Although transmission electron microscopy (TEM) may be one of the most efficient techniques available for studying the morphological characteristics of nanoparticles, analyzing them quantitatively in a statistical manner is exceedingly difficult. Herein, we report a method for mass-throughput analysis of the morphologies of nanoparticles by applying a genetic algorithm to an image analysis technique. The proposed method enables the analysis of over 150,000 nanoparticles with a high precision of 99.75% and a low false discovery rate of 0.25%. Furthermore, we clustered nanoparticles with similar morphological shapes into several groups for diverse statistical analyses. We determined that at least 1,500 nanoparticles are necessary to represent the total population of nanoparticles at a 95% credible interval. In addition, the number of TEM measurements and the average number of nanoparticles in each TEM image should be considered to ensure a satisfactory representation of nanoparticles using TEM images. Moreover, the statistical distribution of polydisperse nanoparticles plays a key role in accurately estimating their optical properties. We expect this method to become a powerful tool and aid in expanding nanoparticle-related research into the statistical domain for use in big data analysis.
We demonstrate a strategy for the synthesis of discrete and uniform gold nanorod (GNR)@mesoporous silica (mSiO2) core–shell nanoparticles (NPs) with finely tuned shell thickness by significantly suppressing the formation of undesired core-free NPs. We could control the thickness of the mSiO2 shell with high precision, close to 1 nm, and hence the rotational diffusion mode of NPs by simply controlling the silica precursor injection times. The growth of the mSiO2 shell on the GNR seeds and the formation of core-free mSiO2 NPs could be explained by two models based on the modified LaMer’s theory. Between these two, we found the most suitable one for the synthesis of GNR@mSiO2 NPs with a precisely controlled shell thickness and negligible core-free NPs as the synthesis mostly occurs via heterogeneous nucleation on GNR seeds. As our results are very simple and highly reproducible, we expect this work to provide profound insights into the synthesis of a variety of heterogeneous nanostructures.
The stability of gold nanoparticles (AuNPs) in biological samples is very important for their biomedical applications. Although various molecules such as polystyrenesulfonate (PSS), phosphine, DNA, and polyethylene glycol (PEG) have been used to stabilize AuNPs, it is still very difficult to stabilize large AuNPs. As a result, biomedical applications of large (30-100 nm) AuNPs are limited, even though they possess more favorable optical properties and are easier to be taken up by cells than smaller AuNPs. To overcome this limitation, we herein report a novel method of preparing large (30-100 nm) AuNPs with a high colloidal stability and facile chemical or biological functionality, via surface passivation with an amphiphilic polymer polyvinylpyrrolidone (PVP). This PVP passivation results in an extraordinary colloidal stability for 13, 30, 50, 70, and 100 nm AuNPs to be stabilized in PBS for at least 3 months. More importantly, the PVP capped AuNPs (AuNP-PVP) were also resistant to protein adsorption in the presence of serum containing media and exhibit a negligible cytotoxicity. The AuNP-PVPs functionalized with a DNA aptamer AS1411 remain biologically active, resulting in significant increase in the uptake of the AuNPs (∼12,200 AuNPs per cell) in comparison with AuNPs capped by a control DNA of the same length. The novel method developed in this study to stabilize large AuNPs with high colloidal stability and biological activity will allow much wider applications of these large AuNPs for biomedical applications, such as cellular imaging, molecular diagnosis, and targeted therapy.
The interdependence of 'size' and 'volume-fraction' hinders the identification of their individual role in the interface properties of metal nanoparticles (NPs) embedded in a matrix. Here, the case of Cu NPs embedded in a C matrix is presented for their profound antibacterial activity. Cu:C nanocomposite thin films with fixed Cu content (≈12 atomic%) are prepared using a plasma process where plasma energy controls the size of Cu NPs (from 9 nm to 16 nm). An inverse relationship between the size-effect on antibacterial activity against Escherichia coli and Staphylococcus aureus bacteria is established through the real time monitoring of an aliquot by inductively coupled plasma mass spectrometry, which confirmed the inverse relationship of Cu ion release from the nanocomposite with varied Cu NP sizes. It was found that enhancing the total power density increases the plasma density as well as effective kinetic energy of the plasma species, which in turn creates a large number of nucleation sites and restricts the island kind of growth of Cu NPs. The mechanism of NP size-control is illustrated on the basis of ion density and nucleation and the growth regime of plasma species. This physical approach to NP size reduction anticipates a contamination-free competitive recipe of size-control to capping based chemical methods.
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