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.
Upon incorporation of nanoparticles (NPs) into the body, they are exposed to biological fluids, and their interaction with the dissolved biomolecules leads to the formation of the so-called protein corona on the surface of the NPs. The composition of the corona plays a crucial role in the biological fate of the NPs. While the effects of various physicochemical parameters on the composition of the corona have been explored in depth, the role of temperature upon its formation has received much less attention. In this work, we have probed the effect of temperature on the protein composition on the surface of a set of NPs with various surface chemistries and electric charges. Our results indicate that the degree of protein coverage and the composition of the adsorbed proteins on the NPs' surface depend on the temperature at which the protein corona is formed. Also, the uptake of NPs is affected by the temperature. Temperature is, thus, an important parameter that needs to be carefully controlled in quantitative studies of bionano interactions.
Synthesis, characterization, and applications of colloidal nanoparticles have been a prominent topic of current research interests within the last two decades. Available reports in the literature that describe the synthesis of colloidal nanoparticles are abundant with various degrees of reproducibility and simplicity. Moreover, different methods for the characterization of colloidal nanoparticles' basic properties are employed, resulting in conflicting results in many cases. Herein, we describe "in detail" selected standard protocols for the synthesis, purification, and characterization of various types of colloidal inorganic nanoparticles including gold nanoparticles, silver nanoparticles, iron oxide nanoparticles, and quantum dots. This report consists of five main parts: The first and the second part are dedicated to describing the synthesis of various types of hydrophobic and hydrophilic nanoparticles in organic solvents and in aqueous solutions, respectively. The third part describes surface modification of nanoparticles with focus on ligand exchange reactions, to allow phase transfer of nanoparticles from aqueous to organic solvents and vice versa. The fourth and the fifth part describe various general purification and characterization techniques used to purify and characterize nanoparticles, respectively. Collectively, this contribution does not aim to cover all available protocols in the literature to prepare inorganic nanoparticles, but rather provides detailed synthetic procedures to important inorganic nanocrystals with full description of their purification and characterization process.
A set of three types of silver nanoparticles (Ag NPs) are prepared, which have the same Ag cores, but different surface chemistry. Ag cores are stabilized with mercaptoundecanoic acid (MUA) or with a polymer shell [poly(isobutylene-alt-maleic anhydride) (PMA)]. In order to reduce cellular uptake, the polymer-coated Ag NPs are additionally modifi ed with polyethylene glycol (PEG). Corrosion (oxidation) of the NPs is quantifi ed and their colloidal stability is investigated. MUA-coated NPs have a much lower colloidal stability than PMA-coated NPs and are largely agglomerated. All Ag NPs corrode faster in an acidic environment and thus more Ag(I) ions are released inside endosomal/lysosomal compartments. PMA coating does not reduce leaching of Ag(I) ions compared with MUA coating. PEGylation reduces NP cellular uptake and also the toxicity. PMA-coated NPs have reduced toxicity compared with MUA-coated NPs. All studied Ag NPs were less toxic than free Ag(I) ions. All in all, the cytotoxicity of Ag NPs is correlated on their uptake by cells and agglomeration behavior
The innovative use of engineered nanomaterials in medicine, be it in therapy or diagnosis, is growing dramatically. This is motivated by the current extraordinary control over the synthesis of complex nanomaterials with a variety of biological functions (e.g. contrast agents, drug-delivery systems, transducers, amplifiers, etc.). Engineered nanomaterials are found in the bio-context with a variety of applications in fields such as sensing, imaging, therapy or diagnosis. As the degree of control to fabricate customized novel and/or enhanced nanomaterials evolves, often new applications, devices with enhanced performance or unprecedented sensing limits can be achieved. Of course, interfacing any novel material with biological systems has to be critically analyzed as many undesirable adverse effects can be triggered (e.g. toxicity, allergy, genotoxicity, etc.) and/or the performance of the nanomaterial can be compromised due to the unexpected phenomena in physiological environments (e.g. corrosion, aggregation, unspecific absorption of biomolecules, etc.). Despite the need for standard protocols for assessing the toxicity and bio-performance of each new functional nanomaterial, these are still scarce or currently under development. Nonetheless, nanotoxicology and relating adverse effects to the physico-chemical properties of nanomaterials are emerging areas of the utmost importance which have to be continuously revisited as any new material emerges. This review highlights recent progress concerning the interaction of nanomaterials with biological systems and following adverse effects.
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