Ultrastructure and Surface Composition of Glutathione-Terminated Ultrasmall Silver, Gold, Platinum, and Alloyed Silver–Platinum Nanoparticles (2 nm)

Wolff, Natalie; Loza, Kateryna; Heggen, Marc; Schaller, Torsten; Niemeyer, Felix; Bayer, Peter; Beuck, Christine; Oliveira, Cristiano L. P.; Prymak, Oleg; Weidenthaler, Claudia; Epple, Matthias

doi:10.1021/acs.inorgchem.3c02879

Cited by 6 publications

(14 citation statements)

References 80 publications

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“…As a consequence, the signals of the bound ligands showed an increased peak width compared with the free ligands. In addition, a characteristic downfield shift of the signals to higher frequencies was observed. , …”

Section: Resultsmentioning

confidence: 94%

“…It is remarkable that the footprints determined here for tripeptides A 2 C (0.25 nm 2 ) and A 1 CA 1 (0.29 nm 2 ) were significantly higher. It was shown by Wolff et al and Wetzel et al for ultrasmall silver and platinum nanoparticles that the footprint of glutathione also depended on the core metal of the nanoparticles. Karki et al used NMR spectroscopy and DFT calculations to investigate how the peptides Ala-Ala-Cys and the reverse variant attached to gold nanoparticles via the thiol group.…”

Section: Resultsmentioning

confidence: 97%

“…Surface properties and successful surface functionalization of ultrasmall gold nanoparticles can be investigated by NMR spectroscopy, in contrast to larger nanoparticles where the resolution is limited due to very broad or even absent NMR signals. ,,, Indeed, NMR spectroscopy, also multidimensional, has been used to elucidate the ligand nature in atom-sharp gold clusters like Au 102 (pMBA) 44 (pMBA: para-mercaptobenzoic acid) and Au 144 (SR) 60 (R = Et, Pr) . NMR spectroscopy can also be used to determine the number of ligands per nanoparticle.…”

Section: Resultsmentioning

confidence: 99%

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The Molecular Footprint of Peptides on the Surface of Ultrasmall Gold Nanoparticles (2 nm) Is Governed by Steric Demand

Wagner,

Prymak,

Schaller

et al. 2024

J. Phys. Chem. B

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Ultrasmall gold nanoparticles were functionalized with peptides of two to seven amino acids that contained one cysteine molecule as anchor via a thiol−gold bond and a number of alanine residues as nonbinding amino acid. The cysteine was located either in the center of the molecule or at the end (C-terminus). For comparison, gold nanoparticles were also functionalized with cysteine alone. The particles were characterized by UV spectroscopy, differential centrifugal sedimentation (DCS), highresolution transmission electron microscopy (HRTEM), and small-angle X-ray scattering (SAXS). This confirmed the uniform metal core (2 nm diameter). The hydrodynamic diameter was probed by 1 H-DOSY NMR spectroscopy and showed an increase in thickness of the hydrated peptide layer with increasing peptide size (up to 1.4 nm for heptapeptides; 0.20 nm per amino acid in the peptide). 1 H NMR spectroscopy of water-dispersed nanoparticles showed the integrity of the peptides and the effect of the metal core on the peptide. Notably, the NMR signals were very broad near the metal surface and became increasingly narrow in a distance. In particular, the methyl groups of alanine can be used as probe for the resolution of the NMR spectra. The number of peptide ligands on each nanoparticle was determined using quantitative 1 H NMR spectroscopy. It decreased with increasing peptide length from about 100 for a dipeptide to about 12 for a heptapeptide, resulting in an increase of the molecular footprint from about 0.1 to 1.1 nm 2 .

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Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

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The Molecular Footprint of Peptides on the Surface of Ultrasmall Gold Nanoparticles (2 nm) Is Governed by Steric Demand

Wagner,

Prymak,

Schaller

et al. 2024

J. Phys. Chem. B

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“…The increased sensitivity of high-field spectrometers in combination with cryoprobes enables the investigation of diluted nanoparticle solutions with significantly broadened NMR resonance lines. 48,50,84 While dynamic nuclear (hyper)polarization (DNP) is more often used in solid state NMR, it can be applied to enhance sensitivity in solution as well. 85,86 Broadband 1 H decoupling is often used in 1D 13 C spectra – not only to collapse splitting due to 1 H– 13 C J -coupling, but also to increase the sensitivity via a steady-state heteronuclear NOE.…”

Section: Introductionmentioning

confidence: 99%

Possibilities and limitations of solution-state NMR spectroscopy to analyze the ligand shell of ultrasmall metal nanoparticles

Wolff,

Beuck,

Schaller

et al. 2024

Nanoscale Adv.

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“…As capping agents, organic ligands with the soft Lewis base donor atoms sulfur and phosphorus are generally preferred because they form a strong bond to the soft Lewis-acidic noble metals, in contrast to weakly binding oxygen-terminated ligands like citrate . Besides monatomic clusters, bimetallic clusters and ultrasmall nanoalloys , have also been prepared. In the following, we will concentrate on metallic nanoparticles, in particular gold nanoparticles, although many conclusions will also apply to particles of the same size but of a different chemical nature.…”

Section: Introductionmentioning

confidence: 99%

The Why and How of Ultrasmall Nanoparticles

Epple,

Rotello,

Dawson

2023

Acc. Chem. Res.

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In this Account, we describe our research into ultrasmall nanoparticles, including their unique properties, and outline some of the new opportunities they offer. We will summarize our perspective on the current state of the field and highlight what we see as key questions that remain to be solved. First, there are several nanostructure size-scale regimes, with qualitatively distinct functional biological attributes. Broadly generalized, larger particles (e.g., larger than 300 nm) tend to be more efficiently swept away by the first line of the immune system (for example macrophages). In the "middle-sized" regime (20−300 nm), nanoparticle surfaces and shapes can be recognized by energy-dependent cellular reorganizations, then organized locally in a spatial and temporally coherent way. That energy is gated and made available by specific cellular recognition processes. The relationship between particle surface design, endogenously derived nonspecific biomolecular corona, and architectural features recognized by the cell is complex and only purposefully and very precisely designed nanoparticle architectures are able to navigate to specific targets. At sufficiently small sizes (<10 nm including the ligand shell, associated with a core diameter of a few nm at most) we enter the "quasimolecular regime" in which the endogenous biomolecular environment exchanges so rapidly with the ultrasmall particle surface that larger scale cellular and immune recognition events are often greatly simplified. As an example, ultrasmall particles can penetrate cellular and biological barriers within tissue architectures via passive diffusion, in much the same way as small molecule drugs do. An intriguing question arises: what happens at the interface of cellular recognition and ultrasmall quasi-molecular size regimes? Succinctly put, ultrasmall conjugates can evade defense mechanisms driven by larger scale cellular nanoscale recognition, enabling them to flexibly exploit molecular interaction motifs to interact with specific targets. Numerous advances in control of architecture that take advantage of these phenomena have taken place or are underway. For instance, syntheses can now be sufficiently controlled that it is possible to make nanoparticles of a few hundreds of atoms or metalloid clusters of several tens of atoms that can be characterized by single crystal X-ray structure analysis. While the synthesis of atomically precise clusters in organic solvents presents challenges, water-based syntheses of ultrasmall nanoparticles can be upscaled and lead to well-defined particle populations. The surface of ultrasmall nanoparticles can be covalently modified with a wide variety of ligands to control the interactions of these particles with biosystems, as well as drugs and fluorophores. And, in contrast to larger particles, many advanced molecular analytical and separation tools can be applied to understand their structure. For example, NMR spectroscopy allows us to obtain a detailed image of the particle surface and the attached ligands. The...

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Ultrastructure and Surface Composition of Glutathione-Terminated Ultrasmall Silver, Gold, Platinum, and Alloyed Silver–Platinum Nanoparticles (2 nm)

Cited by 6 publications

References 80 publications

The Molecular Footprint of Peptides on the Surface of Ultrasmall Gold Nanoparticles (2 nm) Is Governed by Steric Demand

The Molecular Footprint of Peptides on the Surface of Ultrasmall Gold Nanoparticles (2 nm) Is Governed by Steric Demand

Possibilities and limitations of solution-state NMR spectroscopy to analyze the ligand shell of ultrasmall metal nanoparticles

The Why and How of Ultrasmall Nanoparticles

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