Tailoring Density and Optical and Thermal Behavior of Gold Surfaces and Nanoparticles Exploiting Aromatic Dithiols

Bruno, Giovanni; Babudri, Francesco; Operamolla, Alessandra; Bianco, Giuseppe Valerio; Losurdo, Maria; Giangregorio, Maria M.; Omar, Omar Hassan; Mavelli, Fabio; Farinola, Gianluca M.; Capezzuto, P.; Naso, Francesco

doi:10.1021/la101082t

Cited by 41 publications

(63 citation statements)

References 68 publications

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“…For these SAMs, the estimated molecular height is 9 and 12 Å, respectively, 26 which is consistent with the measured thickness considering an experimental uncertainty of no more than ±2 Å.…”

Section: Azide-functionalized Self-assembled Monolayerssupporting

confidence: 85%

Poly(l-lysine) Interfaces via Dual Click Reactions on Surface-Bound Custom-Designed Dithiol Adsorbates

2015

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Surfaces modified with poly(L-lysine) can be used to immobilize selected biomolecules electrostatically. This report describes the preparation of a set of self-assembled monolayers (SAMs) from three different azide-terminated adsorbates as platforms for performing controlled surface attachments and as a means of determining the parameters that afford stable poly(L-lysine)-modified SAM surfaces having controlled packing densities. A maleimide-terminated alkyne linker was "clicked" to the azide-terminated surfaces via a copper-catalyzed cycloaddition reaction to produce the attachment sites for the polypeptides. A thiol-Michael addition was then used to immobilize cysteine-terminated poly(L-lysine) moieties on the gold surface, avoiding adsorbate self-reactions with this two-step procedure. Each step in this process was analyzed by ellipsometry, X-ray photoelectron spectroscopy, polarization modulation infrared reflection-absorption spectroscopy, and contact angle goniometry to determine which adsorbate structure most effectively produced the targeted polypeptide interface. Additionally, a series of mixed SAMs using an azidoalkanethiol in combination with a normal alkanethiol having an equivalent alkyl chain were prepared to provide data to determine how dilution of the azide reactive site on the SAM surface influences the initial click reaction. Overall, the collected data demonstrate the advantages of an appropriately designed bidentate absorbate and its potential to form effective platforms for biomolecule surface attachment via click reactions.

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Section: Azide-functionalized Self-assembled Monolayerssupporting

confidence: 85%

Poly(l-lysine) Interfaces via Dual Click Reactions on Surface-Bound Custom-Designed Dithiol Adsorbates

2015

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“…The peculiarity of the remote hydrogen plasma is that it prevents any heating or sputtering effect and allows a pure chemical SAM ablation by atomic hydrogen without damaging the gold surface and nanoparticles and avoiding the surface contamination by oxidized sulfur species occurring when O 2 or N 2 plasma is used. 17, 18 The study is performed functionalizing both thin gold films and gold nanoparticles (NPs) with the aliphatic n-dodecylthiol (C12) and the aromatic 4-methoxyterphenyl-3 00 ,5 00 -dimethanethiol (TPDMT), 19 which differ in dipole moment as well as in surface packing density and geometry of bonding to gold through one or two sulfur functionalities. The kinetics of the interaction with hydrogen and its impact on SAM optical and structural properties are monitored in real time using spectroscopic ellipsometry (SE), by recording variations of the surface plasmon resonance (SPR) of Au NPs and of the dielectric function of Au thin films.…”

Section: ' Introductionmentioning

confidence: 99%

Insight into Gold Nanoparticle–Hydrogen Interaction: A Way To Tailor Nanoparticle Surface Charge and Self-Assembled Monolayer Chemisorption

et al. 2011

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The interaction of hydrogen with gold nanoparticles (Au NPs) and gold thin films also functionalized with thiols is investigated. Au NPs deposited on silicon substrates by radio frequency sputtering of a gold target and gold thin films have been exposed to a remote H2 plasma and subsequently functionalized by the aromatic (4-methoxyterphenyl-3″,5″-dimethanethiol) and aliphatic (dodecanethiol) thiols. The impact of hydrogenation on changes of the charge on gold surfaces and nanoparticles, on the kinetics of the thiol self-assembled monolayer (SAM) formation, and on the density of the resulting SAMs has been investigated combining spectroscopic ellipsometry (SE), Raman spectroscopy, and surface potential Kelvin probe microscopy (SP-KPM) in conjunction with noncontact atomic force microscopy (AFM). We found that remote H2 plasma pretreatments of gold surfaces are effective in improving thiolate adsorption, making SAMs more uniform and densely packed. We also demonstrate that hydrogenation of nanoparticles improves stability of thiol functionalized Au NPs, avoiding their aggregation. Additionally, we demonstrate that a remote H2 plasma processing is also effective in the selective removal of the carbon chain and of sulfur atoms from gold surfaces, therefore allowing tailoring of their optical and chemical properties.

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“…[31] L1 was characterized by 1 H, 13 C and 31 P NMR and high-resolution mass spectrometry (HRMS) (m/z (MALDI) = 609.22786). [34][35][36][37][38][39][40][41] Therefore we inserted a triazole ring as an alternative since it is easy to generate via CuAAC (click) chemistry. A structurally closely related 6,6Ј-dimethyl-2,2Ј-bipyridine with phosphonic acid groups was reported by Housecroft et al for its utilization as an anchoring ligand for copper(I) dyes in n-type DSSCs.…”

Section: Synthesismentioning

confidence: 99%

Modular Synthesis of Elongated Phosphonate Bipyridines

et al. 2015

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The synthesis and the photophysical properties of a series of bpy‐R2 derivatives L1–L3 (bpy = 2,2′‐bipyridine, R represents the substitution at the 4‐ and 4′‐positions of the bpy) are described. R includes phosphonic ester groups as precursors for potent phosphonate anchoring groups, which enable immobilization on transition metal oxide semiconductor surfaces for applications like dye‐sensitized solar cells (DSSCs) or dye‐sensitized photoelectrosynthesis cells (DSPECs). The ligands L1–L3 differ in the length of conjugated linker units between bpy core and anchoring groups. Phenylene and triazole moieties serve as building blocks for linker elongation. The resulting adjustability of the distance between semiconductor and chromophore represents a viable route to improve cell efficiency, as it will allow tuning of charge carrier recombination and dye aggregation. Furthermore the photophysical studies of the free ligands reveal a pronounced effect of the aryl substitution. The solid‐state structures of L1 and L2 are reported within this contribution, enabling the determination of distances between bipyridine nitrogen donor and anchoring group.

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Tailoring Density and Optical and Thermal Behavior of Gold Surfaces and Nanoparticles Exploiting Aromatic Dithiols

Cited by 41 publications

References 68 publications

Poly(l-lysine) Interfaces via Dual Click Reactions on Surface-Bound Custom-Designed Dithiol Adsorbates

Poly(l-lysine) Interfaces via Dual Click Reactions on Surface-Bound Custom-Designed Dithiol Adsorbates

Insight into Gold Nanoparticle–Hydrogen Interaction: A Way To Tailor Nanoparticle Surface Charge and Self-Assembled Monolayer Chemisorption

Modular Synthesis of Elongated Phosphonate Bipyridines

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