutics14010145"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"309","DOI":"10.1016\/j.ijbiomac.2018.10.008","article-title":"Snakegourd root\/Astragalus polysaccharide hydrogel preparation and application in 3D printing","volume":"121","author":"Yan","year":"2019","journal-title":"Int. J. Biol. Macromol."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"110394","DOI":"10.1016\/j.matdes.2022.110394","article-title":"3D-printed polycaprolactone-chitosan based drug delivery implants for personalized administration","volume":"214","author":"Yang","year":"2022","journal-title":"Mater. Des."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"820","DOI":"10.1016\/j.ijbiomac.2021.08.022","article-title":"3D printable self-healing hyaluronic acid\/chitosan polycomplex hydrogels with drug release capability","volume":"188","author":"Barroso","year":"2021","journal-title":"Int. J. Biol. Macromol."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"109873","DOI":"10.1016\/j.msec.2019.109873","article-title":"A 3D printed chitosan-pectin hydrogel wound dressing for lidocaine hydrochloride delivery","volume":"104","author":"Long","year":"2019","journal-title":"Mater. Sci. Eng. C"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"6728","DOI":"10.1007\/s10853-019-03332-y","article-title":"3D-printed highly porous and reusable chitosan monoliths for Cu(II) removal","volume":"54","author":"Zhang","year":"2019","journal-title":"J. Mater. Sci."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"62","DOI":"10.1039\/D1GC01799C","article-title":"Chitosan-based inks for 3D printing and bioprinting","volume":"24","author":"Taghizadeh","year":"2022","journal-title":"Green Chem."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1038\/s41598-018-36613-8","article-title":"Study of 3D-printed chitosan scaffold features after different post-printing gelation processes","volume":"9","author":"Bergonzi","year":"2019","journal-title":"Sci. Rep."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"91","DOI":"10.1007\/s40883-019-00134-1","article-title":"Stimuli-Responsive Polysaccharide Hydrogels for Biomedical Applications: A Review","volume":"7","author":"Gholamali","year":"2021","journal-title":"Regen. Eng. Transl. Med."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"150","DOI":"10.1016\/j.jconrel.2020.06.012","article-title":"Chitosan hydrogels for sustained drug delivery","volume":"326","author":"Peers","year":"2020","journal-title":"J. Control. Release"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"117768","DOI":"10.1016\/j.carbpol.2021.117768","article-title":"Chitosan hydrogels in 3D printing for biomedical applications","volume":"260","author":"Rajabi","year":"2021","journal-title":"Carbohydr. Polym."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"233","DOI":"10.1016\/j.carbpol.2018.05.033","article-title":"Chitosan-based hydrogels: From preparation to biomedical applications","volume":"196","author":"Guilherme","year":"2018","journal-title":"Carbohydr. Polym."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"264","DOI":"10.1016\/j.carbpol.2018.08.070","article-title":"Review on recent progress in chitosan-based hydrogels for wastewater treatment application","volume":"201","author":"Peighambardoust","year":"2018","journal-title":"Carbohydr. Polym."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"1800","DOI":"10.1002\/pi.5467","article-title":"Chitosan adsorbents for dye removal: A review","volume":"66","author":"Kyzas","year":"2017","journal-title":"Polym. Int."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"964","DOI":"10.1002\/pi.5787","article-title":"A biopolymer-based 3D printable hydrogel for toxic metal adsorption from water","volume":"68","author":"Appuhamillage","year":"2019","journal-title":"Polym. Int."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"109624","DOI":"10.1016\/j.matdes.2021.109624","article-title":"Mechanical properties of 3D printed mouthguards: Influence of layer height and device thickness","volume":"203","author":"Sousa","year":"2021","journal-title":"Mater. Des."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1038\/srep36005","article-title":"Chitosan Hydrogel Structure Modulated by Metal Ions","volume":"6","author":"Nie","year":"2016","journal-title":"Sci. Rep."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"372","DOI":"10.1016\/j.carbpol.2016.09.046","article-title":"Fabrication and characterization of a self-crosslinking chitosan hydrogel under mild conditions without the use of strong bases","volume":"156","author":"Xu","year":"2017","journal-title":"Carbohydr. Polym."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1038\/srep07635","article-title":"Orientation in multi-layer chitosan hydrogel: Morphology, mechanism, and design principle","volume":"5","author":"Nie","year":"2015","journal-title":"Sci. Rep."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"782","DOI":"10.1016\/j.matdes.2011.07.001","article-title":"Mechanical and tribological response of ABS polymer matrix filled with graphite powder","volume":"34","author":"Kharrat","year":"2012","journal-title":"Mater. Des."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"117106","DOI":"10.1016\/j.carbpol.2020.117106","article-title":"Ionic and covalent crosslinking in chitosan-succinic acid membranes: Effect on physicochemical properties","volume":"251","author":"Gabriele","year":"2021","journal-title":"Carbohydr. Polym."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.vibspec.2017.10.005","article-title":"FTIR spectroscopy studies on the spontaneous neutralization of chitosan acetate films by moisture conditioning","volume":"94","author":"Salazar","year":"2018","journal-title":"Vib. Spectrosc."},{"key":"ref_45","first-page":"1","article-title":"Swelling kinetics, mechanical properties, and release characteristics of chitosan-based semi-IPN hydrogels","volume":"132","year":"2015","journal-title":"J. Appl. Polym. Sci."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1155\/2011\/809743","article-title":"Consequences of Neutralization on the Proliferation and Cytoskeletal Organization of Chondrocytes on Chitosan-Based Matrices","volume":"2011","author":"Noriega","year":"2011","journal-title":"Int. J. Carbohydr. Chem."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"117","DOI":"10.1016\/j.carbpol.2011.07.025","article-title":"Determination of the degree of N-acetylation (DA) of chitin and chitosan in the presence of water by first derivative ATR FTIR spectroscopy","volume":"87","author":"Beil","year":"2012","journal-title":"Carbohydr. Polym."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"25","DOI":"10.1016\/j.carbpol.2015.05.077","article-title":"NaOH treatment of chitosan films: Impact on macromolecular structure and film properties","volume":"132","author":"Takara","year":"2015","journal-title":"Carbohydr. Polym."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"3569","DOI":"10.1016\/S0032-3861(00)00713-8","article-title":"An infrared investigation in relation with chitin and chitosan characterization","volume":"42","author":"Brugnerotto","year":"2001","journal-title":"Polymer."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1103\/PhysRevE.91.022305","article-title":"Swelling of p H -sensitive hydrogels","volume":"91","author":"Drozdov","year":"2015","journal-title":"Phys. Rev. E\u2014Stat. Nonlinear Soft Matter Phys."}],"container-title":["Polymers"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4360\/14\/13\/2530\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T23:36:40Z","timestamp":1760139400000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4360\/14\/13\/2530"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,6,21]]},"references-count":50,"journal-issue":{"issue":"13","published-online":{"date-parts":[[2022,7]]}},"alternative-id":["polym14132530"],"URL":"https:\/\/doi.org\/10.3390\/polym14132530","relation":{},"ISSN":["2073-4360"],"issn-type":[{"type":"electronic","value":"2073-4360"}],"subject":[],"published":{"date-parts":[[2022,6,21]]}}}