Search results for "Nanoclusters"

Ab initio simulation of yttrium oxide nanocluster formation on fcc Fe lattice

2010

Using results of density functional theory (DFT) calculations the first attempt towards the understanding of Y2O3 particles formation in oxide dispersed strengthened (ODS) ferritic–martensitic steels was performed. The present work includes modeling of single defects (O impurity atom, Fe vacancy and Y substitute atom), interaction between substituted Y atoms, Y–Fe vacancy pairs and oxygen impurity atoms in the iron matrix. The calculations have showed the repulsive interaction between the two Y substitute atoms at any separation distances that might mean that the oxygen atoms or O atoms with vacancies are required to form binding between atoms in the yttrium oxide nanoclusters.

Electrical fluctuations in monolayer-protected metal nanoclusters

2008

Abstract Monolayer-protected clusters (MPCs) are formed by a neutral or charged metallic core surrounded by an organic ligand monolayer. We estimate the electric potential fluctuations of a MPC in an electrolyte solution by using the equilibrium fluctuation–dissipation theorem and the non-linear Poisson–Boltzmann equation extended to account for ion penetration in the monolayer. Significant fluctuations are predicted because the MPC capacitance is small (approximately 1 aF). We study also the non-equilibrium case of a MPC sandwiched between two electrodes and estimate the current noise considering the nanocluster as a single electron transistor and using a theoretical approach based on the …

Inside Cover: Poly(polyoxotungstate)s with 20 Nickel Centers: From Nanoclusters to One-Dimensional Chains (Angew. Chem. Int. Ed. 39/2009)

2009

[Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster

2016

Engineering the surface ligands of metal nanoparticles is critical in designing unique arrangements of metal atoms. Here, we report the synthesis and total structure determination of a large box-shaped Ag67 nanocluster (NC) protected by a mixed shell of thiolate (2,4-dimethylbenzenethiolate, SPhMe2) and phosphine (triphenylphosphine, PPh3) ligands. Single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS) revealed the cluster formula to be [Ag67(SPhMe2)32(PPh3)8]3+. The crystal structure shows an Ag23 metal core covered by a layer of Ag44S32P8 arranged in the shape of a box. The Ag23 core was formed through an unprecedented centered cuboctahedron, i.e.,…

Synthesis of Cuboctahedral CeO2 Nanoclusters and Their Assembly into Cuboid Nanoparticles by Oriented Attachment

2017

Here, we describe a simple approach to control the oriented attachment process through selective ligand scavenging from the {100} facets of CeO2 nanoclusters. Aggregates of these nanoclusters smaller than 10 nm with controlled shapes and exposed facets were obtained. For the synthesis of the cuboctahedral CeO2 nanoclusters, we developed a solvent-controlled synthesis approach based on a non-hydrolytic sol–gel process and used an ester aminolysis reaction to control ligand scavenging from the {100} facets. First-principle calculations allowed us to understand and interpret, at the atomic level, the effects of shape control on the synthesis. Fine-tuning of the desired morphologies can be achi…

Reversible pH-induced fluorescence colour change of gold nanoclusters based on pH-regulated surface interactions.

2019

To prepare water-dispersible, biocompatible, ratiometric pH nanosensors is challenging. We report here for the first time that the emission colour of NAD+-capped AuNCs responds to the mono-/bidentate anchoring of the phosphoric groups of the ligand. The AuNCs exhibit a high luminescence (21% quantum yield) and an outstanding performance as fluorescent ratiometric pH sensors over a broad pH range.

Treatment of grazing-incidence small-angle X-ray scattering data taken above the critical angle

2001

The equations taking into account refraction at the sample surface in grazing-incidence small-angle X-ray scattering (GISAXS) when the angle between the incoming beam and the sample surface is slightly larger than the critical angle are derived and discussed. It is demonstrated that the refraction of both the incoming and the scattered beam at the sample surface affects the GISAXS pattern and that, when a planar bidimensional detector perpendicular to the incoming beam is used, the effect depends on the azimuthal detector angle. The smearing of the pattern depending on the size of the illuminated sample area in grazing incidence is estimated by simulations with Cauchy functions of different…

Dynamic Diglyme-Mediated Self-Assembly of Gold Nanoclusters

2015

We report the assembly of gold nanoclusters by the nonthiolate ligand diglyme into discrete and dynamic assemblies. To understand this surprising phenomenon, the assembly of Au20(SC2H4Ph)15-diglyme into Au20(SC2H4Ph)15-diglyme-Au20(SC2H4Ph)15 is explored in detail. The assembly is examined by high-angle annular dark field scanning transmission electron microscopy, size exclusion chromatography, mass spectrometry, IR spectroscopy, and calorimetry. We establish a dissociation constant for dimer to monomer conversion of 20.4 μM. Theoretical models validated by transient absorption spectroscopy predict a low-spin monomer and a high-spin dimer, with assembly enabled through weak diglyme oxygen-g…

Effects of Silver Doping on the Geometric and Electronic Structure and Optical Absorption Spectra of the Au_{25-n}Ag_{n}(SH)_{18}^{-} (n = 1, 2, 4, 6…

2012

The effect of silver doping of the Au25(SH)18– nanoparticle is studied by investigating Au25–nAgn(SH)18– (n = 1, 2, 4, 6, 8, 10, 12) systems using DFT. For n = 1, doping of the icosahedral shell of the metal core is energetically more favorable than doping of the metal–thiolate units or the center of the core. For n ≥ 2, only doping of the core surface is considered, and arrangements where the silver dopants are in close proximity tend to be slightly less favorable. However, energy differences are small, and all conformations are accessible under experimental conditions. Boltzmann-averaged excitation spectra for these systems show similar features to the undoped Au25(SH)18–. The main differ…

Site-specific targeting of enterovirus capsid by functionalized monodisperse gold nanoclusters

2014

Development of precise protocols for accurate site-specific conjugation of monodisperse inorganic nanoparticles to biological material is one of the challenges in contemporary bionanoscience and nanomedicine. We report here a successful site-specific covalent conjugation of functionalized atomically monodisperse gold clusters with 1.5-nm metal cores to viral surfaces. Water-soluble Au102(para-mercaptobenzoic acid)44 clusters, functionalized by maleimide linkers to target cysteines of viral capsid proteins, were synthesized and conjugated to enteroviruses echovirus 1 and coxsackievirus B3. Quantitative analysis of transmission electron microscopy images and the known virus structures showed …