In this work, we applied advanced Synchrotron Radiation (SR) induced techniques to the study of the chemisorption of the Self Assembling Peptide EAbuK16, i.e., H-Abu-Glu-Abu-Glu-Abu-Lys-Abu-Lys-Abu-Glu-Abu-Glu-Abu-Lys-Abu-Lys-NH₂ that is able to spontaneously aggregate in anti-parallel β-sheet conformation, onto annealed Ti25Nb10Zr alloy surfaces. This synthetic amphiphilic oligopeptide is a good candidate to mimic extracellular matrix for bone prosthesis, since its β-sheets stack onto each other in a multilayer oriented nanostructure with internal pores of 5-200 nm size. To prepare the biomimetic material, Ti25Nb10Zr discs were treated with aqueous solutions of EAbuK16 at different pH values. Here we present the results achieved by performing SR-induced X-ray Photoelectron Spectroscopy (SR-XPS), angle-dependent Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, FESEM and AFM imaging on Ti25Nb10Zr discs after incubation with self-assembling peptide solution at five different pH values, selected deliberately to investigate the best conditions for peptide immobilization.

Department of Industrial Engineering University of Padua Via Marzolo 9 Padua 35131 Italy

Department of Science Roma Tre University of Rome Via della Vasca Navale 79 00146 Rome Italy

Department of Surface and Plasma Science Faculty of Mathematics and Physics Charles University 5 Holešovičkách 2 18000 Prague Czech Republic

National Institute for Optoelectronics 409 Atomistilor St 077125 Magurele Romania

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Faria A.C.L., Rodrigues R.C.S., Rosa A.L., Ribeiro R.F. Experimental titanium alloys for dental applications. J. Prosthet. Dent. 2014;112:1448–1460. doi: 10.1016/j.prosdent.2013.12.025. PubMed DOI

Textor M., Sittig C., Frauchiger V., Tosatti S., Brunette D.M. Titanium in Medicine. Springer; Berlin/Heidelberg, Germany: 2001. Properties and biological significance of natural oxide films on titanium and its alloys; pp. 171–230.

Shah F.A., Trobos M., Thomsen P., Palmquist A. Commercially pure titanium (cp-Ti) versus titanium alloy (Ti6Al4V) materials as bone anchored implants—Is one truly better than the other? Mater. Sci. Eng. C. 2016;62:960–966. doi: 10.1016/j.msec.2016.01.032. PubMed DOI

Dettin M., Zamuner A., Brun P., Castagliuolo I., Iucci G., Battocchio C., Messina M., Marletta G. Covalent grafting of Ti surfaces with peptide hydrogel decorated with growth factors and self-assembling adhesive sequences. J. Pept. Sci. 2014;20:585–594. doi: 10.1002/psc.2652. PubMed DOI

Liu X., Chu P.K., Ding C. Surface modification of titanium, titanium alloys, and related materials for biomedical applications. Mater. Sci. Eng. R. 2004;47:49–121. doi: 10.1016/j.mser.2004.11.001. DOI

Özcan M., Hämmerle C. Review: Titanium as a Reconstruction and Implant Material in Dentistry: Advantages and Pitfalls. Materials. 2012;5:1528–1545. doi: 10.3390/ma5091528. DOI

Brown S.A., Lemons J.E. Medical Applications of Titanium and Its Alloys: The Material and Biological Issues. ASTM; West Conshohocken, PA, USA: 1996.

Elias C.N., Lima J.H.C., Valiev R., Meyers A. Biomedical applications of titanium and its alloys. JOM. 2008;60:46–49. doi: 10.1007/s11837-008-0031-1. DOI

Khorasani A.M., Goldberg M., Doeven E.H., Littlefair G. Titanium in biomedical applications—Properties and fabrication: A review. J. Biomater. Tissue Eng. 2015;5:593–619. doi: 10.1166/jbt.2015.1361. DOI

Veiga C., Davim J.P., Loureiro A.J.R. Properties and applications of titanium alloys: A brief review. Rev. Adv. Mater. Sci. 2012;32:133–148.

Geetha M., Singh A.K., Asokamani R., Gogia A.K. Ti based biomaterials, the ultimate choice for orthopaedic implants—A review. Prog. Mater. Sci. 2009;54:397–425. doi: 10.1016/j.pmatsci.2008.06.004. DOI

Sidambe A.T. Biocompatibility of Advanced Manufactured Titanium Implants—A Review. Materials. 2014;7:8168–8188. doi: 10.3390/ma7128168. PubMed DOI PMC

Katzer A., Hockertz S., Buchhorn G.H., Loehr J.F. In vitro toxicity and mutagenicity of CoCrMo and Ti6Al wear particles. Toxicology. 2003;190:145–154. doi: 10.1016/S0300-483X(03)00147-1. PubMed DOI

Satoh K., Sato S., Wagatsuma K. Formation mechanism of toxic-element-free oxide layer on Ti–6Al–4V alloy in d.c. glow discharge plasma with pure oxygen gas. Surf. Coat. Technol. 2016;302:82–87. doi: 10.1016/j.surfcoat.2016.05.080. DOI

Lecocq M., Félix M.S., Linares J.-M., Chaves-Jacob J., Decherchi P., Dousset E. Titanium implant impairment and surrounding muscle cell death following neuro-myoelectrostimulation: An in vivo study. J. Biomed. Mater. Res. Part B. 2015;103:1594–1601. doi: 10.1002/jbm.b.33353. PubMed DOI

Hussein M.A., Mohammed A.S., Al-Aqeeli N. Wear Characteristics of Metallic Biomaterials: A Review. Materials. 2015;8:2749–2768. doi: 10.3390/ma8052749. DOI

Mahapatro A.J. Metals for biomedical applications and devices. J. Biomater. Tissue Eng. 2012;2:259–268. doi: 10.1166/jbt.2012.1059. DOI

Niinomi M., Nakai M., Hieda J. Development of new metallic alloys for biomedical applications. Acta Biomater. 2012;8:3888–3903. doi: 10.1016/j.actbio.2012.06.037. PubMed DOI

Okazaki Y., Rao S., Asao S., Tateishi T., Katsuda S., Furuki Y. Effects of Ti, Al and V concentrations on cell viability. Mater. Trans. JIM. 1998;39:1053–1062. doi: 10.2320/matertrans1989.39.1053. DOI

Zhang L.-C., Attar H., Calin M., Eckert J. Review on manufacture by selective laser melting and properties of titanium based materials for biomedical applications. J. Mater. Technol. 2016;31:66–76. doi: 10.1179/1753555715Y.0000000076. DOI

Li Y., Yang C., Zhao H., Qu S., Li X., Li Y. New Developments of Ti-Based Alloys for Biomedical Applications. Materials. 2014;7:1709–1800. doi: 10.3390/ma7031709. PubMed DOI PMC

Hao Y.-L., Li S.-J., Yang R. Biomedical titanium alloys and their additive manufacturing. Rare Met. 2016;35:661–671. doi: 10.1007/s12598-016-0793-5. DOI

Wang L., Lu W., Qin J., Zhang F., Zhang D. Influence of cold deformation on martensite transformation and mechanical properties of Ti–Nb–Ta–Zr alloy. J. Alloys Compd. 2009;469:512–518. doi: 10.1016/j.jallcom.2008.02.032. DOI

Tane M., Hagihara K., Ueda M., Nakano T., Okuda Y. Elastic-modulus enhancement during room-temperature aging and its suppression in metastable Ti–Nb-Based alloys with low body-centered cubic phase stability. Acta Mater. 2016;102:373–384. doi: 10.1016/j.actamat.2015.09.030. DOI

Stenlund P., Omar O., Brohede U., Norgren S., Norlindh B., Johansson A., Lausmaa J., Thomsen P., Palmquist A. Bone response to a novel Ti–Ta–Nb–Zr alloy. Acta Biomater. 2015;20:165–175. doi: 10.1016/j.actbio.2015.03.038. PubMed DOI

Okazaki Y. A New Ti–15Zr–4Nb–4Ta alloy for medical applications. Curr. Opin. Solid State Mater. Sci. 2001;5:45–53. doi: 10.1016/S1359-0286(00)00025-5. DOI

Okazaki Y., Gotoh E. Comparison of fatigue strengths of biocompatible Ti-15Zr-4Nb-4Ta alloy and other titanium materials. Mater. Sci. Eng. C. 2011;31:325–333. doi: 10.1016/j.msec.2010.09.015. DOI

Banerjee R., Nag S., Stechschulte J., Fraser H.L. Strengthening mechanisms in Ti–Nb–Zr–Ta and Ti–Mo–Zr–Fe orthopaedic alloys. Biomaterials. 2004;25:3413–3419. doi: 10.1016/j.biomaterials.2003.10.041. PubMed DOI

Nag S., Banerjee R., Fraser H.L. Microstructural evolution and strengthening mechanisms in Ti–Nb–Zr–Ta, Ti–Mo–Zr–Fe and Ti–15Mo biocompatible alloys. Mater. Sci. Eng. C. 2005;25:357–362. doi: 10.1016/j.msec.2004.12.013. PubMed DOI

Liu Y.Z., Zu X.T., Qiu S.Y., Wang L., Ma W.G., Wei C.F. Surface characterization and corrosion resistance of Ti–Al–Zr alloy by niobium ion implantation. Nucl. Instrum. Methods Phys. Res. Sect. B. 2006;244:397–402. doi: 10.1016/j.nimb.2005.10.025. DOI

Chaves J.M., Florêncio O., Silva P.S., Marques P.W.B., Afonso C.R.M. Influence of phase transformations on dynamical elastic modulus and anelasticity of beta Ti–Nb–Fe alloys for biomedical applications. J. Mech. Behav. Biomed. Mater. 2015;46:184–196. doi: 10.1016/j.jmbbm.2015.02.030. PubMed DOI

Miyazaki S., Kim H.Y., Hosoda H. Development and characterization of Ni-free Ti-base shape memory and superelastic alloys. Mater. Sci. Eng. A. 2006;438–440:18–24. doi: 10.1016/j.msea.2006.02.054. DOI

Bai Y., Hao Y.L., Li S.J., Hao Y.Q., Yang R., Prima F. Corrosion behavior of biomedical Ti–24Nb–4Zr–8Sn alloy in different simulated body solutions. Mater. Sci. Eng. C. 2013;33:2159–2167. doi: 10.1016/j.msec.2013.01.036. PubMed DOI

Fojt J., Joska L., Málek J. Corrosion behaviour of porous Ti–39Nb alloy for biomedical applications. Corros. Sci. 2013;71:78–83. doi: 10.1016/j.corsci.2013.03.007. DOI

Okazaki Y., Rao S., Asao S., Tateishi T. Effects of metallic concentrations other than Ti, Al and V on cell viability. Mater. Trans. JIM. 1998;39:1070–1079. doi: 10.2320/matertrans1989.39.1070. DOI

Li Y., Wong C., Xiong J., Hodgson P., Wen C. Cytotoxicity of titanium and titanium alloying elements. J. Dent. Res. 2010;89:493–497. doi: 10.1177/0022034510363675. PubMed DOI

Matsuno H., Yokoyama A., Watari F., Uo M., Kawasaki T. Biocompatibility and osteogenesis of refractory metal implants, titanium, hafnium, niobium, tantalum and rhenium. Biomaterials. 2001;22:1253–1262. doi: 10.1016/S0142-9612(00)00275-1. PubMed DOI

Hickman J.W., Gulbransen E.A. Oxide films formed on titanium, zirconium, and their alloys with nickel, copper, and cobalt. Anal. Chem. 1948;20:158–165. doi: 10.1021/ac60014a016. DOI

Yilmazbayhan A., Motta A.T., Comstock R.J., Sabol G.P., Laid B., Cai Z. Structure of zirconium alloy oxides formed in pure water studied with synchrotron radiation and optical microscopy: Relation to corrosion rate. J. Nucl. Mater. 2004;324:6–22. doi: 10.1016/j.jnucmat.2003.08.038. DOI

Motta A.T., Gomes da Silva M.J., Yilmazbayhan A., Comstock R.J., Cai Z., Lai B. Microstructural characterization of oxides formed on model Zr alloys using synchrotron radiation. J. ASTM Int. 2008;5:1–20. doi: 10.1520/JAI101257. DOI

Wang B.L., Zheng Y.F., Zhao L.C. Electrochemical corrosion behavior of biomedical Ti–22Nb and Ti–22Nb–6Zr alloys in saline medium. Mater. Corros. 2009;60:788–794. doi: 10.1002/maco.200805173. DOI

Ishii M., Kaneko M., Oda T. Titanium and Its Alloys as Key Materials for Corrosion Protection Engineering. Shin-Nittetsu Giho; Tokyo, Japan: 2002. pp. 49–56.

Abdel-Hady M., Fuwa H., Hinoshita K., Kimura H., Shinzato Y., Morinaga M. Phase stability change with Zr content in β-type Ti–Nb alloys. Scr. Mater. 2007;57:1000–1003. doi: 10.1016/j.scriptamat.2007.08.003. DOI

Kim J.I., Kim H.Y., Inamura T., Hosoda H., Miyazaki S. Shape memory characteristics of Ti–22Nb–(2–8)Zr(at %) biomedical alloys. Mater. Sci. Eng. A. 2005;403:334–339. doi: 10.1016/j.msea.2005.05.050. DOI

Wang B.L., Li L., Zheng Y.F. In vitro cytotoxicity and hemocompatibility studies of Ti-Nb, Ti-Nb-Zr and Ti-Nb-Hf biomedical shape memory alloys. Biomed. Mater. 2010;5:44102. doi: 10.1088/1748-6041/5/4/044102. PubMed DOI

Kim J.I., Kim H.Y., Inamura T., Hosoda H., Miyazaki S. Effect of annealing temperature on microstructure and shape memory characteristics of Ti–22Nb–6Zr (at %) biomedical alloy. Mater. Trans. 2006;47:505–512. doi: 10.2320/matertrans.47.505. DOI

Nayak S., Dey T., Naskar D., Kundu S.C. The promotion of osseointegration of titanium surfaces by coating with silk protein sericin. Biomaterials. 2013;34:2855–2864. doi: 10.1016/j.biomaterials.2013.01.019. PubMed DOI

Franchi S., Battocchio C., Galluzzi M., Navisse E., Zamuner A., Dettin M., Iucci G. Self-assembling peptide hydrogels immobilized on silicon surfaces. Mater. Sci. Eng. C. 2016;69:200–207. doi: 10.1016/j.msec.2016.06.060. PubMed DOI

Gambaretto R., Tonin L., Di Bello C., Dettin M. Self-assembling peptides: Correlation among sequence, secondary structure in solution and film formation. Biopolymers. 2008;89:906–915. doi: 10.1002/bip.21030. PubMed DOI

Iucci G., Battocchio C., Dettin M., Gambaretto R., Polzonetti G. A NEXAFS and XPS study of the adsorption of self-assembling peptides on TiO2: The influence of the side chains. Surf. Interface Anal. 2008;40:210–214. doi: 10.1002/sia.2717. DOI

Battocchio C., Iucci G., Dettin M., Carravetta V., Monti S., Polzonetti G. Self-assembling behaviour of self-complementary oligopeptides on biocompatible substrates. Mater. Sci. Eng. B. 2010;169:36–42. doi: 10.1016/j.mseb.2009.12.051. DOI

Kokubo T., Takadama H. How useful is SBF in predicting in vivo bone bioactivity? Biomaterials. 2006;27:2907–2915. doi: 10.1016/j.biomaterials.2006.01.017. PubMed DOI

Gilewicz A., Chmielewska P., Murzynski D., Dobruchowska E., Warcholinski B. Corrosion resistance of CrN and CrCN/CrN coatings deposited using cathodic arc evaporation in Ringer’s and Hank’s solutions. Surf. Coat. Technol. 2016;299:7–14. doi: 10.1016/j.surfcoat.2016.04.069. DOI

Mansfeld F., Oldham K.B. A modification of the Stern—Geary linear polarization equation. Corros. Sci. 1971;11:787–796. doi: 10.1016/S0010-938X(71)80012-4. DOI

Erika G., Ruslan O., Florian S., Hikmet S., Alexander F. LowDosePES: An End-Station for Low-Dose, Angular-Resolved and Time-Resolved Photoelectron Spectroscopy at BESSY II; Proceedings of the Scientific Opportunities with Electron Spectroscopy and RIXS, HZB/BESSY II; Berlin, Germany. 16–18 October 2017.

Moulder J.F., Stickle W.F., Sobol P.E., Bomben K.D. Handbook of X-ray Photoelectron Spectroscopy. Physical Electronics Inc.; Eden Prairie, MN, USA: 1996.

Beamson G., Briggs D. High Resolution XPS of Organic Polymers, The Scienta ESCA300 Database. John Wiley & Sons; Chichester, UK: 1992.

Briggs D., Seah M.P. Practical Surface Analysis, Vol. 1, Auger and X-ray Photoelectron Spectroscopy. John Wiley & Sons; Chichester, UK: 1994.

Nannarone S., Borgatti F., De Luisa A., Doyle B.P., Gazzadi G.C., Gigli A., Finetti P., Mahne N., Pasquali L., Pedio M., et al. The BEAR Beamline at Elettra. AIP Conf. Proc. 2004;705:450–453.

Kim H.Y., Ikehara Y., Kim J.I., Hosoda H., Miyazaki S. Martensitic transformation, shape memory effect and superelasticity of Ti–Nb binary alloys. Acta Mater. 2006;54:2419–2429. doi: 10.1016/j.actamat.2006.01.019. DOI

Bowen A.W. Omega phase embrittlement in aged Ti-15%Mo. Scr. Metall. 1971;5:709–715. doi: 10.1016/0036-9748(71)90258-4. DOI

Sass S.L. The ω phase in a Zr-25 at % Ti alloy. Acta Metall. 1969;17:813–820. doi: 10.1016/0001-6160(69)90100-X. DOI

Isaacs H.S., Ishikawa Y. Current and Potential Transients during Localized Corrosion of Stainless Steel. J. Electrochem. Soc. 1985;132:1288–1293. doi: 10.1149/1.2114104. DOI

Thirumalaikumarasamy D., Shanmugam K., Balasubramanian V. Comparison of the corrosion behaviour of AZ31B magnesium alloy under immersion test and potentiodynamic polarization test in NaCl solution. J. Magnes. Alloys. 2014;2:36–49. doi: 10.1016/j.jma.2014.01.004. DOI

Song G. Control of biodegradation of biocompatable magnesium alloys. Corros. Sci. 2007;49:1696–1701. doi: 10.1016/j.corsci.2007.01.001. DOI

Cotrut C.M., Parau A.C., Gherghilescu A.I., Titorencu I., Pana I., Cojocaru D.V., Pruna V., Constantin L., Dan I., Vranceanu D.M., et al. Mechanical, in vitro corrosion resistance and biological compatibility of casted and annealed Ti25Nb10Zr alloy. Metals. 2017;7:86. doi: 10.3390/met7030086. DOI

Stohr J. In: NEXAFS Spectroscopy. Gomer C., editor. Springer; Berlin, Germany: 1991. (Springer Series in Surface Sciences).