Ion-mediated charge-charge interactions drive aggregation of surface-functionalized gold nanoparticles

Monolayer-protected metal nanoparticles (NPs) are not only promising materials with a wide range of potential industrial and biological applications, but they are also a powerful tool to investigate the behavior of matter at nanoscopic scales, including the stability of dispersions and colloidal systems. This stability is dependent on a delicate balance between electrostatic and steric interactions that occur in the solution, and it is described in quantitative terms by the classic Derjaguin-Landau-Vewey-Overbeek (DLVO) theory, that posits that aggregation between NPs is driven by hydrophobic interactions and opposed by electrostatic interactions. To investigate the limits of this theory at the nanoscale, where the continuum assumptions required by the DLVO theory break down, here we investigate NP dimerization by computing the Potential of Mean Force (PMF) of this process using fully atomistic MD simulations. Serendipitously, we find that electrostatic interactions can lead to the formation of metastable NP dimers. These dimers are stabilized by complexes formed by negatively charged ligands belonging to distinct NPs that are bridged by positively charged ions present in solution. We validate our findings by collecting tomographic EM images of NPs in solution and by quantifying their radial distribution function, that shows a marked peak at interparticle distance comparable with that of MD simulations. Taken together, our results suggest that not only hydrophobic interactions, but also electrostatic interactions, contribute to attraction between nano-sized charged objects at very short length scales.

Particle interactions and their effect on magnetic particle imaging and spectroscopy

Tracer and thus signal stability is crucial for an accurate diagnosis via magnetic particle imaging (MPI). However, MPI-tracer nanoparticles frequently agglomerate during their in vivo applications leading to particle interactions. Here, we investigate the influence of such magnetic coupling phenomena on the MPI signal. We prepared and characterized Zn0.4Fe2.6O4 nanoparticles and controlled their interparticle distance by varying SiO2 coating thickness. The silica shell affected the magnetic properties indicating stronger particle interactions for a smaller interparticle distance. The SiO2-coated Zn0.4Fe2.6O4 outperformed the bare sample in magnetic particle spectroscopy (MPS) in terms of signal/noise, however, the shell thickness itself only weakly influenced the MPS signal. To investigate the importance of magnetic coupling effects in more detail, we benchmarked the MPS signal of the bare and SiO2-coated Zn-ferrites against commercially available PVP-coated Fe3O4 nanoparticles in water and PBS. PBS is known to destabilize nano-particles mimicking an agglomeration in vivo. The bare and coated Zn-ferrites showed excellent signal stability, despite their agglomeration in PBS. We attribute this to their aggregated morphology formed during their flame-synthesis. On the other hand, the MPS signal of commercial PVP-coated Fe3O4 strongly decreased in PBS compared to water, indicating strongly changed particle interactions. The relevance of this effect was further investigated in a mammalian cell model. For PVP-coated Fe3O4, we could detect a strong discrepancy between the particle concentration obtained from the MPS signal and the actual concentration determined via ICP-MS. The same trend was observed during their MPI analysis; while SiO2-coated Zn-ferrites could be precisely located in water and PBS, PVP-coated Fe3O4 could not be detected in PBS at all. This drastically limits the sensitivity and also general applicability of MPI using such standard commercial tracers and highlights the advantages of our flame-made Zn-ferrites concerning signal stability and ultimately diagnostic accuracy.

Real-time observation of nucleation and growth of Au on CdSe quantum dot templates

Semiconductor quantum dot (QD) arrays can be useful for optical devices such as lasers, solar cells and light-emitting diodes. As the size distribution influences the band-gap, it is worthwhile to investigate QDs prepared using different solvents because each of them could influence the overall morphology differently, depending on the ligand network around individual QDs. Here, we follow the nucleation and growth of gold (Au) on CdSe QD arrays to investigate the influence of surface ligands and thereby realized interparticle distance between QDs on Au growth behaviour. We particularly emphasize on the monolayer stage as the Au decoration on individual QDs is expected at this stage. Therefore, we sputter-deposit Au on each QD array to investigate the morphological evolution in real-time using time-resolved grazing-incidence small-angle X-ray scattering (GISAXS). The growth kinetics - independent of the template - signifies that the observed template-mediated nucleation is limited only to the very first few monolayers. Delicate changes in the Au growth morphology are seen in the immediate steps following the initial replicated decoration of the QD arrays. This is followed by a subsequent clustering and finally a complete Au coverage of the QD arrays.

Workability and Compressive Strength Behavior of a Cemented High-Porosity Backfill Material

A full understanding of the workability and unconfined compressive strength (UCS) of the cemented high-porosity (CHPB) material, made of surface sand, widely distributed in the western mining area, foam, and cementing materials, is important for applying in ecologically fragile mining areas of western China. In this article, the influence of solid content, density grade, sand/binder ratio, and silica fume dosage in binder on workability and strength development of CHPB samples in different curing ages is studied. Test results show that the fresh CHPB mix has good workability, due to the existence of a large number of bubbles. With the increase of density grade, the UCS of the CHPB sample increases exponentially. Workability of fresh CHPB samples significantly decreases with increasing solid content due to the reduction of interparticle distance. For a given mix proportion, the optimal solid content of CHPB samples is 83.7%. The variation of the sand/binder ratio from 3 to 4.5 results in a slight increase of workability and a significant increase of the UCS. Silica fume demonstrates improvement on workability and strength behavior, and the optimal dosage in the binder should not exceed 10%.

THEORETICAL-EXPERIMENTAL POSSIBILLITIES OF MICROSTRUCTURE QUANTIFICATION OF DISPERSION STRENGTHENED MATERIALS

The present paper is devoted to the possibilities to classify the spatial arrangement of the elements (features) of a stochastic process with geometrical objects. The fundamental quantities describing point processes were introduced. Experimental possibilities of structural objects determination, possibilities of evaluation of the size distribution of the secondary phases, testing of planar point structures (estimation of the process intensity, square method and characteristics of the second order) were estimated. Interparticle distances, namely mean interparticle distance, mean minimum distance, mean visibility and mean path of spherical contact were defined. Selected processes were described and demonstrated from simulated realizations on Al-Al4C3 dispersion strengthened material, prepared by a powder metallurgy method of reaction milling. Interparticle distances of Al4C3 particles were evaluated. Polygonal methods and quadrant counts method were used for characterization of the particle arrangement.

Magneto-Plasmonic Nanoparticle Grid Biosensor with Enhanced Raman Scattering and Electrochemical Transduction for the Development of Nanocarriers for Targeted Delivery of Protected Anticancer Drugs

Safe administration of highly cytotoxic chemotherapeutic drugs is a challenging problem in cancer treatment due to the adverse side effects and collateral damage to non-tumorigenic cells. To mitigate these problems, promising new approaches, based on the paradigm of controlled targeted drug delivery (TDD), and utilizing drug nanocarriers with biorecognition ability to selectively target neoplastic cells, are being considered in cancer therapy. Herein, we report on the design and testing of a nanoparticle-grid based biosensing platform to aid in the development of new targeted drug nanocarriers. The proposed sensor grid consists of superparamagnetic gold-coated core–shell Fe2Ni@Au nanoparticles, further functionalized with folic acid targeting ligand, model thiolated chemotherapeutic drug doxorubicin (DOX), and a biocompatibility agent, 3,6-dioxa-octanethiol (DOOT). The employed dual transduction method based on electrochemical and enhanced Raman scattering detection has enabled efficient monitoring of the drug loading onto the nanocarriers, attaching to the sensor surface, as well as the drug release under simulated intracellular conditions. The grid’s nanoparticles serve here as the model nanocarriers for new TDD systems under design and optimization. The superparamagnetic properties of the Fe2Ni@Au NPs aid in nanoparticles’ handling and constructing a dense sensor grid with high plasmonic enhancement of the Raman signals due to the minimal interparticle distance.