This review contributes to the current understanding of NPs cellular uptake and gives an overview about molecules, which can enhance or decrease cellular internalization of NPs.

The synthesis of anisotropic metallic nanoparticles (NPs) has been a field of intense and challenging research in the past decade. In this communication, we report on the reproducible and highly controllable synthesis of monodisperse branched gold nanoparticles in a droplet-based microfluidics platform. The process has been automated by adapting two different bulk synthetic strategies to microdroplets, acting as microreactors, for NP synthesis: a surfactant-free synthesis and a surfactant-assisted synthesis. Microdroplets were generated in two different microfluidic devices designed to accommodate the requirements of both bulk syntheses. The epitaxial growth of AuNSTs inside the microdroplets allowed for a fine control of reagent mixing and local concentrations during particle formation. This is the first time branched gold NPs have been synthesised in a microfluidics platform. The monodispersity of the product was comparable to the synthesis in bulk, proving the potential of this technology for the continuous synthesis of high quality anisotropic NPs with improved reproducibility.

PAPER Jorge Pérez-Juste et al. Reversible assembly of metal nanoparticles induced by penicillamine. Dynamic formation of SERS hot spotsThemed issue: Self-organisation of nanoparticles Reversible assembly of metal nanoparticles induced by penicillamine.We report a systematic study of the surface modification of gold and silver nanoparticles with DLpenicillamine (PEN) and N-acetyl-DL-penicillamine (NAP), motivated by the possibility of inducing pH-controlled reversible nanoparticle assembly. The interaction of PEN and NAP with the metal nanoparticle surface was studied by isothermal titration calorimetry (ITC). The results indicate that equilibrium is reached with the formation of a submonolayer corresponding to ca. 40% and 64% of total surface coverage for PEN and NAP, respectively. Both PEN and NAP modified nanoparticles could be reversibly aggregated at acidic pH due to the protonation of the carboxylic groups, leading to a decrease in their stability by electrostatic interactions and the advent of hydrogen bonding interactions which promote interparticle linkage. The process was monitored by UV-Vis spectroscopy, transmission electron microscopy (TEM) and surface enhanced Raman scattering (SERS) spectroscopy. Interestingly, the SERS characterization demonstrated the pH-controlled formation of hot-spots.

The long-term fate of biomedically relevant nanoparticles (NPs) at the single cell level after uptake is not fully understood yet. We report that lysosomal exocytosis of NPs is not a mechanism to reduce the particle load. Biopersistent NPs such as nonporous silica and gold remain in cells for a prolonged time. The only reduction of the intracellular NP number is observed via cell division, e.g., mitosis. Additionally, NP distribution after cell division is observed to be asymmetrical, likely due to the inhomogeneous location and distribution of the NP-loaded intracellular vesicles in the mother cells. These findings are important for biomedical and hazard studies as the NP load per cell can vary significantly. Furthermore, we highlight the possibility of biopersistent NP accumulation over time within the mononuclear phagocyte system.

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Small plastic particles such as micro- (<5 mm), sub-micro- (1 µm–100 nm) and nanoplastics (<100 nm) are known to be ubiquitous within our surrounding environment. However, to date relatively few methods exist for the reliable detection of nanoplastic particles in relevant sample matrices such as foods or environmental samples. This lack of relevant data is likely a result of key limitations (e.g., resolution and/or scattering efficiency) for common analytical techniques such as Fourier transform infrared or Raman spectroscopy. This study aims to address this knowledge gap in the field through the creation of surface-enhanced Raman scattering spectroscopy substrates utilizing spherical gold nanoparticles with 14 nm and 46 nm diameters to improve the scattering signal obtained during Raman spectroscopy measurements. The substrates are then used to analyze polystyrene particles with sizes of 161 nm or 33 nm and poly(ethylene terephthalate) particles with an average size of 62 nm. Through this technique, plastic particles could be detected at concentrations as low as 10 µg/mL, and analytical enhancement factors of up to 446 were achieved.

Nanoparticle adsorption to substrates pose a unique challenge to understand uptake mechanisms as it involves the organization of complex cytoskeletal components by cells to perform endocytosis/phagocytosis. In particular, it is not well-understood from a cell mechanics perspective how the adhesion of particles on substrate will influence the ease of material clearance. By using a particle model, key contributing factors underlying cell adhesion on nonporous silica particle surfaces, migration and engulfment, are simulated and studied. Following a 24 h incubation period, monocyte-derived macrophages and A549 epithelial cells are able to adhere and remove particles in their local vicinity through induction of adhesive pulling arise from cell traction forces and phagocytic/endocytic mechanisms, in a size-dependent manner. It is observed that such particle-decorated surfaces can be used to address the influence of surface topography on cell behavior. Substrates which presented 480 nm silica particles are able to induce greater development and maturation of focal adhesions, which play an important role in cellular mechanoregulation. Moreover, under a chemotactic influence, in the presence of 30% fetal bovine serum, macrophages are able to uptake the particles and be directed to translocate along a concentration gradient, indicating that local mechanical effects do not substantially impair normal physiological functions.

A major problem associated with nitric oxide (NO) donors is the release of the desired amount of NO at a specific site. A number of platforms have been developed for the regulation of NO dosage. We present the use of citrate-stabilized gold nanoparticles as a platform to regulate NO release. Because of the affinity between gold and thiols, the characteristic -S-NO bond of S-nitrosothiols (RSNOs) breaks in the presence of gold nanoparticles, thereby releasing NO and modifying the gold nanoparticle surface with the corresponding thiol. This system allows for surface-controlled NO release, where the amount of NO released is proportional to the number of thiols bound to the gold nanoparticle surface. Moreover, by employing an amperometric technique to detect the maximum NO release, we were able to estimate the stoichiometry of the reaction, that is, the number of adsorbed RSNO molecules per gold nanoparticle. A kinetic model for NO release and its subsequent decomposition is proposed and used to fit the experimental results. The reaction was found to be zeroth- and first-order with respect to RSNO and gold nanoparticles, respectively.