The physico-chemical properties of colloidal nanoparticles (NPs) are influenced by their local environment, as, in turn, the local environment influences the physico-chemical properties of the NPs. In other words, the local environment around NPs has a profound impact on the NPs, and it is different from bulk due to interaction with the NP surface. So far, this important effect has not been addressed in a comprehensive way in the literature. The vicinity of NPs can be sensitively influenced by local ions and ligands, with effects already occurring at extremely low concentrations. NPs in the Hü ckel regime are more sensitive to fluctuations in the ionic environment, because of a larger Debye length. The local ion concentration hereby affects the colloidal stability of the NPs, as it is different from bulk owing to Debye Hü ckel screening caused by the charge of the NPs. This can have subtle effects, now caused by the environment to the performance of the NP, such as for example a buffering effect caused by surface reaction on ultrapure ligandfree nanogold, a size quenching effect in the presence of specific ions and a significant impact on fluorophore-labelled NPs acting as ion sensors. Thus, the aim of this review is to clarify and give an unifying view of the complex interplay between the NP's surface with their nanoenvironment.

Specific ion effects ranking in the Hofmeister sequence are ubiquitous in biochemical, industrial, and atmospheric processes. In this experimental study specific ion effects inexplicable by the classical DLVO theory have been investigated at curved water-metal interfaces of gold nanoparticles synthesized by a laser ablation process in liquid in the absence of any organic stabilizers. Notably, ion-specific differences in colloidal stability occurred in the Hückel regime at extraordinarily low salinities below 50 μM, and indications of a direct influence of ion-specific effects on the nanoparticle formation process are found. UV-vis, zeta potential, and XPS measurements help to elucidate coagulation properties, electrokinetic potential, and the oxidation state of pristine gold nanoparticles. The results clearly demonstrate that stabilization of ligand-free gold nanoparticles scales proportionally with polarizability and antiproportionally with hydration of anions located at defined positions in a direct Hofmeister sequence of anions. These specific ion effects might be due to the adsorption of chaotropic anions (Br(-), SCN(-), or I(-)) at the gold/water interface, leading to repulsive interactions between the partially oxidized gold particles during the nanoparticle formation process. On the other hand, kosmotropic anions (F(-) or SO4(2-)) seem to destabilize the gold colloid, whereas Cl(-) and NO3(-) give rise to an intermediate stability. Quantification of surface charge density indicated that particle stabilization is dominated by ion adsorption and not by surface oxidation. Fundamental insights into specific ion effects on ligand-free aqueous gold nanoparticles beyond purely electrostatic interactions are of paramount importance in biomedical or catalytic applications, since colloidal stability appears to depend greatly on the type of salt rather than on the amount.

Size control of laser-fabricated surfactant-free gold nanoparticles is a challenging endeavor. In this work, we show that size control can be achieved by adding ions with low salinity during synthesis. In addition, this approach offers the opportunity to fundamentally study ion interactions with bare nanoparticle surfaces and can help to elucidate the nanoparticle formation mechanism. The studies were carried out in a flow-through reactor and in the presence of NaCl, NaBr and sodium phosphate buffer at minimal ionic strengths. A significant size quenching effect at ionic strengths from 1-50 μM was found, which allowed surfactant-free nanoparticle size control with average diameters of 6-30 nm. This effect went along with low polydispersity and minimal aggregation tendencies and was confirmed by UV-vis spectroscopy, TEM, SEM and analytical disk centrifugation. Our findings indicate that size quenching originates from an anionic electrostatic stabilization depending on the nanoparticle surface area, which may be caused by specific ion adsorption. By subsequent delayed bioconjugation in liquid-flow using bovine serum albumin as a stabilizing agent, nano-bioconjugates with good stability in cell culture media were obtained, which are applicable in toxicology and cell biology.

Sustainable societies require the development of engineered hybrid materials. Bio-inspired mineralization of the wood cell wall architecture with calcium carbonate offers a green alternative to conventional fire-retardant systems.

Anisotropic and hierarchical structures are bound in nature and highly desired in engineered materials, due to their outstanding functions and performance. Mimicking such natural features with synthetic materials and methods has been a highly active area of research in the last decades. Unlike these methods, we use the native biomaterial wood, with its intrinsic anisotropy and hierarchy as a directional scaffold for the incorporation of magnetic nanoparticles inside the wood material. Nanocrystalline iron oxide particles were synthesized in situ via coprecipitation of ferric and ferrous ions within the interconnected pore network of bulk wood. Imaging with low-vacuum and cryogenic electron microscopy as well as spectral Raman mapping revealed layered nanosize particles firmly attached to the inner surface of the wood cell walls. The mineralogy of iron oxide was identified by XRD powder diffraction and Raman spectroscopy as a mixture of the spinel phases magnetite and maghemite. The intrinsic structural architecture of native wood entails a three-dimensional assembly of the colloidal iron oxide which results in direction-dependent magnetic features of the wood-mineral hybrid material. This superinduced magnetic anisotropy, as quantified by direction-dependent magnetic hysteresis loops and low-field susceptibility tensors, allows for directional lift, drag, alignment, (re)orientation, and actuation, and opens up novel applications of the natural resource wood.

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Wood can be considered as a highly porous, three-dimensional organic scaffold. It can be mineralized to create hierarchically structured organic-inorganic hybrid materials with novel properties. In the present paper, the precipitation of CaCO3 mineral in Norway spruce and European beech wood has been studied by alternating impregnation with aqueous and alcoholic electrolyte solutions. Microstructural imaging by SEM and confocal Raman microscopy shows the distribution of calcite and vaterite as two CaCO3 polymorphs, which are deposited deep inside the cellular structure of the wood. The confined microenvironment of the wood cell wall seems to favor a formation of vaterite, as visible by XRD and Raman spectroscopy. In view of a practical application, the mineralization of wood opens up ways for sustainable wood-based hybrid materials with a significantly improved fire resistance, as proven via pyrolysis combustion flow calorimetry and cone calorimetry tests. Beyond that, this versatile solute-exchange approach provides an opportunity for the incorporation of a broad range of different mineral phases into wood for novel material property combinations.

A "grafting-from" polymerization approach within and at the complex and heterogeneous macromolecular assembly of wood cell walls is shown. The approach allows for the implementation of novel functionalities in renewable and functional wood-based materials. The native wood structure is retained and used as a hierarchical multiscale framework for a modular two-step polymerization process. The versatility and potential of the approach is shown by a polymerization of either hydrophobic or hydrophilic and pH-responsive monomers in the wood structure. Characterization of the modified wood reveals the presence of polymer in the cell wall, and the new properties of these wood materials are discussed.