Abstract
A silica-based sol-gel antibacterial coating has been prepared, and its performance has been compared with an antibacterial hydroxyapatite-based coating when applied to Ti6Al4V alloy. The antibacterial functionality has been provided by silver nanoparticles (Ag NPs) deposited after Ag+ reduction. This reduction was achieved by a low-temperature treatment in the case of the silica-based coating (<100 °C) and with high temperature in the case of the hydroxyapatite one (500 °C). Field emission scanning electron microscopy (FESEM) showed a better and more homogeneous distribution of Ag NPs on the coating in the case of the silica coating. Atomic force microscopy (AFM) characterization with a 1 nm diameter tip showed the formation of Ag NPs with a diameter of around 30 nm. Ag+ release in simulated body fluid at 37 °C, measured by inductively coupled plasma-mass spectrometry (ICP-MS), showed a continued release of Ag+ with time, achieving 2.68 mg Ag+/L after 40 days in the case of silica-based coating (approximately a fivefold when compared to hydroxyapatite (HA) coating). Antibacterial activity for both coatings was tested against Staphylococcus aureus and Staphylococcus epidermidis, showing a 99.9% lethality compared to the sol-gel coatings without Ag NPs. The silica-based coating combines the advantages of low-temperature synthesis, excellent distribution of Ag NPs, good antibacterial properties, and sustained release for 40 days.
Graphical abstract

The proposed sol-gel method of synthesis of bactericidal coatings showed the formation of Ag NPs of around 30 nm over the entire surface of the silica coating, as observed by FESEM and AFM characterization.
Highlights
-
Silica-based antibacterial coatings with silver nanoparticles have been obtained by sol-gel.
-
Silver nanoparticles (Ag NPs) are generated at low temperature (80 °C).
-
Ag NPs are synthesized due to a redox reaction between Ag+ with GPTMS as observed by FTIR.
-
Atomic force microscopy showed the formation of 30 nm diameter Ag NPs on the surface.
-
Transmission electron microscopy showed the formation of Ag NPs inside the coating.
This is a preview of subscription content, access via your institution.
















References
Neoh KG, Kang ET (2011) Combating Bacterial Colonization on Metals via Polymer Coatings: Relevance to Marine and Medical Applications. ACS Appl Mater Interfac 3:2808–2819. https://doi.org/10.1021/am200646t
Echeverria C, Torres MDT, Fernández-García M, de la Fuente-Núñez C, Muñoz-Bonilla A (2020) Physical methods for controlling bacterial colonization on polymer surfaces. Biotechnol Adv 43:107586. https://doi.org/10.1016/j.biotechadv.2020.107586
Reinosa JJ, Enríquez E, Fuertes V, Liu S, Menéndez J, Fernández JF (2022) The challenge of antimicrobial glazed ceramic surfaces. Ceram Int 48:7393–7404. https://doi.org/10.1016/j.ceramint.2021.12.121
Munir MT, Pailhories H, Eveillard M, Aviat F, Lepelletier D, Belloncle C, Federighi M (2019) Antimicrobial Characteristics of Untreated Wood: Towards a Hygienic Environment. Health 11:152–170. https://doi.org/10.4236/health.2019.112014
Chen J-C, Munir MT, Aviat F, Lepelletier D, Pape PL, Dubreil L, Irle M, Federighi M, Belloncle C, Eveillard M, Pailhoriès H (2020) Survival of Bacterial Strains on Wood (Quercus petraea) Compared to Polycarbonate, Aluminum and Stainless Steel. Antibiotics 9:804. https://doi.org/10.3390/antibiotics9110804
Wißmann JE, Kirchhoff L, Brüggemann Y, Todt D, Steinmann J, Steinmann E (2021) Persistence of Pathogens on Inanimate Surfaces: A Narrative Review. Microorganisms 9:343. https://doi.org/10.3390/microorganisms9020343
Kramer A, Schwebke I, Kampf G (2006) How long do nosocomial pathogens persist on inanimate surfaces? A systematic review. BMC Infect Dis 6:130. https://doi.org/10.1186/1471-2334-6-130
Kawaguchi Y, Shibuya M, Kinoshita I, Yatabe J, Narumi I, Shibata H, Hayashi R, Fujiwara D, Murano Y, Hashimoto H, Imai E, Kodaira S, Uchihori Y, Nakagawa K, Mita H, Yokobori S-i, Yamagishi A (2020) DNA Damage and Survival Time Course of Deinococcal Cell Pellets During 3 Years of Exposure to Outer Space. Front Microbiol 11:2050. https://doi.org/10.3389/fmicb.2020.02050
Salazar CB, Spencer P, Mohamad K, Jabeen A, Abdulmonem WA, Fernández N (2022) Future pandemics might be caused by bacteria and not viruses: Recent advances in medical preventive practice. Int J Health Sci 16:1–3
Zheng S, Bawazir M, Dhall A, Kim H-E, He L, Heo J, Hwang G (2021) Implication of Surface Properties, Bacterial Motility, and Hydrodynamic Conditions on Bacterial Surface Sensing and Their Initial Adhesion. Front Bioeng Biotechnol 9:643722. https://doi.org/10.3389/fbioe.2021.643722
Grinberg M, Orevi T, Kashtan N (2019) Bacterial surface colonization, preferential attachment and fitness under periodic stress. PLOS Comput Biol 15:e1006815. https://doi.org/10.1371/journal.pcbi.1006815
Flemming H-C, Wingender J, Szewzyk U, Steinberg P, Rice SA, Kjelleberg S (2016) Biofilms: an emergent form of bacterial life. Nat Rev Microbiol 14:563–575. https://doi.org/10.1038/nrmicro.2016.94
Tande AJ, Patel R (2014) Prosthetic Joint Infection. Clin Microbiol Rev 27:302–345. https://doi.org/10.1128/CMR.00111-13
Salar-Vidal L, Auñón Á, Esteban J (2023) Molecular Diagnosis of Osteoarticular Implant-Associated Infection: Available Techniques and How We Can Use Them. Prosthesis 5:1–12. https://doi.org/10.3390/prosthesis5010001
Trampuz A, Zimmerli W (2005) Prosthetic joint infections: update in diagnosis and treatment. Swiss Med Wkly 135:243–251. https://doi.org/10.4414/smw.2005.10934
Staphylococcus epidermidis Infection (2023) StatPearls Publishing (FL). https://www.ncbi.nlm.nih.gov/books/NBK563240/. Accessed 22 August 2023.
Lowy FD (1998) Staphylococcus aureus infections. N Engl J Med 339:520–532. https://doi.org/10.1056/NEJM199808203390806
Lee AS, de Lencastre H, Garau J, Kluytmans J, Malhotra-Kumar S, Peschel A, Harbarth S (2018) Methicillin-resistant Staphylococcus aureus. Nat Rev Dis Prim 4:18033. https://doi.org/10.1038/nrdp.2018.33
Andrade-Del Olmo J, Ruiz-Rubio L, Pérez-Alvarez L, Sáez-Martínez V, Vilas-Vilela JL (2020) Antibacterial Coatings for Improving the Performance of Biomaterials. Coatings 10:139. https://doi.org/10.3390/coatings10020139
Cloutier M, Mantovani D, Rosei F (2015) Antibacterial Coatings: Challenges, Perspectives, and Opportunities. Trends Biotechnol 33:637–652. https://doi.org/10.1016/j.tibtech.2015.09.002
Chen X, Zhou J, Qian Y, Zhao L (2023) Antibacterial coatings on orthopedic implants. Mater Today Bio 19:100586. https://doi.org/10.1016/j.mtbio.2023.100586
Lemire JA, Harrison JJ, Turner RJ (2013) Antimicrobial activity of metals: Mechanisms, molecular targets and applications. Nat Rev Microbiol 11:371–384. https://doi.org/10.1038/nrmicro3028
Bokov D, Jalil AT, Chupradit S, Suksatan W, Ansari MJ, Shewael IH, Valiev GH, Kianfar E (2021) Nanomaterial by Sol-Gel Method: Synthesis and Application. Adv Mater Sci Eng 2021:5102014. https://doi.org/10.1155/2021/5102014
Danks AE, Hall SR, Schnepp Z (2016) The evolution of ‘sol–gel’ chemistry as a technique for materials synthesis. Mater Horiz 3:91–112. https://doi.org/10.1039/C5MH00260E
Mahltig B, Grethe T, Haase H (2018) In: Klein L, Aparicio M, Jitianu A (ed) Handbook of Sol-Gel Science and Technology, Springer, Cham. https://doi.org/10.1007/978-3-319-19454-7_102-1
Xie K, Zhou Z, Guo Y, Wang L, Li G, Zhao S, Liu X, Li J, Jiang W, Wu S, Hao Y (2019) Long-term prevention of bacterial infection and enhanced osteoinductivity of a hybrid coating with selective silver toxicity. Adv Health Mater 8:1801465. https://doi.org/10.1002/adhm.201801465
Radin S, Ducheyne P (2007) Controlled release of vancomycin from thin sol–gel films on titanium alloy fracture plate material. Biomaterials 28:1721–1729. https://doi.org/10.1016/j.biomaterials.2006.11.035
Jia Z, Zhou W, Yan J, Xiong P, Guo H, Cheng Y, Zheng Y (2018) Constructing multilayer silk protein/Nanosilver biofunctionalized hierarchically structured 3D printed Ti6Al4 V scaffold for repair of infective bone defects. ACS Biomater Sci Eng 5:244–261. https://doi.org/10.1021/acsbiomaterials.8b00857
Wang X, Sun W, Yang W, Gao S, Sun C, Li Q (2019) Mesoporous silica-protected silver nanoparticle disinfectant with controlled Ag+ ion release, efficient magnetic separation, and effective antibacterial activity. Nanoscale Adv 1:840–848. https://doi.org/10.1039/C8NA00275D
Liu M, Huang F, Hung C-T, Wang L, Bi W, Liu Y, Li W (2022) An implantable antibacterial drug-carrier:mesoporous silica coatings with size-tunable vertical mesochannels. Nano Res 15:4243–4250. https://doi.org/10.1007/s12274-021-4055-y
Celebioglu A, Topuz F, Yildiz ZI, Uyar T (2019) One-step green synthesis of antibacterial silver nanoparticles embedded in electrospun cyclodextrin nanofibers. Carbohydr Polym 207:471–479. https://doi.org/10.1016/j.carbpol.2018.12.008
Monerris MJ, Broglia MF, Yslas EI, Barbero C, Rivarola C (2017) Antibacterial Polymeric Nanocomposites Synthesized by In-Situ Photoreduction of Silver Ions without Additives inside Biocompatible Hydrogel Matrices Based on N-Isopropylacrylamide and Derivatives. Express Polym Lett 11:946–962. https://doi.org/10.3144/expresspolymlett.2017.91
Du L, Wang YJ, Wang K, Shen C, Luo GS (2016) In situ dispersion of oil-based Ag nanocolloids by microdroplet coalescence and their applications in SERS detection. RSC Adv 6:59639–59647. https://doi.org/10.1039/C6RA05269J
Qu J, Lu X, Li D, Ding Y, Leng Y, Weng J, Qu S, Feng B, Watari F (2011) Silver/hydroxyapatite composite coatings on porous titanium surfaces by sol-gel method. J Biomed Mater Res B Appl Biomater 97B:40–48. https://doi.org/10.1002/jbm.b.31784
https://www.spmtips.com/afm-tip-hires-c14-cr-au. Accessed 03 August 2023
Kokubo T, Kushitani H, Sakka S, Kitsugi T, Yamamuro T (1990) Solutions able to reproduce in vivo surface-structure changes in bioactive glass-ceramic A-W. J Biomed Mater Res 24:721–734. https://doi.org/10.1002/jbm.820240607
Stetefeld J, McKenna SA, Patel TR (2016) Dynamic light scattering: a practical guide and applications in biomedical sciences. Biophys Rev 8:409–427. https://doi.org/10.1007/s12551-016-0218-6
Alexander M, Dalgleish DG (2006) Dynamic Light Scattering Techniques and Their Applications in Food Science. Food Biophys 1:2–13. https://doi.org/10.1007/s11483-005-9000-1
Carvalho PM, Felício MR, Santos NC, Gonçalves S, Domingues MM (2018) Application of Light Scattering Techniques to Nanoparticle Characterization and Development. Front Chem 6:237. https://doi.org/10.3389/fchem.2018.00237
Jia Z, Li J, Gao L, Yang D, Kanaev A (2023) Dynamic Light Scattering: A Powerful Tool for In Situ Nanoparticle Sizing. Coll Interfac 7:15. https://doi.org/10.3390/colloids7010015
Shibayama M, Norisuye T (2002) Gel Formation Analyses by Dynamic Light Scattering. Bull Chem Soc Jpn 75:641–659. https://doi.org/10.1246/bcsj.75.641
Pal S, Nisi R, Licciulli A (2022) Antibacterial Activity of In Situ Generated Silver Nanoparticles in Hybrid Silica Films. Photochem 2:479–488. https://doi.org/10.3390/photochem2030033
Molina J, Oliveira FR, Souto AP, Esteves MF, Bonastre J, Cases F (2013) Enhanced Adhesion of Polypyrrole/PW12O403- Hybrid Coatings on Polyester Fabrics. J Appl Polym Sci 129:422–433. https://doi.org/10.1002/app.38652
Hench LL (1998) Bioceramics. J Am Ceram Soc 81:1705–1728. https://doi.org/10.1111/j.1151-2916.1998.tb02540.x
Ma G, Liu XY (2009) Hydroxyapatite: Hexagonal or Monoclinic? Cryst Growth Des 9:2991–2994. https://doi.org/10.1021/cg900156w
Lu X, Zhang H, Guo Y, Wang Y, Ge X, Leng Y, Watari F (2011) Hexagonal hydroxyapatite formation on TiO2 nanotubes under urea modulation. CrystEngComm 13:3741–3749. https://doi.org/10.1039/C0CE00971G
Sivachidambaram S, Rao SM (2012) Iodide Retention by Modified Kaolinite in the Context of Safe Disposal of High Level Nuclear Waste. J Hazard Toxic Radioact Waste 16:192–200. https://doi.org/10.1061/(ASCE)HZ.2153-5515.0000121
Reynaud C, Thomas C, Casale S, Nowak S, Costentin G (2021) Development of a thermodynamic approach to assist the control of the precipitation of hydroxyapatites and associated calcium phosphates in open systems. CrystEngComm 23:4857–4870. https://doi.org/10.1039/D1CE00482D
Ehrt D, Jäger C (1988) Investigations of Solid State Reactions of Binary Polyphosphate—Fluoride Systems by Means of Thermal Analysis, X-Ray Diffraction and NMR Spectroscopy. Z Phys Chem Neue Folge 159:89–102. https://doi.org/10.1524/zpch.1988.159.Part_1.089
Bulina NV, Makarova SV, Baev SG, Matvienko AA, Gerasimov KB, Logutenko OA, Bystrov VS (2021) A Study of Thermal Stability of Hydroxyapatite. Minerals 11:1310. https://doi.org/10.3390/min11121310
Swanson HE, Tatge E (1953) Standard X-ray Diffraction Powder Patterns. Natl Bur Stand Circ 539:23
Bellotti R, Picotto GB, Ribotta L (2022) AFM Measurements and Tip Characterization of Nanoparticles with Diferent Shapes. Nanomanuf Metrol 5:127–138. https://doi.org/10.1007/s41871-022-00125-x
Grobelny J, Del Rio FW, Namboodiri P, Kim D-I, Hackley VA, Cook RF (2012) Standard Guide for Size Measurement of Nanoparticles Using Atomic Force Microscopy. ASTM E2859-11, International Standard. https://doi.org/10.1520/E2859-11
Palchoudhury S, Baalousha M, Lead JR (2015) Chapter 5 - Methods for Measuring Concentration (Mass, Surface Area and Number) of Nanomaterials. Front Nanosci 8:153–181. https://doi.org/10.1016/B978-0-08-099948-7.00005-1
Zhang H, Huang J, Wang Y, Liu R, Huai X, Jiang J, Anfuso C (2018) Atomic force microscopy for two-dimensional materials: A tutorial review. Opt Commun 406:3–17. https://doi.org/10.1016/j.optcom.2017.05.015
Yamashita S, Kikkawa J, Yanagisawa K, Nagai T, Ishizuka K, Kimoto K (2018) Atomic number dependence of Z contrast in scanning transmission electron microscopy. Sci Rep 8:12325. https://doi.org/10.1038/s41598-018-30941-5
Balgude D, Konge K, Sabnis A (2014) Synthesis and characterization of sol–gel derived CNSL based hybrid anticorrosive coatings. J Sol-Gel Sci Technol 69:155–165. https://doi.org/10.1007/s10971-013-3198-z
Golub P, Doroshenko I, Pogorelov V, Sablinskas V, Balevicius V, Ceponkus J (2013) Temperature Evolution of Cluster Structures in Ethanol. Dataset Pap Phys 2013:473294. https://doi.org/10.1155/2013/473294
Hernández-Barrios CA, Cuao CA, Jaimes MA, Coy AE, Viejo F (2017) Effect of the catalyst concentration, the immersion time and the aging time on the morphology, composition and corrosion performance of TEOS-GPTMS sol-gel coatings deposited on the AZ31 magnesium alloy. Surf Coat Technol 325:257–269. https://doi.org/10.1016/j.surfcoat.2017.06.047
Khalil KMS (2007) Cerium modified MCM-41 nanocomposite materials via a nonhydrothermal direct method at room temperature. J Coll Interfac Sci 315:562–568. https://doi.org/10.1016/j.jcis.2007.07.030
Jeon H-J, Yi S-C, Oh S-G (2003) Preparation and antibacterial effects of Ag–SiO2 thin films by sol–gel method. Biomaterials 24:4921–4928. https://doi.org/10.1016/S0142-9612(03)00415-0
Monteiro DA, Gozzi G, Chinaglia D, Oliveira ON, de Vicente FS (2020) Proton conduction mechanisms in GPTMS/TEOS-derived organic/silica hybrid films prepared by sol-gel process. Synth Met 267:116448. https://doi.org/10.1016/j.synthmet.2020.116448
Pandey PC, Chauhan DS (2012) 3-Glycidoxypropyltrimethoxysilane mediated in situ synthesis of noble metal nanoparticles: Application to hydrogen peroxide sensing. Analyst 137:376–385. https://doi.org/10.1039/c1an15843k
Ahlawat DS, Rachna RK, Yadav I (2014) Synthesis and Characterization of Sol–Gel Prepared Silver Nanoparticles. Int J Nanosci 13:1450004. https://doi.org/10.1142/S0219581X14500045
Acknowledgements
J. Belda is gratefully acknowledged for carrying out ICP-MS measurements. The Electron Microscopy Service of the UPV (Universitat Politècnica de València) is gratefully acknowledged for help with FESEM and EDX characterization. Instituto de Tecnología Química is gratefully acknowledged for carrying out XRD measurements.
Funding
This work was supported by the Instituto Valenciano de Competitividad Empresarial (IVACE) (project reference IMDEEA/2019/10) and the European Union (FEDER).
Author information
Authors and Affiliations
Contributions
Conceptualization: [JM]; Methodology: [JM, AV-G, SP-M, MSI-P, FB]; Formal analysis and investigation: [JM, AV-G, SP-M, MSI-P, FB]; Writing— original draft preparation: [JM, AV-G]; Writing—review and editing: [JM, AV-G, SP-M, MSI-P, FB]; Funding acquisition: [JM, AV-G, FB]; Resources: [FB].
Corresponding author
Ethics declarations
Conflict of interest
The authors declare no competing interests.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Molina, J., Valero-Gómez, A., Pocoví-Martínez, S. et al. Simple and effective sol-gel methodology to obtain a bactericidal coating for prostheses. J Sol-Gel Sci Technol 108, 809–826 (2023). https://doi.org/10.1007/s10971-023-06237-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10971-023-06237-0