Monodisperse citrate-stabilized gold nanoparticles with a uniform quasi-spherical shape of up to ∼200 nm and a narrow size distribution were synthesized following a kinetically controlled seeded growth strategy via the reduction of HAuCl(4) by sodium citrate. The inhibition of any secondary nucleation during homogeneous growth was controlled by adjusting the reaction conditions: temperature, gold precursor to seed particle concentration, and pH. This method presents improved results regarding the traditional Frens method in several aspects: (i) it produces particles of higher monodispersity; (ii) it allows better control of the gold nanoparticle size and size distribution; and (iii) it leads to higher concentrations. Gold nanoparticles synthesized following this method can be further functionalized with a wide variety of molecules, hence this method appears to be a promising candidate for application in the fields of biomedicine, photonics, and electronics, among others.
Highly monodisperse sodium citrate-coated
spherical silver nanoparticles
(Ag NPs) with controlled sizes ranging from 10 to 200 nm have been
synthesized by following a kinetically controlled seeded-growth approach
via the reduction of silver nitrate by the combination of two chemical
reducing agents: sodium citrate and tannic acid. The use of traces
of tannic acid is fundamental in the synthesis of silver seeds, with
an unprecedented (nanometric resolution) narrow size distribution
that becomes even narrower, by size focusing, during the growth process.
The homogeneous growth of Ag seeds is kinetically controlled by adjusting
reaction parameters: concentrations of reducing agents, temperature,
silver precursor to seed ratio, and pH. This method produces long-term
stable aqueous colloidal dispersions of Ag NPs with narrow size distributions,
relatively high concentrations (up to 6 × 1012 NPs/mL),
and, more important, readily accessible surfaces. This was proved
by studying the catalytic properties of as-synthesized Ag NPs using
the reduction of Rhodamine B (RhB) by sodium borohydride as a model
reaction system. As a result, we show the ability of citrate-stabilized
Ag NPs to act as very efficient catalysts for the degradation of RhB
while the coating with a polyvinylpyrrolidone (PVP) layer dramatically
decreased the reaction rate.
Highly-monodisperse biocompatible and functionalizable sub-10 nm citrate-stabilized gold nanoparticles (Au NPs) have been synthesized following a kinetically controlled seeded-growth strategy. The use of traces of tannic acid together with an excess of sodium citrate during nucleation is fundamental in the formation of a high number (7•10 13 NP/mL) of small ~3.5 nm seeds with a very narrow distribution. A homogeneous nanometric growth of these seeds is then achieved by adjusting the reaction parameters: pH, temperature, sodium citrate concentration and gold precursor to seeds ratio. We use this method to produce Au NPs with a precise control over their sizes between 3.5 and 10 nm and a versatile surface chemistry allowing studying the size-dependent optical properties in this transition size regime lying between clusters and nanoparticles. Interestingly, an inflexion point is observed for NPs smaller than 8 nm in which the sensitivity of the Localized Surface Plasmon Resonance (LSPR) peak position as a function of NPs size and surface modifications dramatically increased. These studies are relevant in the design of the final selectivity, activity and compatibility of Au NPs, especially in those (bio)applications where size is a critical parameter (e.g. biodistribution, multiplex labeling and protein interaction).
Surface modifications of highly monodisperse citrate-stabilized gold nanoparticles (AuNPs) with sizes ranging from 3.5 to 150 nm after their exposure to cell culture media supplemented with fetal bovine serum were studied and characterized by the combined use of UV-vis spectroscopy, dynamic light scattering, and zeta potential measurements. In all the tested AuNPs, a dynamic process of protein adsorption was observed, evolving toward the formation of an irreversible hard protein coating known as Protein Corona. Interestingly, the thickness and density of this protein coating were strongly dependent on the particle size, making it possible to identify different transition regimes as the size of the particles increased: (i) NP-protein complexes (or incomplete corona), (ii) the formation of a near-single dense protein corona layer, and (iii) the formation of a multilayer corona. In addition, the different temporal patterns in the evolution of the protein coating came about more quickly for small particles than for the larger ones, further revealing the significant role that size plays in the kinetics of this process. Since the biological identity of the NPs is ultimately determined by the protein corona and different NP-biological interactions take place at different time scales, these results are relevant to biological and toxicological studies.
The use of magnetic nanoparticles in the development of ultra-high-density recording media is the subject of intense research. Much of the attention of this research is devoted to the stability of magnetic moments, often neglecting the influence of dipolar interactions. Here, we explore the magnetic microstructure of different assemblies of monodisperse cobalt single-domain nanoparticles by magnetic force microscopy and magnetometric measurements. We observe that when the density of particles per unit area is higher than a determined threshold, the two-dimensional self-assemblies behave as a continuous ferromagnetic thin film. Correlated areas (similar to domains) of parallel magnetization roughly ten particles in diameter appear. As this magnetic percolation is mediated by dipolar interactions, the magnetic microstructure, its distribution and stability, is strongly dependent on the topological distribution of the dipoles. Thus, the magnetic structures of three-dimensional assemblies are magnetically soft, and an evolution of the magnetic microstructure is observed with consecutive scans of the microscope tip.
The local heat delivered by metallic nanoparticles selectively attached to their target can be used as a molecular surgery to safely remove toxic and clogging aggregates. We apply this principle to protein aggregates, in particular to the amyloid beta protein (Abeta) involved in Alzheimer's disease (AD), a neurodegenerative disease where unnaturally folded Abeta proteins self-assemble and deposit forming amyloid fibrils and plaques. We show the possibility to remotely redissolve these deposits and to interfere with their growth, using the local heat dissipated by gold nanoparticles (AuNP) selectively attached to the aggregates and irradiated with low gigahertz electromagnetic fields. Simultaneous tagging and manipulation by AuNP of Abeta at different stages of aggregation allow both, noninvasive exploration and dissolution of molecular aggregates.
The effect of solvent isotopic replacement (H for D) on the size of gold nanoparticles (Au NPs) prepared by sodium citrate reduction has been investigated. With increasing replacement of water by deuterium oxide, smaller sizes of Au NPs are obtained, which is interpreted as a consequence of a faster reduction. A mechanism in which a substitution complex, [AuCl 3 (C 6 H 5 O 7 ) -2 ] -, is formed from AuCl 4 and citrate ions prior to its rate-limiting disproportionation into products is suggested. This novel procedure offers an attractive alternative to the existing ones and opens a full range of possibilities for biological studies.
In this report, we show how the classical and widely used Turkevich synthesis can be improved significantly by simple adjustments. The gold nanoparticles (AuNPs) produced with the optimized protocol have a much narrower size distribution (5-8% standard deviation), and their diameters can be reproduced with unrivaled little variation (<3%). Moreover, large volumes of these particles can be produced in one synthesis; we routinely synthesize 1000 mL of ∼3.5 nM AuNPs. The key features of the improved protocol are the control of the pH by using a citrate buffer instead of a citrate solution as the reducing agent or stabilizer and optimized mixing of reagents. Further, the shape uniformity of the particles can be improved by addition of 0.02 mM EDTA. While the proposed protocol is as straightforward as the original Turkevich protocol, it is more tolerant against variations in precursor concentration.
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