{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,16]],"date-time":"2026-10-16T17:57:12Z","timestamp":1792173432590,"version":"4.4.0"},"reference-count":48,"publisher":"MDPI AG","issue":"2","license":[{"start":{"date-parts":[[2018,1,27]],"date-time":"2018-01-27T00:00:00Z","timestamp":1517011200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Nobel Biocare UK"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Micromachines"],"abstract":"<jats:p>Current commercially available barrier membranes for oral surgery have yet to achieve a perfect design. Existing materials used are either non-resorbable and require a second surgery for their extraction, or alternatively are resorbable but suffer from poor structural integrity or degrade into acidic by-products. Silk has the potential to overcome these issues and has yet to be made into a commercially available dental barrier membrane. Reactive inkjet printing (RIJ) has recently been demonstrated to be a suitable method for assembling silk in its regenerated silk fibroin (RSF) form into different constructs. This paper will establish the properties of RSF solutions for RIJ and the suitability of RIJ for the construction of RSF barrier membranes. Printed RSF films were characterised by their crystallinity and surface properties, which were shown to be controllable via RIJ. RSF films degraded in either phosphate buffered saline or protease XIV solutions had degradation rates related to RSF crystallinity. RSF films were also printed with the inclusion of nano-hydroxyapatite (nHA). As reactive inkjet printing could control RSF crystallinity and hence its degradation rate, as well as offering the ability to incorporate bioactive nHA inclusions, reactive inkjet printing is deemed a suitable alternative method for RSF processing and the production of dental barrier membranes.<\/jats:p>","DOI":"10.3390\/mi9020046","type":"journal-article","created":{"date-parts":[[2018,1,29]],"date-time":"2018-01-29T07:46:20Z","timestamp":1517211980000},"page":"46","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":22,"title":["Reactive Inkjet Printing of Regenerated Silk Fibroin Films for Use as Dental Barrier Membranes"],"prefix":"10.3390","volume":"9","author":[{"given":"Patrick","family":"Rider","sequence":"first","affiliation":[{"name":"School of Clinical Dentistry, The University of Sheffield, Sheffield S10 2TA, UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ian.","family":"Brook","sequence":"additional","affiliation":[{"name":"School of Clinical Dentistry, The University of Sheffield, Sheffield S10 2TA, UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Patrick","family":"Smith","sequence":"additional","affiliation":[{"name":"Department of Mechanical Engineering, The University of Sheffield, Sheffield S1 3JD, UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6062-6254","authenticated-orcid":false,"given":"Cheryl","family":"Miller","sequence":"additional","affiliation":[{"name":"School of Clinical Dentistry, The University of Sheffield, Sheffield S10 2TA, UK"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2018,1,27]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"914","DOI":"10.1177\/0022034512457373","article-title":"Prevalence of periodontitis in adults in the United States: 2009 and 2010","volume":"91","author":"Eke","year":"2012","journal-title":"J. Dent. Res."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"101","DOI":"10.1016\/S1532-3382(12)70022-2","article-title":"The development of guided regeneration: Making the impossible possible and the unpredictable predictable","volume":"12","author":"Scantlebury","year":"2012","journal-title":"J. Evid. Dent. Pract."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"703","DOI":"10.1016\/j.dental.2012.04.022","article-title":"Recent advances in the development of GTR\/GBR membranes for periodontal regeneration\u2014A materials perspective","volume":"28","author":"Bottino","year":"2012","journal-title":"Dent. Mater."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"528","DOI":"10.1126\/science.1188936","article-title":"New opportunities for an ancient material","volume":"329","author":"Omenetto","year":"2010","journal-title":"Science"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"291","DOI":"10.1177\/0885328210384890","article-title":"Review paper: Absorbable polymeric surgical sutures: Chemistry, production, properties, biodegradability, and performance","volume":"25","author":"Pillai","year":"2010","journal-title":"J. Biomater. Appl."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"457","DOI":"10.1016\/j.addr.2012.09.043","article-title":"Silk fibroin biomaterials for tissue regenerations","volume":"65","author":"Kundu","year":"2013","journal-title":"Adv. Drug Deliv. Rev."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"991","DOI":"10.1016\/j.progpolymsci.2007.05.013","article-title":"Silk as a biomaterial","volume":"32","author":"Vepari","year":"2007","journal-title":"Prog. Polym. Sci."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"357","DOI":"10.1016\/S0142-9612(02)00326-5","article-title":"Enzymatic degradation behavior of porous silk fibroin sheets","volume":"24","author":"Li","year":"2003","journal-title":"Biomaterials"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"2926","DOI":"10.1016\/j.biomaterials.2009.12.026","article-title":"Mechanism of enzymatic degradation of beta-sheet crystals","volume":"31","author":"Numata","year":"2010","journal-title":"Biomaterials"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"1241","DOI":"10.1002\/adfm.200400405","article-title":"Water-stable silk films with reduced \u03b2-sheet content","volume":"15","author":"Jin","year":"2005","journal-title":"Adv. Funct. Mater."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"1514","DOI":"10.3390\/ijms10041514","article-title":"Biodegradation of silk biomaterials","volume":"10","author":"Cao","year":"2009","journal-title":"Int. J. Mol. Sci."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1080","DOI":"10.1021\/bm101422j","article-title":"Degradation mechanism and control of silk fibroin","volume":"12","author":"Lu","year":"2011","journal-title":"Biomacromolecules"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"379","DOI":"10.1002\/bit.20252","article-title":"Engineering cartilage-like tissue using human mesenchymal stem cells and silk protein scaffolds","volume":"88","author":"Meinel","year":"2004","journal-title":"Biotechnol. Bioeng."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"6064","DOI":"10.1016\/j.biomaterials.2006.07.008","article-title":"Stem cell-based tissue engineering with silk biomaterials","volume":"27","author":"Wang","year":"2006","journal-title":"Biomaterials"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"147","DOI":"10.1016\/j.biomaterials.2004.02.047","article-title":"The inflammatory responses to silk films in vitro and in vivo","volume":"26","author":"Meinel","year":"2005","journal-title":"Biomaterials"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"4309","DOI":"10.1016\/j.polymer.2008.08.006","article-title":"Polymeric materials based on silk proteins","volume":"49","author":"Hardy","year":"2008","journal-title":"Polymer"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"185","DOI":"10.1002\/pol.1981.180190117","article-title":"Physical properties and structure of silk. VII. Crystallization of amorphous silk fibroin induced by immersion in methanol","volume":"19","author":"Magoshi","year":"1981","journal-title":"J. Polym. Sci. Polym. Phys."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"219","DOI":"10.1007\/s00339-005-3428-5","article-title":"Processing and modification of films made from recombinant spider silk proteins","volume":"82","author":"Huemmerich","year":"2006","journal-title":"Appl. Phys. A"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"676","DOI":"10.1021\/bm201509b","article-title":"Shear-induced self-assembly of native silk proteins into fibrils studied by atomic force microscopy","volume":"13","author":"Greving","year":"2012","journal-title":"Biomacromolecules"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"6161","DOI":"10.1021\/ma0610109","article-title":"Determining beta-sheet crystallinity in fibrous proteins by thermal analysis and infrared spectroscopy","volume":"39","author":"Hu","year":"2006","journal-title":"Macromolecules"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"8625","DOI":"10.1007\/s10853-016-0121-3","article-title":"Biocompatible silk fibroin scaffold prepared by reactive inkjet printing","volume":"51","author":"Rider","year":"2016","journal-title":"J. Mater. Sci."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"731","DOI":"10.3233\/BME-130861","article-title":"Nucleation of hydroxyapatite on Antheraea pernyi (A. pernyi) silk fibroin film","volume":"24","author":"Yang","year":"2014","journal-title":"Bio-med. Mater. Eng."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"3918","DOI":"10.1002\/jbm.a.35061","article-title":"Polylactide nanofibers with hydroxyapatite as growth substrates for osteoblast-like cells","volume":"102","author":"Novotna","year":"2014","journal-title":"J. Biomed. Mater. Res. A"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"1612","DOI":"10.1038\/nprot.2011.379","article-title":"Materials fabrication from bombyx mori silk fibroin","volume":"6","author":"Rockwood","year":"2011","journal-title":"Nat. Protoc."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"404","DOI":"10.7763\/IJESD.2010.V1.78","article-title":"Regenerated silk fibroin from B. mori silkcocoon for tissue engineering applications","volume":"1","author":"Sah","year":"2010","journal-title":"Int. J. Environ. Sci. Dev."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"1083","DOI":"10.1016\/j.msec.2017.02.170","article-title":"The relationship between particle morphology and rheological properties in injectable nano-hydroxyapatite bone graft substitutes","volume":"75","author":"Ryabenkova","year":"2017","journal-title":"Mate. Sci. Eng. C"},{"key":"ref_27","unstructured":"Lopes, J., Dias, M., and Da Silva, V. (2009). Production Method for Calcium Phosphate Nano-Particles with High Purity and Their Use. (20,090,263,497), U.S. Patent."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"e3","DOI":"10.5334\/jors.97","article-title":"Pendent_drop: An imagej plugin to measure the surface tension from an image of a pendent drop","volume":"4","author":"Daerr","year":"2016","journal-title":"J. Open Res. Softw."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"676","DOI":"10.1038\/nmeth.2019","article-title":"Fiji: An open-source platform for biological-image analysis","volume":"9","author":"Schindelin","year":"2012","journal-title":"Nat. Methods"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"518","DOI":"10.1002\/mrd.22489","article-title":"The ImageJ ecosystem: An open platform for biomedical image analysis","volume":"82","author":"Schindelin","year":"2015","journal-title":"Mol. Reprod. Dev."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"92","DOI":"10.1016\/j.colsurfa.2006.03.008","article-title":"A snake-based approach to accurate determination of both contact points and contact angles","volume":"286","author":"Stalder","year":"2006","journal-title":"Colloids Surf. A"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"311","DOI":"10.1002\/mabi.201200323","article-title":"Effect of silk protein processing on drug delivery from silk films","volume":"13","author":"Pritchard","year":"2013","journal-title":"Macromol. Biosci."},{"key":"ref_33","unstructured":"Petrova, T., and Dooley, R.B. (2014, January 23\u201327). Revised release on surface tension of ordinary water substance. Proceedings of the International Association for the Properties of Water and Steam, Moscow, Russia."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"395","DOI":"10.1146\/annurev-matsci-070909-104502","article-title":"Inkjet printing of functional and structural materials: fluid property requirements, feature stability, and resolution","volume":"40","author":"Derby","year":"2010","journal-title":"Annu. Rev. Mater. Res."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"703","DOI":"10.1039\/b711984d","article-title":"Inkjet printing as a deposition and patterning tool for polymers and inorganic particles","volume":"4","author":"Tekin","year":"2008","journal-title":"Soft Matter"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"140","DOI":"10.1021\/je00024a011","article-title":"Density, viscosity, surface tension, and carbon dioxide solubility and diffusivity of methanol, ethanol, aqueous propanol, and aqueous ethylene glycol at 25 \u00b0C","volume":"26","author":"Won","year":"1981","journal-title":"J. Chem. Eng. Data"},{"key":"ref_37","doi-asserted-by":"crossref","unstructured":"Smith, P.J., and Morrin, A. (2017). Chapter 7: Reactive inkjet printing of silk barrier membranes for dental applications. Reactive Inkjet Printing, Royal Society of Chemistry.","DOI":"10.1039\/9781788010511"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"072102","DOI":"10.1063\/1.2217929","article-title":"An experimental study of drop-on-demand drop formation","volume":"18","author":"Dong","year":"2006","journal-title":"Phys. Fluids"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"625","DOI":"10.1038\/nphys1682","article-title":"Formation of beads-on-a-string structures during break-up of viscoelastic filaments","volume":"6","author":"Bhat","year":"2010","journal-title":"Nat. Phys."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"261","DOI":"10.1122\/1.3302451","article-title":"Evaluation of the inkjet fluid\u2019s performance using the \u201cCambridge Trimaster\u201d filament stretch and break-up device","volume":"54","author":"Vadillo","year":"2010","journal-title":"J. Rheol."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"9705","DOI":"10.1039\/c2sm26054a","article-title":"Behavior of silk protein at the air-water interface","volume":"8","author":"Yang","year":"2012","journal-title":"Soft Matter"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"094903","DOI":"10.1063\/1.1888026","article-title":"Ink-jet delivery of particle suspensions by piezoelectric droplet ejectors","volume":"97","author":"Reis","year":"2005","journal-title":"J. Appl. Phys."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"313","DOI":"10.1007\/s00397-013-0688-4","article-title":"Generation of inkjet droplet of non-Newtonian fluid","volume":"52","author":"Yoo","year":"2013","journal-title":"Rheol. Acta"},{"key":"ref_44","unstructured":"Rider, P.M. (2017). Reactive Inkjet Printing of Novel Silk Dental Barrier Membranes. [Ph.D. Thesis, The University of Sheffield]."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"6766","DOI":"10.1021\/ma034466o","article-title":"Molecular dynamics simulation of conformational change of poly(ala-gly) from silk I to silk II in relation to fiber formation mechanism of bombyxmorisilk fibroin","volume":"36","author":"Yamane","year":"2003","journal-title":"Macromolecules"},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"2690","DOI":"10.1016\/S0006-3495(00)76813-5","article-title":"Conformational transitions in model silk peptides","volume":"78","author":"Wilson","year":"2000","journal-title":"Biophys. J."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"2563","DOI":"10.1021\/bm050294m","article-title":"Structural study of irregular amino acid sequences in the heavy chain of bombyxmorisilk fibroin","volume":"6","author":"Ha","year":"2005","journal-title":"Biomacromolecules"},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"1380","DOI":"10.1016\/j.actbio.2009.10.041","article-title":"Water-insoluble silk films with silk I structure","volume":"6","author":"Lu","year":"2010","journal-title":"Acta Biomater."}],"container-title":["Micromachines"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2072-666X\/9\/2\/46\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T14:52:46Z","timestamp":1760194366000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2072-666X\/9\/2\/46"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2018,1,27]]},"references-count":48,"journal-issue":{"issue":"2","published-online":{"date-parts":[[2018,2]]}},"alternative-id":["mi9020046"],"URL":"https:\/\/doi.org\/10.3390\/mi9020046","relation":{},"ISSN":["2072-666X"],"issn-type":[{"value":"2072-666X","type":"electronic"}],"subject":[],"published":{"date-parts":[[2018,1,27]]}}}