{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,14]],"date-time":"2025-10-14T00:33:44Z","timestamp":1760402024668,"version":"build-2065373602"},"reference-count":52,"publisher":"MDPI AG","issue":"2","license":[{"start":{"date-parts":[[2020,1,8]],"date-time":"2020-01-08T00:00:00Z","timestamp":1578441600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100004663","name":"Ministry of Science and Technology, Taiwan","doi-asserted-by":"publisher","award":["MOST-104-2221-E-010-004-MY3"],"award-info":[{"award-number":["MOST-104-2221-E-010-004-MY3"]}],"id":[{"id":"10.13039\/501100004663","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Sensors"],"abstract":"<jats:p>A silk fibroin composite film that can simultaneously scavenge and probe H2O2 in situ was developed for possibly examining local concentrations of H2O2 for biomedical applications. A multi-functional composite film (GDES) that consists of graphene oxide (G), a photothermally responsive element that was blended with polydopamine (PDA, D)\/horseradish peroxidase (HRP, E) (or DE complex), and then GDE microaggregates were coated with silk fibroin (SF, S), a tyrosine-containing protein. At 37 \u00b0C, the H2O2-scavenging ability of a GDES film in solution at approximately 7.5 \u00d7 10\u22123 \u03bcmol H2O2\/mg film was the highest compared with those of S and GS films. The intensities of UV-excitable blue fluorescence of a GDES film linearly increased with increasing H2O2 concentrations from 4.0 \u03bcM to 80 \u03bcM at 37 \u00b0C. Interestingly, after a GDES film scavenged H2O2, the UV-excitable blue fluorescent film could be qualitatively monitored by eye, making the film an eye-probe H2O2 sensor. A GDES film enabled to heat H2O2-containing samples to 37 \u00b0C or higher by the absorption of near-IR irradiation at 808 nm. The good biocompatibility of a GDES film was examined according to the requirements of ISO-10993-5. Accordingly, a GDES film was developed herein to scavenge and eye-probe H2O2 in situ and so it has potential for biomedical applications.<\/jats:p>","DOI":"10.3390\/s20020366","type":"journal-article","created":{"date-parts":[[2020,1,9]],"date-time":"2020-01-09T03:07:11Z","timestamp":1578539231000},"page":"366","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Developing a Silk Fibroin Composite Film to Scavenge and Probe H2O2 Associated with UV-Excitable Blue Fluorescence"],"prefix":"10.3390","volume":"20","author":[{"given":"Tze-Wen","family":"Chung","sequence":"first","affiliation":[{"name":"Department of Biomedical Engineering, National Yang-Ming University, No.155, Sec.2, Linong Street, Taipei 11221, Taiwan"},{"name":"The Center for Advanced Pharmaceutics and Drug Delivery Research, National Yang-Ming University, Taipei 11221, Taiwan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Chun-Yi","family":"Chang","sequence":"additional","affiliation":[{"name":"Department of Biomedical Engineering, National Yang-Ming University, No.155, Sec.2, Linong Street, Taipei 11221, Taiwan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Chun-Ning","family":"Chang","sequence":"additional","affiliation":[{"name":"Department of Biomedical Engineering, National Yang-Ming University, No.155, Sec.2, Linong Street, Taipei 11221, Taiwan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Chiu-Hsun","family":"Liao","sequence":"additional","affiliation":[{"name":"Miaoli District Agricultural Research and Extension Station, Council of Agriculture, Executive Yuan, Miaoli County 36346, Taiwan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yun-Jen","family":"Jan","sequence":"additional","affiliation":[{"name":"Miaoli District Agricultural Research and Extension Station, Council of Agriculture, Executive Yuan, Miaoli County 36346, Taiwan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Li-Ting","family":"Chen","sequence":"additional","affiliation":[{"name":"Department of Biomedical Engineering, National Yang-Ming University, No.155, Sec.2, Linong Street, Taipei 11221, Taiwan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5585-7445","authenticated-orcid":false,"given":"Weng-Pin","family":"Chen","sequence":"additional","affiliation":[{"name":"Department of Mechanical Engineering, National Taipei University of Technology, Taipei 10608, Taiwan"},{"name":"Additive Manufacturing Center for Mass Customization Production, National Taipei University of Technology, Taipei 10608, Taiwan"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2020,1,8]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"722","DOI":"10.1038\/nrm2240","article-title":"Hydrogen peroxide: A metabolic by-product or a common mediator of ageing signals?","volume":"8","author":"Giorgio","year":"2007","journal-title":"Nat. Rev. Mol. Cell Biol."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"64","DOI":"10.1186\/2045-3701-4-64","article-title":"Recent advances in hydrogen peroxide imaging for biological applications","volume":"4","author":"Guo","year":"2014","journal-title":"Cell Biosci."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"427","DOI":"10.1002\/jcb.24683","article-title":"Hydrogen peroxide as a damage signal in tissue injury and inflammation: Murderer, mediator, or messenger?","volume":"115","year":"2014","journal-title":"J. Cell. Biochem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"219","DOI":"10.1177\/0022034509359125","article-title":"Factors affecting wound healing","volume":"89","author":"Guo","year":"2010","journal-title":"J. Dent. Res."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"113","DOI":"10.1159\/000322643","article-title":"Antioxidant therapies for wound healing: A clinical guide to currently commercially available products","volume":"24","author":"Fitzmaurice","year":"2011","journal-title":"Skin Pharmacol. Physiol."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"301","DOI":"10.1159\/000475501","article-title":"Hydrogen Peroxide: A potential wound therapeutic target?","volume":"26","author":"Zhu","year":"2017","journal-title":"Med. Princ. Pract."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"228","DOI":"10.1039\/B917103G","article-title":"The chemistry of graphene oxide","volume":"39","author":"Dreyer","year":"2010","journal-title":"Chem. Soc. Rev."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"190","DOI":"10.1016\/j.addr.2016.05.022","article-title":"Functionalized graphene nanocomposites for enhancing photothermal therapy in tumor treatment","volume":"105","author":"Chen","year":"2016","journal-title":"Adv. Drug Deliv. Rev."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"203","DOI":"10.1007\/s12274-008-8021-8","article-title":"Nano-graphene oxide for cellular imaging and drug delivery","volume":"1","author":"Sun","year":"2008","journal-title":"Nano Res."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"3298","DOI":"10.1002\/adma.201200373","article-title":"Graphene oxide as an optical biosensing platform","volume":"24","year":"2012","journal-title":"Adv. Mater."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"3055","DOI":"10.1016\/j.electacta.2010.01.035","article-title":"A novel hydrogen peroxide biosensor based on Au\u2013graphene\u2013HRP\u2013chitosan biocomposites","volume":"55","author":"Zhou","year":"2010","journal-title":"Electrochim. Acta"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"5785","DOI":"10.1039\/c2an36237f","article-title":"Catalytic activity and stability of glucose oxidase\/horseradish peroxidase co-confined in macroporous silica foam","volume":"137","author":"Cao","year":"2012","journal-title":"Analyst"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"781","DOI":"10.1039\/C0AN00379D","article-title":"A novel H2O2 sensor based on the enzymatically induced deposition of polyaniline at a horseradish peroxide\/aligned single-wall carbon nanotubes modified Au electrode","volume":"136","author":"Tang","year":"2011","journal-title":"Analyst"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"105","DOI":"10.1016\/j.ymeth.2016.07.016","article-title":"Quantification of hydrogen peroxide in plant tissues using Amplex Red","volume":"109","author":"Chakraborty","year":"2016","journal-title":"Methods"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"76","DOI":"10.1039\/C7AY02459B","article-title":"Enhanced peroxidase-like activity of Mo doped ceria nanoparticles for sensitive colorimetric detection of glucose","volume":"10","author":"Xue","year":"2018","journal-title":"Anal. Methods"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"117","DOI":"10.1016\/j.talanta.2015.11.047","article-title":"Horseradish peroxidase-catalyzed polymerization of L-DOPA for mono-\/bi-enzyme immobilization and amperometric biosensing of H2O2 and uric acid","volume":"149","author":"Dai","year":"2016","journal-title":"Talanta"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1357","DOI":"10.1016\/j.snb.2014.04.079","article-title":"Graphene-based field effect transistor enzymatic glucose biosensor using silk protein for enzyme immobilization and device substrate","volume":"202","author":"You","year":"2014","journal-title":"Sens. Actuator B-Chem."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"426","DOI":"10.1126\/science.1147241","article-title":"Mussel-inspired surface chemistry for multifunctional coatings","volume":"318","author":"Lee","year":"2007","journal-title":"Science"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"625","DOI":"10.1021\/bm101281b","article-title":"Bioinspired polymerization of dopamine to generate melanin-like nanoparticles having an excellent free-radical-scavenging property","volume":"12","author":"Ju","year":"2011","journal-title":"Biomacromolecules"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1353","DOI":"10.1002\/adma.201204683","article-title":"Dopamine-melanin colloidal nanospheres: An efficient near-infrared photothermal therapeutic agent for in vivo cancer therapy","volume":"25","author":"Liu","year":"2013","journal-title":"Adv. Mater."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"799","DOI":"10.1002\/mabi.201300482","article-title":"Silk pectin hydrogel with superior mechanical properties, biodegradability, and biocompatibility","volume":"14","author":"Numata","year":"2014","journal-title":"Macromol. Biosci."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"128","DOI":"10.1016\/j.jconrel.2010.11.007","article-title":"Silk fibroin as a vehicle for drug delivery applications","volume":"150","author":"Wenk","year":"2011","journal-title":"J. Control. Release"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"4615","DOI":"10.1002\/adfm.201400526","article-title":"Highly tunable elastomeric silk biomaterials","volume":"24","author":"Partlow","year":"2014","journal-title":"Adv. Funct. Mater."},{"key":"ref_24","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_25","doi-asserted-by":"crossref","first-page":"160","DOI":"10.1002\/mabi.201600173","article-title":"Promoting cardiomyogenesis of hBMSC with a forming self-assembly hBMSC microtissues\/HA-GRGD\/SF-PCL cardiac patch is mediated by the synergistic functions of HA-GRGD","volume":"17","author":"Chung","year":"2017","journal-title":"Macromol. Biosci."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"e1852","DOI":"10.1002\/term.2616","article-title":"Morphological transformation of hBMSC from 2D monolayer to 3D microtissue on low-crystallinity SF-PCL patch with promotion of cardiomyogenesis","volume":"12","author":"Lo","year":"2018","journal-title":"J. Tissue Eng. Regen. Med."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"8","DOI":"10.1016\/j.jtice.2015.10.006","article-title":"Gelatin\/PLGA hydrogel films and their delivery of hydrophobic drugs","volume":"60","author":"Chung","year":"2016","journal-title":"J. Taiwan Inst. Chem. Eng."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"248","DOI":"10.1016\/0003-2697(76)90527-3","article-title":"A rapid and sensitive method for the quantitation of microgram quantities of protein utilizing the principle of protein-dye binding","volume":"72","author":"Bradford","year":"1976","journal-title":"Anal. Biochem."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"531","DOI":"10.1016\/S0021-9258(18)74509-2","article-title":"Colorimetric determination of the components of 3,4-Dihydro-xyphenyl-alanine-Tyrosine mixtures","volume":"118","author":"Arnow","year":"1937","journal-title":"J. Biol. Chem."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1393","DOI":"10.1007\/s10811-017-1310-4","article-title":"Influence of sea grapes (Caulerpa racemosa) supplementation on physical, functional, and anti-oxidant properties of semi-sweet biscuits","volume":"30","author":"Kumar","year":"2018","journal-title":"J. Appl. Phycol."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"124","DOI":"10.5530\/fra.2016.1.15","article-title":"A Sensitive in vitro spectrophotometric hydrogen peroxide scavenging Assay using 1, 10-phenanthroline","volume":"6","author":"Mukhopadhyay","year":"2016","journal-title":"Free Radic. Antioxid."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"4253","DOI":"10.1007\/s10570-017-1433-4","article-title":"Photo-crosslinked methacrylated chitosan-based nanofibrous scaffolds as potential skin substitute","volume":"24","author":"Zhou","year":"2017","journal-title":"Cellulose"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"5464","DOI":"10.1021\/acs.chemrev.5b00620","article-title":"Noncovalent functionalization of graphene and graphene oxide for energy materials, biosensing, catalytic, and biomedical applications","volume":"116","author":"Georgakilas","year":"2016","journal-title":"Chem. Rev."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"8271","DOI":"10.1039\/C4CS00185K","article-title":"Jack of all trades: Versatile catechol crosslinking mechanisms","volume":"43","author":"Yang","year":"2014","journal-title":"Chem. Soc. Rev."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"251","DOI":"10.1016\/j.bios.2013.06.039","article-title":"Graphene-based nanoprobes and a prototype optical biosensing platform","volume":"50","author":"Xu","year":"2013","journal-title":"Biosens. Bioelectron."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"189","DOI":"10.1016\/j.aca.2015.11.014","article-title":"Amplified inhibition of the electrochemical signal of ferrocene by enzyme-functionalized graphene oxide nanoprobe for ultrasensitive immunoassay","volume":"902","author":"Lai","year":"2016","journal-title":"Anal. Chim. Acta"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"9873","DOI":"10.1021\/acs.langmuir.6b02141","article-title":"Investigation of dopamine analogues: Synthesis, mechanistic understanding, and structure\u2013property relationship","volume":"32","author":"Hu","year":"2016","journal-title":"Langmuir"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"4806","DOI":"10.1021\/nn1006368","article-title":"Improved synthesis of graphene oxide","volume":"4","author":"Marcano","year":"2010","journal-title":"ACS Nano"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"68","DOI":"10.1016\/j.carbon.2008.09.002","article-title":"Synthesis of enhanced hydrophilic and hydrophobic graphene oxide nanosheets by a solvent thermal Method","volume":"47","author":"Wang","year":"2009","journal-title":"Carbon"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"146","DOI":"10.1016\/j.elecom.2013.08.021","article-title":"Immobilization and catalytic activity of horseradish peroxidase on molybdenum disulfide nanosheets modified electrode","volume":"35","author":"Wang","year":"2013","journal-title":"Electrochem. Commun."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"8619","DOI":"10.1021\/la400587j","article-title":"Characterization of polydopamine thin films deposited at short times by autoxidation of dopamine","volume":"29","author":"Zangmeister","year":"2013","journal-title":"Langmuir"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"153","DOI":"10.1007\/s12221-014-0153-8","article-title":"Effect of molecular weight and concentration on crystallinity and post drawing of wet spun silk fibroin fiber","volume":"15","author":"Um","year":"2014","journal-title":"Fiber Polym."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"6739","DOI":"10.1021\/nn500504s","article-title":"Poly (vinyl alcohol) reinforced and toughened with poly(dopamine)-treated graphene oxide, and its use for humidity sensing","volume":"8","author":"Hwang","year":"2014","journal-title":"ACS Nano"},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"3334","DOI":"10.1021\/jp2102226","article-title":"Simultaneous reduction and surface functionalization of graphene oxide for hydroxyapatite mineralization","volume":"116","author":"Liu","year":"2012","journal-title":"J. Phys. Chem. C"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"51","DOI":"10.1016\/j.cca.2008.04.031","article-title":"Prostate-specific antigen detection by using a reusable amperometric immunosensor based on reversible binding and leasing of HRP-anti-PSA from phenylboronic acid modified electrode","volume":"395","author":"Liu","year":"2008","journal-title":"Clin. Chim. Acta"},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"89","DOI":"10.1016\/j.aca.2015.02.024","article-title":"Intrinsic peroxidase-like catalytic activity of nitrogen-doped graphene quantum dots and their application in the colorimetric detection of H2O2 and glucose","volume":"869","author":"Lin","year":"2015","journal-title":"Anal. Chim. Acta"},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"27","DOI":"10.1016\/j.radphyschem.2015.03.020","article-title":"Electron beam induced water-soluble silk fibroin nanoparticles as a natural antioxidant and reducing agent fora green synthesis of gold nano-colloid","volume":"118","author":"Wongkrongsak","year":"2016","journal-title":"Radiat. Phys. Chem."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"1533","DOI":"10.2147\/IJN.S174962","article-title":"Multifunctional PLGA-based nanoparticles as a controlled release drug delivery system for antioxidant and anticoagulant therapy","volume":"14","author":"Lee","year":"2019","journal-title":"Int. J. Nanomed."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"1163","DOI":"10.1002\/jcb.24459","article-title":"Polyphenols suppress hydrogen peroxide-induced oxidative stress in human bone-marrow derived mesenchymal stem cells","volume":"114","author":"Yagi","year":"2013","journal-title":"J. Cell. Biochem."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"33","DOI":"10.1016\/j.freeradbiomed.2014.02.005","article-title":"Short time exposure to hydrogen peroxide induces sustained glutathione export from cultured neurons","volume":"70","author":"Hohnholt","year":"2014","journal-title":"Free Radic. Biol. Med."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"2064","DOI":"10.1021\/jacs.5b11411","article-title":"Mechanisms of the antimicrobial activities of graphene materials","volume":"138","author":"Zou","year":"2016","journal-title":"J. Am. Chem. Soc."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"2607","DOI":"10.1021\/am200428v","article-title":"Cytotoxicity of graphene oxide and graphene in human erythrocytes and skin fibroblasts","volume":"3","author":"Liao","year":"2011","journal-title":"ACS Appl. Mater. Interfaces"}],"container-title":["Sensors"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1424-8220\/20\/2\/366\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T13:19:16Z","timestamp":1760361556000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1424-8220\/20\/2\/366"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,1,8]]},"references-count":52,"journal-issue":{"issue":"2","published-online":{"date-parts":[[2020,1]]}},"alternative-id":["s20020366"],"URL":"https:\/\/doi.org\/10.3390\/s20020366","relation":{},"ISSN":["1424-8220"],"issn-type":[{"type":"electronic","value":"1424-8220"}],"subject":[],"published":{"date-parts":[[2020,1,8]]}}}