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Sterilization is a major prerequisite for the utilization of nanoparticle colloids in biomedicine, a process well examined for particles derived from chemical synthesis although highly underexplored for electrostatically stabilized ligand-free gold nanoparticles (AuNPs). Hence, in this work, we comprehensively examined and compared the physicochemical characteristics of laser-generated ligand-free colloidal AuNPs exposed to steam sterilization and sterile filtration as a function of particle size and mass concentration and obtained physicochemical insight into particle growth processes. These particles exhibit long-term colloidal stability (up to 3 months) derived from electrostatic stabilization without using any ligands or surfactants. We show that particle growth attributed to cluster-based ripening occurs in smaller AuNPs (∼5 nm) following autoclaving, while larger particles (∼10 and ∼30 nm) remain stable. Sterile filtration, as an alternative effective sterilizing approach, has no substantial impact on the colloidal stability of AuNPs, regardless of particle size, although a mass loss of 5–10% is observed. Finally, we evaluated the impact of the sterilization procedures on potential particle functionality in proton therapy, using the formation of reactive oxygen species (ROS) as a readout. In particular, 5 nm AuNPs exhibit a significant loss in activity upon autoclaving, probably dedicated to specific surface area reduction and surface restructuring during particle growth. The filtered analog enhanced the ROS release by up to a factor of ∼2.0, at 30 ppm gold concentration. Our findings highlight the need for carefully adapting the sterilization procedure of ligand-free NPs to the desired biomedical application with special emphasis on particle size and concentration.

Electrophoretic deposition (EPD) of platinum nanoparticles (PtNPs) on platinum–iridium (Pt–Ir) neural electrode surfaces is a promising strategy to tune the impedance of electrodes implanted for deep brain stimulation in various neurological disorders such as advanced Parkinson’s disease and dystonia. However, previous results are contradicting as impedance reduction was observed on flat samples while in three-dimensional (3D) structures, an increase in impedance was observed. Hence, defined correlations between coating properties and impedance are to date not fully understood. In this work, the influence of direct current (DC) and pulsed-DC electric fields on NP deposition is systematically compared and clear correlations between surface coating homogeneity and in vitroimpedance are established. The ligand-free NPs were synthesized via pulsed laser processing in liquid, yielding monomodal particle size distributions, verified by analytical disk centrifugation (ADC). Deposits formed were quantified by UV–vis supernatant analysis and further characterized by scanning electron microscopy (SEM) with semiautomated interparticle distance analyses. Our findings reveal that pulsed-DC electric fields yield more ordered surface coatings with a lower abundance of particle assemblates, while DC fields produce coatings with more pronounced aggregation. Impedance measurements further highlight that impedance of the corresponding electrodes is significantly reduced in the case of more ordered coatings realized by pulsed-DC depositions. We attribute this phenomenon to the higher active surface area of the adsorbed NPs in homogeneous coatings and the reduced particle−electrode electrical contact in NP assemblates. These results provide insight for the efficient EPD of bare metal NPs on micron-sized surfaces for biomedical applications in neuroscience and correlate coating homogeneity with in vitrofunctionality.

A ligand exchange strategy has been employed to understand the role of ligands on the structural and optical properties of atomically precise 29 atom silver nanoclusters (NCs). By ligand optimization, ∼44-fold quantum yield (QY) enhancement of Ag29(BDT)12–x(DHLA)xNCs (x= 1–6) was achieved, where BDT and DHLA refer to 1,3-benzene-dithiol and dihydrolipoic acid, respectively. High-resolution mass spectrometry was used to monitor ligand exchange, and structures of the different NCs were obtained through density functional theory (DFT). The DFT results from Ag29(BDT)11(DHLA) NCs were further experimentally verified through collisional cross-section (CCS) analysis using ion mobility mass spectrometry (IM MS). An excellent match in predicted CCS values and optical properties with the respective experimental data led to a likely structure of Ag29(DHLA)12NCs consisting of an icosahedral core with an Ag16S24shell. Combining the experimental observation with DFT structural analysis of a series of atomically precise NCs, Ag29–yAuy(BDT)12–x(DHLA)x(where y, x= 0,0; 0,1; 0,12 and 1,12; respectively), it was found that while the metal core is responsible for the origin of photoluminescence (PL), ligands play vital roles in determining their resultant PLQY.

Gold–silver alloy nanoparticles are interesting for multiple applications, including heterogeneous catalysis, optical sensing, and antimicrobial properties. The inert element gold acts as a stabilizer for silver to prevent particle corrosion, or conversely, to control the release kinetics of antimicrobial silver ions for long-term efficiency at minimum cytotoxicity. However, little is known about the kinetics of silver ion leaching from bimetallic nanoparticles and how it is correlated with silver content, especially not on a single-particle level. To characterize the kinetics of silver ion release from gold–silver alloy nanoparticles, we employed a combination of electron microscopy and single-particle hyperspectral imaging with an acquisition speed fast enough to capture the irreversible silver ion leaching. Single-particle leaching profiles revealed a reduction in silver ion leaching rate due to the alloying with gold as well as two leaching stages, with a large heterogeneity in rate constants. We modeled the initial leaching stage as a shrinking-particle with a rate constant that exponentially depends on the silver content. The second, slower leaching stage is controlled by the electrochemical oxidation potential of the alloy being steadily increased by the change in relative gold content and diffusion of silver atoms through the lattice. Interestingly, individual nanoparticles with similar sizes and compositions exhibited completely different silver ion leaching yields. Most nanoparticles released silver completely, but 25% of them appeared to arrest leaching. Additionally, nanoparticles became slightly porous. Alloy nanoparticles, produced by scalable laser ablation in liquid, together with kinetic studies of silver ion leaching, provide an approach to design the durability or bioactivity of alloy nanoparticles.

Bimetallic core–shell nanoparticles (CSNPs), where a ferromagnetic core (e.g., Co) is surrounded by a noble-metal thin plasmonic shell (e.g., Au), are highly interesting for applications in biomedicine and catalysis. Chemical synthesis of such structures, however, requires multistep procedures and often suffers from impaired oxidation resistance of the core. Here, we utilized a one-step environmentally friendly laser ablation in liquid technique to fabricate colloidal Co–Au CSNPs with core–shell yields up to 78% in mass. An in-depth analysis of the CSNPs down to single-particle levels revealed the presence of a unique nested core–shell structure with a very thin gold-rich shell, a nanocrystalline ε-cobalt sublayer, and a nested gold-rich core. The generated Co–Au CSNPs feature soft magnetic properties, while all gold-rich phases (thin shells and nested cores) exhibit a face-centered cubic solid solution with substantial cobalt substitution. The experimental findings are backed by refined thermodynamic surface energy calculations, which more accurately predict the predominance of solid solution and core–shell phase structures in correlation with particle size and nominal composition. Based on the Co–Au bulk phase diagram and in conjunction with previously reported results on the Fe–Au core–shell system as well as Co–Pt controls, we deduce four general rules for core–shell formation in non- or partially miscible laser-generated bimetallic nanosystems.

Pulsed laser ablation in liquids (PLAL) is a promising technique for the generation of colloidal alloy nanoparticles that are of high demand in a broad range of fields, including catalysis, additive manufacturing, and biomedicine. Many of the applications have stringent requirements on the nanoparticle composition and size distributions, which can only be met through innovations in the PLAL technique guided by a clear understanding of the nanoparticle formation mechanisms. In this work, we undertake a combined computational and experimental study of the nanoparticle formation mechanisms in ultrashort PLAL of Ag/Cu and Cu/Ag bilayer thin films. Experimental probing of the composition of individual nanoparticles and predictions from large-scale atomistic simulations provide consistent evidence of limited mixing between the two components from bilayer films by PLAL. The simulated and experimental distributions of nanoparticle compositions exhibit an enhanced abundance of Ag-rich and Cu-rich nanoparticles, as well as a strongly depressed population of well-mixed alloy nanoparticles. The surprising observation that the nanoscale phase separation of the two components in the bilayer films manifests itself in the sharp departure from the complete quantitative mixing in the colloidal nanoparticles is explained by the complex dynamic interaction between the ablation plume and liquid environment revealed in the simulations of the initial stage of the ablation process. The simulations predict that rapid deceleration of the ablation plume by the liquid environment results in the formation of a transient hot and dense metal region at the front of the plume, which hampers the mixing of the two components and, at the same time, contributes to the stratification of the plume in the emerging cavitation bubble. As a result, nanoparticles of different sizes and compositions are produced in different parts of the emerging cavitation bubble during the first nanoseconds of the ablation process. Notably, the diameters of the largest nanoparticles generated in the simulations of the initial stage of the ablation process are more than twice larger than the thickness of the original bilayer films. This observation provides a plausible scenario for the formation of large nanoparticles observed in the experiments. The conclusion on limited elemental mixing in the nanoparticles is validated in simulations of bilayers with different spatial order of Cu and Ag layers, even though the two systems exhibit some notable quantitative differences mainly related to the different strength of electron–phonon coupling in Cu and Ag. Overall, the results of this study provide new insights into the formation mechanism of bimetallic nanoparticles in ultrashort PLAL from thin bilayer targets and suggest that the formation of alloy nanoparticles from immiscible elements may be hampered for targets featuring distinctive elemental segregation.

Laser fragmentation in liquids (LFL) allows the synthesis of fully inorganic, ultrasmall gold nanoparticles, usAu NPs (<3 nm). Although the general method is well established, there is a lack of understanding the chemical processes that are triggered by the laser pulses, which may dictate the surface properties that are highly important in heterogeneous oxidation catalytic reactions. We observed the formation of radical oxygen species during LFL, which suggested that LFL is a physicochemical process that leads to particle size reductions and initiates oxidative processes. When the ionic strength in the nanoenvironment was increased, the oxidation of the first atomic layer saturated at 50%, whereby the surface charge density increases continuously. We found a correlation between the surface charge density after synthesis of colloidal nanoparticles and its behavior in catalysis. The properties of the laser-generated nanoparticles in the colloidal state appear to have predetermined the catalytic performance. We found that a smaller surface charge density of the usAu NPs was beneficial for the catalytic activity in CO and ethanol oxidation, while their peroxidase-like activity was affected less. The catalytic activity was 2 times higher for samples prepared by chloride-free LFL after ozone pretreatment compared to samples prepared in pure water.

A laboratory class was developed and evaluated to illustrate the synthesis of metal nanoclusters (NCs) and to explain their photoluminescence properties for the case of silver. The described experiment employs a synthetic protocol that consists of two sequential phases in a single reaction pot: the reduction of silver ions into plasmonic silver nanoparticles (NPs) (bottom-up), followed by etching the formed silver NPs into ultrasmall atomically precise fluorescent silver NCs (top-down), Ag29(DHLA)12(DHLA: dihydrolipoic acid). UV–vis absorption and fluorescence spectroscopy were employed as a function of reaction time to confirm the development of the plasmonic character of silver NPs (reaction intermediate) and, later on, the onset of fluorescence emission of the silver NCs (final product). Collectively, this experiment was found to be simple to carry out, safe, reproducible, and cost-effective, and it achieved the intended learning outcomes. Participating students found this laboratory class suitable to be implemented into an upper-division undergraduate or graduate curriculum.

Gold nanoclusters (AuNCs) with diameters smaller than 3 nm are an emerging field of research because they possess interesting optical properties, such as photoluminescence. However, to date, it is still difficult to distinguish whether these properties originate from the cores of the nanoparticles or from the adsorbates on their surfaces. Hence, there is a high demand for ligand-free, ultra-small particles because they make it possible to study ligand and core effects separately. Pulsed laser fragmentation in liquids (LFL) is a convenient route for the synthesis of ligand-free AuNCs. The influence of physical parameters, such as melting and evaporation, on the LFL process is well understood both theoretically and experimentally. However, the impact of the chemical composition of the medium during LFL, which critically affects the particle formation process, has been less well examined. Therefore, in this work, we elucidate the extent to which the ionic strength, the pH value, and the nature of the halide anion that is present, that is, F–, Cl–, Br–, or I–, influence the particle size distribution of the LFL product and the mean yield of small particles (<3 nm) of the product. We showed that the yield of small particles can be enhanced by the synergism between pH and specific ion effects, which probably is attributable to the adsorption of specific anions. In addition, our findings indicated that anion-based stabilization depends critically on the type of anion. A direct Hofmeister effect was observed for anions in the neutral pH regime, whereas an indirect Hofmeister series was reported in alkaline solution, which probably was due to the more hydrophilic surfaces of the AuNCs that were formed.

Tailoring the morphology of nanoporous structures widens the scope of applications in catalysis and sensing. The synthesis of versatile nanoporous morphologies with the spatial distribution of porosity is permitted by the dealloying of unique, metastable Au–Fe alloy template nanoparticles generated by laser ablation in liquids. This approach opens the door to a novel process, which involves a special transformation mechanism, including oxidation and Kirkendall effect, which is decisive for the stabilization of hollow structures with the spatial distribution of porosity and represents a memory effect of morphology. Within this work, nanoporous Au particles, hollow nanoporous Au shells with the spatial distribution of porosity, and yolk–shell-like Au nanoparticles encapsulated in ultrathin Au shells are synthesized. A distinct variation of crystallinity and an increased lattice strain is observed, which implies an improved catalytic activity for oxidation reactions.

The bactericidal effects of silver nanoparticles (Ag NPs) against infectious strains of multiresistant bacteria is a well‐studied phenomenon, highly relevant for many researchers and clinicians battling bacterial infections. However, little is known about the uptake of the Ag NPs into the bacteria, the related uptake mechanisms, and how they are connected to antimicrobial activity. Even less information is available on AgAu alloy NPs uptake. In this work, the interactions between colloidal silver–gold alloy nanoparticles (AgAu NPs) and Staphylococcus aureus(S. aureus) using advanced electron microscopy methods are studied. The localization of the nanoparticles is monitored on the membrane and inside the bacterial cells and the elemental compositions of intra‐ and extracellular nanoparticle species. The findings reveal the formation of pure silver nanoparticles with diameters smaller than 10 nm inside the bacteria, even though those particles are not present in the original colloid. This finding is explained by a local RElease PEnetration Reduction (REPER) mechanism of silver cations emitted from the AgAu nanoparticles, emphasized by the localization of the AgAu nanoparticles on the bacterial membrane by aptamer targeting ligands. These findings can deepen the understanding of the antimicrobial effect of nanosilver, where the microbes are defusing the attacking silver ions via their reduction, and aid in the development of suitable therapeutic approaches. This study uses targeting silver‐gold alloy nanoparticles to show that silver nanoparticles found inside bacteria follow a RElease‐PEnetration‐Reduction (REPER) mechanism of the emitted silver cations, with the microbes thereby potentially defusing the therapeutic effect related to silver ions.

Directing the assembly of atoms into core–shell particles generally requires elegant but sophisticated procedures. Here we show how the thermodynamic driving force to minimization of surface and interface energy can be exploited to produce colloidal Fe–Au core–shell nanoparticles in one step and with a yield approaching 99.7% in mass. This is obtained by laser ablation with nanosecond pulses of thin bimetallic films immersed in acetone. The Fe–Au core–shell nanoparticles show magnetic and plasmonic properties, and a surface available to bioconjugation and analytical assays. This laser assisted synthetic method represents a step forward in the facile preparation of core–shell nanospheres with multiple appealing functionalities.

Laser-inducd fragmentation is a promising tool for controlling the particle size of ligand-free colloidal nanoparticles and to synthesize ligand-free gold nanoclusters. However, because the underlying mechanisms are not fully understood, increasing the yield of this process remains challenging. In this work, we examine the pulsed laser fragmentation of gold nanoparticles in liquid under statistical single-pulse conditions with high-fluence nanosecond pulses and correlate them with the educt particle size, number of pulses, and laser fluence. We conclusively prove that the fragmentation process of gold nanoparticles is a one-pulse and one-step event, which yields monomodal particles of ≪10 nm down to 2.8 +/- 0.1 nm when exceeding a pulse peak power of 1.6 × 1012W/m2and when all educt particles are larger than 13.4 nm. This size threshold for quantitative fragmentation fits well with the size limit of 13.1 nm calculated with respect to the evaporation–heat–energy balance. Furthermore, we found strong evidence that the number of irradiation cycles, varied within the regime of one to four laser pulses/colloid volume, can be used to tune the surface chemistry and surface charge of the resulting nanoparticles in an aqueous medium.

Three-dimensional morphology changes of bimetallic nanoparticles (NPs) with nominal composition Au50Fe50and Au20Fe80, generated by pulsed laser ablation in liquid, are monitored in situand ex situvia scanning transmission electron microscopy and electron tomography. The samples are made up of a chemically segregated core–shell (CS) NPs structure, with an Au-rich shell and Fe-rich core, and solid solution (SS) NPs in the pristine state. Further, the examinations reveal information about a sequence of characteristic changes from the pristine metastable and intermediate ultrastructures up to thermodynamically stable products. In the case of the Au20Fe80sample, a metastable spherical CS morphology is transformed at equilibrium conditions into a cube-shaped Fe-rich core faceted by truncated Au-rich pyramids. For the Au50Fe50sample, the Au-rich shell is solved into the Fe-rich core, and chemically homogeneous (SS) NPs are formed. Interestingly, this transformation was proven to occur via an intermediate ultrastructure with lamellar segregation, not previously reported as a transient state during in situheating. On the basis of these observations, a correlation between the composition and the morphology at equilibrium is suggested, in accordance with the bulk phase diagram of Au–Fe. At the same time, our examinations directly prove that laser ablation synthesis creates nonequilibrium NP morphologies, frozen in metastable, spherical core–shell particles.

Therapeutically active small molecules represent promising nonimmunogenic alternatives to antibodies for specifically targeting disease-relevant receptors. However, a potential drawback compared to antibody–antigen interactions may be the lower affinity of small molecules toward receptors. Here, we overcome this low-affinity problem by coating the surface of nanoparticles (NPs) with multiple ligands. Specifically, we explored the use of gold and platinum nanoparticles to increase the binding affinity of Aβ-specific small molecules to inhibit Aβ peptide aggregation into fibrils in vitro. The interactions of bare NPs, free ligands, and NP-bound ligands with Aβ are comprehensively studied viaphysicochemical methods (spectroscopy, microscopy, immunologic tests) and cell assays. Reduction of thioflavin T fluorescence, as an indicator for β-sheet content, and inhibition of cellular Aβ excretion are even more effective with NP-bound ligands than with the free ligands. The results from this study may have implications in the development of therapeutics for treating Alzheimer’s disease.

The mechanical stability of implant coatings is crucial for medical approval and transfer to clinical applications. Here, electrophoretic deposition (EPD) is a versatile coating technique, previously shown to cause significant post‐surgery impedance reduction of brain stimulation platinum electrodes. However, the mechanical stability of the resulting coating has been rarely systematically investigated. In this work, pulsed‐DC EPD of laser‐generated platinum nanoparticles (PtNPs) on Pt‐based, 3D neural electrodes is performed and the in vitro mechanical stability is examined using agarose gel, adhesive tape, and ultrasonication‐based stress tests. EPD‐generated coatings are highly stable inside simulated brain environments represented by agarose gel tests as well as after in vivo stimulation experiments. Electrochemical stability of the NP‐modified surfaces is tested via cyclic voltammetry and that multiple scans may improve coating stability could be verified, indicated by higher signal stability following highly invasive adhesive tape stress tests. The brain sections post neural stimulation in rats are analyzed via laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). Measurements reveal higher levels of Pt near the region stimulated with coated electrodes, in comparison to uncoated controls. Even though local concentrations in the vicinity of the implanted electrode are elevated, the total Pt mass found is below systemic toxicologically relevant concentrations. The mechanical stability of surface modified neural electrodes via electrophoretic deposition using laser‐generated platinum nanoparticles is evaluated. In vitro stability tests show the lowest impedance increase after agarose gel test. After in vivo deep brain stimulation (DBS) in rats, the amount of biodispersed platinum is higher in coated electrodes though being fourfold lower than toxicologically relevant systemic concentrations.

Electrophoretic deposition of ligand-free platinum nanoparticles has been studied to elucidate how wettability, indicated by contact angle measurements, is linked to vital parameters of the electrophoretic deposition process. These parameters, namely the colloid concentration, electric field strength and deposition time, have been systematically varied in order to determine their influence on the contact angle. Additionally, scanning electron microscopy has been used to confirm the homogeneity of the achieved coatings.

Platinum electrodes are critical components in many biomedical devices, an important example being implantable neural stimulation or recording electrodes. However, upon implantation, scar tissue forms around the electrode surface, causing unwanted deterioration of the electrical contact. We demonstrate that sub-monolayer coatings of platinum nanoparticles (PtNPs) applied to 3D neural electrodes by electrophoretic deposition (EPD) can enhance the electrode's active surface area and significantly lower its impedance. In this work we use ethanol-water mixtures as the EPD solvent, in contrast to our previous studies carried out in water. We show that EPD coating in 30 vol.% ethanol improves the device's electrochemical performance. Computational mesoscale multiparticle simulations were for the first time applied to PtNP-on-Pt EPD, revealing correlations between ethanol concentration, electrochemical properties, and coating homogeneity. Thereto, this optimum ethanol concentration (30 vol.%) balances two opposing trends: (i) the addition of ethanol reduces water splitting and gas bubble formation, which benefits surface coverage, and (ii) increased viscosity and reduced permittivity occur at high ethanol concentrations, which impair the coating quality and favoring clustering. A seven-fold increase in active surface area and significantly reduced in vitro impedance of the nano-modified neural stimulation electrode surfaces highlight the influence of ethanol-water mixtures in PtNP EPD.

This paper highlights a strategy on how totally ligand-free biocompatible gold submicrometer spheres (Au-SMSs) can be synthesized by aggregating laser-fabricated nanoparticles (NPs) with NaCl followed by subsequent post-irradiation using pulsed lasers at a moderate fluence. Interestingly, we observed significant changes in the surface structure of the SMSs, caused by the adsorption of smaller particles following a disaggregation–melting–redeposition–sintering-mechanism. Here, utilization of low fluences yielded perfectly smooth textures while higher fluences lead to wrinkled textures. Furthermore, we elucidate that prior to aggregation, the particle size distribution of the source AuNPs may significantly interfere with the surface texture of the resulting Au-SMSs, indicated by predominant formation of rough surface structures in the presence of smaller source NPs. These findings may highlight novel synthesis strategies for Au-SMSs with rough surface textures, particularly beneficial for SERS applications.

Nano-bio-conjugates, featuring noble metal gold–silver alloy nanoparticles, represent a versatile tool in diagnostics and therapeutics due to their plasmonic and antimicrobial properties tunable by the particle’s gold molar fraction. However, little is known about how the binding of thiolated biomolecules to noble metal nanoparticles is influenced by the fraction of gold and silver atoms on the nanoparticle’s surface and to which extend this would affect the functionality of the conjugated biomolecules. In this work, we generated gold–silver alloy nanoparticles with average diameters of 7–8 nm using the modern, surfactant-free laser ablation in liquids (LAL) synthesis approach. We conjugated them with thiolated miniStrep aptamer ligands at well-controlled aptamer-to-nanoparticle surface area ratios with maxima between 12 and 27 pmol aptamer/cm2particle surface area. The results revealed a clear correlation between surface coverage and the nanoparticles’ nominal gold/silver ratio, with maximum coverage reached for gold-rich alloys and a pronounced maximum for silver-rich alloys. However, the conjugates’ functionality, evaluated by binding of streptavidin, was surprisingly robust and hardly affected by the nominal composition. However, 1.5 times higher surface coverage was needed to obtain maximum functionality in the silver-rich conjugates. Based on these results, it may be concluded that the nominal composition of gold–silver alloy nano-bioconjugates is freely tunable without a pronounced impact on the attached ligands’ functionality, a finding highly relevant for the flexible design of nano-bio-conjugates for future biomedical applications. This study’s results may facilitate the design of alloy nano-bio-conjugates for future applications in therapeutics and diagnostics.

This work highlights the laser-based aqueous synthesis and processing of nanocomposites, composed of zinc or iron nanoparticles embedded in a N-Vinylcaprolactam microgel matrix, with potential applicability as ion releasing fiber pads for wound healing. An in situ laser process for microgel synthesis is developed and optimized for high embedded nanoparticle yields, evaluating influences of laser repetition rate and monomer concentration. The impact of the nanoparticles on polymerization was increased by embedded zinc oxide nanoparticles, and reduced in the presence of iron oxide. Furthermore, TEM images verified that the nanoparticles were homogeneously embedded into the polymer matrix. The nanoparticle-loaded microgels were thermally stable up to 429 °C, which ensures that the composites maintain their integrity after heat sterilization and during rapid prototyping by thermal polymer processing. The general suitability of the hydrogels as active biomaterial for wound healing was assessed in toxicity, cell proliferation and migration assays using human dermal fibroblasts and keratinocytes, where cytocompatibility was verified, while the proliferation was affected by the gel alone as well as the embedded nanoparticles. The hydrogels were processed to suit their use as a biomaterial for wound coverages via electrospinning resulting in a centimeter scale fully cytocompatible fiber pad with the nanoparticle-filled microgel capsules supported on the fiber’s surface.

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 Hückel 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 Hückel 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 ligand-free 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.