The antifouling properties of self-assembled monolayers (SAMs) on gold generated from custom-designed bidentate unsymmetrical spiroalkanedithiols containing both oligo(ethylene glycol) and hydrocarbon tailgroups (EG3C7-C7 and EG3C7-C18) were evaluated and compared to SAMs derived from analogous monodentate octadecanethiol (C18SH) and the tri(ethylene glycol)-terminated alkanethiol EG3C7SH. Complementary techniques, including in situ surface plasmon resonance spectroscopy (SPR), ex situ electrochemical quartz crystal microbalance (QCM) measurements, and ex situ ellipsometric thickness measurements, were employed to assess the protein resistance of the SAMs using proteins having a wide range of sizes, structures, and properties: protamine, lysozyme, bovine serum albumin (BSA), and fibrinogen. The studies found that SAMs generated from the bidentate adsorbates EG3C7-C7 and EG3C7-C18, which contain a 1:1 mixture of OEG and hydrocarbon tailgroups, exhibited a diminished capacity to resist protein adsorption compared to the EG3C7SH SAMs, which possess only OEG tailgroups. The data highlight the critical role of hydration of the OEG matrix for generating antifouling OEG-based surface coatings.
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Lactone-Terminated Self-Assembled Monolayers for Mimicking Nanoscale Polyester Surfaces
Two series of lactone-terminated alkanethiol adsorbates with five- and six-membered lactone groups, γ-COCnSH and δ-COCnSH (n = 11, 12), were synthesized and employed to create nanoscale self-assembled monolayers (SAMs) on gold substrates to mimic the properties of commercially available poly(lactic-co-glycolic acid) (PLGA) and poly(glycolic acid) (PGA) surfaces. 1H and 13C nuclear magnetic resonance (NMR) were employed to characterize the adsorbate molecules. The thicknesses of the corresponding self-assembled monolayers (SAMs) were evaluated by ellipsometry. The conformational characteristics of the SAMs were analyzed using polarization modulation infrared reflection adsorption spectroscopy (PM-IRRAS), with a focus on the C-H antisymmetric stretching vibrations of the alkyl spacers. To evaluate the packing densities of the monolayers, X-ray photoelectron spectroscopy (XPS) measurements were performed. Separately, contact angle measurements provided insights into the wettability of the surfaces. Remarkably, the contact angle data across a broad range of probe liquids for the γ-COC11SH and γ-COC12SH SAMs were consistently similar to each other and to the contact angle values of the PLGA surface, rather than to PGA. This finding suggests that the lactone-terminated SAMs investigated in this study effectively mimic nanoscale polyester surfaces, enabling the exploration of interfacial properties of polyesters in the absence of swelling and/or surface reconstruction phenomena.
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- Award ID(s):
- 2109174
- PAR ID:
- 10553171
- Publisher / Repository:
- Chemistry
- Date Published:
- Journal Name:
- Chemistry
- Volume:
- 6
- Issue:
- 4
- ISSN:
- 2624-8549
- Page Range / eLocation ID:
- 666 to 676
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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