New antimicrobial biomaterials based on recombinant spider silks

Spider silk is a protein-based material with exceptional mechanical properties together with low immunogenicity and pyrogenicity which makes it useful in biomedical applications. The cannibalistic and highly territorial nature of most spiders prevents high-density farming; therefore, the availabilit...

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Main Author: Beinarovica, Jolanta
Format: Thesis (University of Nottingham only)
Language:English
Published: 2022
Subjects:
Online Access:https://eprints.nottingham.ac.uk/68429/
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author Beinarovica, Jolanta
author_facet Beinarovica, Jolanta
author_sort Beinarovica, Jolanta
building Nottingham Research Data Repository
collection Online Access
description Spider silk is a protein-based material with exceptional mechanical properties together with low immunogenicity and pyrogenicity which makes it useful in biomedical applications. The cannibalistic and highly territorial nature of most spiders prevents high-density farming; therefore, the availability of their silk in a usable form is very limited. Recombinant production of silks is explored as an alternative mean of production. This study uses two miniature recombinant silk proteins (mini-spidroins) with distinct biochemical nature -NT2RepCT and 4RepCT - to create new materials for drug delivery. A procedure for a column-free, scale up compatible purification of highly water soluble spidroin NT2RepCT has been developed. NT2RepCT was then processed into a colloidal drug delivery system that could be loaded with a model drug and exhibited a pH-dependent controlled drug release profile. It was found that NT2RepCT particles have a polydisperse size range on a micron scale, and that they are unstable in water, which makes them useful for in situ and temporary embolic applications. Further, the 4RepCT3Aha mini-spidroin was expressed and purified. In this construct, each methionine residue is replaced with a synthetic methionine analogue L-azidohomoalanine (Aha) that carries a terminal azide in its side chain. The azide acts as a selectively chemically reactive, bioorthogonal group for bioconjugations using copper-catalysed azide-alkyne cycloaddition (CuAAC) knows as the “click reaction”. Using this methodology, a selection of antimicrobial ligands (triclosan, chloramphenicol, ciprofloxacin, erythromycin, levofloxacin, and nitroxoline) bearing a labile linker with a terminal alkyne were conjugated to 4RepCT3Aha , creating a library of antimicrobial conjugates. The resulting conjugates were processed into films that showed significant antimicrobial activity against the Gram-negative Escherichia coli (E. coli) and the Gram-positive Staphylococcus aureus (S. aureus) in a novel plate-based, high throughput-compatible assay. Further, it was found that ‘clickable’ antimicrobial ligands could also be conjugated to pre-formed Aha-bearing silk films. When the antimicrobial ligands were conjugated to pre-formed films, their biocidal activity was lower than that of films made from soluble 4RepCT3Aha -ligand conjugates but the activity was statistically significant compared to films dipped in antibiotic solution. In addition, the 4RepCT3Aha mini-spidroin was functionalised with quaternary ammonium-based ligands via a non-labile linker prior to processing of the conjugate into a surface coating. In this approach, a cationic, contact-active antimicrobial surface was created that showed significant antimicrobial effect against E. coli in a range of conventional microbiological assays. For this material, a tailored high-throughput compatible assay to analyse the metabolic activity and biomass increase of surface-adherent bacteria was developed. In this assay, it was found that quaternary-ammonium bearing ligands have activity against E. coli, but not S. aureus or Pseudomonas aeruginosa. In conclusion, this work describes a range of new antimicrobial materials based on miniature spider silks that can serve as a drug delivery vehicle in different biomedically relevant scenarios. By combining silk’s uniquely biocompatible nature with a tailored functionality and modifiable release kinetics, these novel biomaterials are promising candidates for drug delivery applications.
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spelling nottingham-684292025-02-28T15:14:45Z https://eprints.nottingham.ac.uk/68429/ New antimicrobial biomaterials based on recombinant spider silks Beinarovica, Jolanta Spider silk is a protein-based material with exceptional mechanical properties together with low immunogenicity and pyrogenicity which makes it useful in biomedical applications. The cannibalistic and highly territorial nature of most spiders prevents high-density farming; therefore, the availability of their silk in a usable form is very limited. Recombinant production of silks is explored as an alternative mean of production. This study uses two miniature recombinant silk proteins (mini-spidroins) with distinct biochemical nature -NT2RepCT and 4RepCT - to create new materials for drug delivery. A procedure for a column-free, scale up compatible purification of highly water soluble spidroin NT2RepCT has been developed. NT2RepCT was then processed into a colloidal drug delivery system that could be loaded with a model drug and exhibited a pH-dependent controlled drug release profile. It was found that NT2RepCT particles have a polydisperse size range on a micron scale, and that they are unstable in water, which makes them useful for in situ and temporary embolic applications. Further, the 4RepCT3Aha mini-spidroin was expressed and purified. In this construct, each methionine residue is replaced with a synthetic methionine analogue L-azidohomoalanine (Aha) that carries a terminal azide in its side chain. The azide acts as a selectively chemically reactive, bioorthogonal group for bioconjugations using copper-catalysed azide-alkyne cycloaddition (CuAAC) knows as the “click reaction”. Using this methodology, a selection of antimicrobial ligands (triclosan, chloramphenicol, ciprofloxacin, erythromycin, levofloxacin, and nitroxoline) bearing a labile linker with a terminal alkyne were conjugated to 4RepCT3Aha , creating a library of antimicrobial conjugates. The resulting conjugates were processed into films that showed significant antimicrobial activity against the Gram-negative Escherichia coli (E. coli) and the Gram-positive Staphylococcus aureus (S. aureus) in a novel plate-based, high throughput-compatible assay. Further, it was found that ‘clickable’ antimicrobial ligands could also be conjugated to pre-formed Aha-bearing silk films. When the antimicrobial ligands were conjugated to pre-formed films, their biocidal activity was lower than that of films made from soluble 4RepCT3Aha -ligand conjugates but the activity was statistically significant compared to films dipped in antibiotic solution. In addition, the 4RepCT3Aha mini-spidroin was functionalised with quaternary ammonium-based ligands via a non-labile linker prior to processing of the conjugate into a surface coating. In this approach, a cationic, contact-active antimicrobial surface was created that showed significant antimicrobial effect against E. coli in a range of conventional microbiological assays. For this material, a tailored high-throughput compatible assay to analyse the metabolic activity and biomass increase of surface-adherent bacteria was developed. In this assay, it was found that quaternary-ammonium bearing ligands have activity against E. coli, but not S. aureus or Pseudomonas aeruginosa. In conclusion, this work describes a range of new antimicrobial materials based on miniature spider silks that can serve as a drug delivery vehicle in different biomedically relevant scenarios. By combining silk’s uniquely biocompatible nature with a tailored functionality and modifiable release kinetics, these novel biomaterials are promising candidates for drug delivery applications. 2022-03-15 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en cc_by https://eprints.nottingham.ac.uk/68429/1/Beinarovica%20Jolanta%2014304137%20PhD%20Chemistry.pdf Beinarovica, Jolanta (2022) New antimicrobial biomaterials based on recombinant spider silks. PhD thesis, University of Nottingham. spider silk antimicrobial biomaterials drug delivery systems
spellingShingle spider silk
antimicrobial biomaterials
drug delivery systems
Beinarovica, Jolanta
New antimicrobial biomaterials based on recombinant spider silks
title New antimicrobial biomaterials based on recombinant spider silks
title_full New antimicrobial biomaterials based on recombinant spider silks
title_fullStr New antimicrobial biomaterials based on recombinant spider silks
title_full_unstemmed New antimicrobial biomaterials based on recombinant spider silks
title_short New antimicrobial biomaterials based on recombinant spider silks
title_sort new antimicrobial biomaterials based on recombinant spider silks
topic spider silk
antimicrobial biomaterials
drug delivery systems
url https://eprints.nottingham.ac.uk/68429/