Chemical sensing with Au and Ag nanoparticles.

Noble metal nanoparticles (NPs) are ideal scaffolds for the fabrication of sensing devices because of their high surface-to-volume ratio combined with their unique optical and electrical properties which are extremely sensitive to changes in the environment. Such characteristics guarantee high sensitivity in sensing processes. Metal NPs can be decorated with ad hoc molecular building blocks which can act as receptors of specific analytes. By pursuing this strategy, and by taking full advantage of the specificity of supramolecular recognition events, highly selective sensing devices can be fabricated. Besides, noble metal NPs can also be a pivotal element for the fabrication of chemical nose/tongue sensors to target complex mixtures of analytes. This review highlights the most enlightening strategies developed during the last decade, towards the fabrication of chemical sensors with either optical or electrical readout combining high sensitivity and selectivity, along with fast response and full reversibility, with special attention to approaches that enable efficient environmental and health monitoring.

Novel Sensing Strategies Based on Monolayer Protected Gold Nanoparticles for the Detection of Metal Ions and Small Molecules.

Monolayer protected gold nanoparticles (AuNPs) have a huge potential for the development of innovative sensing systems for the detection of metal ions and small molecules. The organic ligand shell, primarily utilized to stabilize the gold core, can be rationally designed to promote selective interactions with a desired analyte. In addition, the outstanding physical and optical properties of AuNPs can be exploited to obtain analytically useful signals upon analyte binding. In this account, we review recent advances in AuNP-based sensing systems emphasizing on the rational design of the ligand shell for detection of heavy metal ions and small molecules. We examine various strategies of detection by evaluating their improvements in terms of sensitivity, selectivity and applicability to real samples.

Evolution of the Ligand Shell Morphology during Ligand Exchange Reactions on Gold Nanoparticles.

Ligand exchange reactions are used to achieve nanoparticles coated with a mixture of ligand molecules. Currently, nothing is known on the evolution of the morphology of the ligand shell during the reaction. Here, we use a recently developed method (based on MALDI-TOF) to follow the evolution of the ligand shell composition and morphology during the reaction. We observe the expected evolution in composition and we find that the ligand shell starts as a random mixture and gradually evolves towards a patchy morphology. When the composition has reached a plateau (i.e. when the reaction is generally assumed to be finished), the ligand shell morphology keeps evolving for days, slowly approaching its equilibrium configuration.

Ligand concentration determines antiviral efficacy of silica multivalent nanoparticles.

We have learned from the recent COVID-19 pandemic that the emergence of a new virus can quickly become a global health burden and kill millions of lives. Antiviral drugs are essential in our fight against viral diseases, but most of them are virus-specific and are prone to viral mutations. We have developed broad-spectrum antivirals based on multivalent nanoparticles grafted with ligands that mimic the target of viral attachment ligands (VALs). We have shown that when the ligand has a sufficiently long hydrophobic tail, the inhibition mechanism switches from reversible (virustatic) to irreversible (virucidal). Here, we investigate further how ligand density and particle size affect antiviral efficacy, both in terms of half-inhibitory concentration (IC50) and of reversible vs irreversible mechanism. We designed antiviral silica nanoparticles modified with 11-mercaptoundecane-1-sulfonic acid (MUS), a ligand that mimics heparan sulfate proteoglycans (HSPG) and we showed that these nanoparticles can be synthesized with different sizes (4-200 nm) and ligand grafting densities (0.59-10.70 /nm2). By testing these particles against herpes simplex virus type 2 (HSV-2), we show that within the size and density ranges studied, the antiviral IC50 is determined solely by equivalent ligand concentration. The nanoparticles are found to be virucidal at all sizes and densities studied.

Quantitative analysis of scanning tunneling microscopy images of mixed-ligand-functionalized nanoparticles.

Ligand-protected gold nanoparticles exhibit large local curvatures, features rapidly varying over small scales, and chemical heterogeneity. Their imaging by scanning tunneling microscopy (STM) can, in principle, provide direct information on the architecture of their ligand shell, yet STM images require laborious analysis and are challenging to interpret. Here, we report a straightforward, robust, and rigorous method for the quantitative analysis of the multiscale features contained in STM images of samples consisting of functionalized Au nanoparticles deposited onto Au/mica. The method relies on the analysis of the topographical power spectral density (PSD) and allows us to extract the characteristic length scales of the features exhibited by nanoparticles in STM images. For the mixed-ligand-protected Au nanoparticles analyzed here, the characteristic length scale is 1.2 ± 0.1 nm, whereas for the homoligand Au NPs this scale is 0.75 ± 0.05 nm. These length scales represent spatial correlations independent of scanning parameters, and hence the features in the PSD can be ascribed to a fingerprint of the STM contrast of ligand-protected nanoparticles. PSD spectra from images recorded at different laboratories using different microscopes and operators can be overlapped across most of the frequency range, proving that the features in the STM images of nanoparticles can be compared and reproduced.

Bimodal atomic force microscopy for the characterization of thiolated self-assembled monolayers.

Surface coatings are becoming an integral part of materials. In recent years, molecular coatings have found larger acceptance and uses. Among them, self-assembled monolayers (SAMs) are attractive due to their inherent versatility, manufacturability, and scale up ease. Understanding their structure-properties relationships in realistic conditions remains a major challenge. Here we present a methodology based on simultaneous topographical and nanomechanical characterization of SAMs using a commercially available setup for bimodal atomic force microscopy (AFM). It allows for accurate and quantitative measurement of surface elasticity, which is correlated to molecular ordering through topographical imaging. Our results indicate that effective surface elasticity (E*) scales with monolayer formation-time and ligand-length, parameters known to affect ligand ordering. The method developed, is extended to provide localization of the chemical species present in thiolated binary SAMs. Within the systems tested phase separation down to ∼10 nm domains could be observed both in the topography and in the elasticity channel.

Response to "Critical Assessment of the Evidence for Striped Nanoparticles".

Stirling et al., (10.1371/journal.pone.0108482) presented an analysis on some of our publications on the formation of stripe-like domains on mixed-ligand coated gold nanoparticles. The authors shed doubts on some of our results however no valid argument is provided against what we have shown since our first publication: scanning tunneling microscopy (STM) images of striped nanoparticles show stripe-like domains that are independent of imaging parameters and in particular of imaging speed. We have consistently ruled out the presence of artifacts by comparing sets of images acquired at different tip speeds, finding invariance of the stipe-like domains. Stirling and co-workers incorrectly analyzed this key control, using a different microscope and imaging conditions that do not compare to ours. We show here data proving that our approach is rigorous. Furthermore, we never solely relied on image analysis to draw our conclusions; we have always used the chemical nature of the particles to assess the veracity of our images. Stirling et al. do not provide any justification for the spacing of the features that we find on nanoparticles: ~1 nm for mixed ligand particles and ~ 0.5 nm for homoligand particles. Hence our two central arguments remain unmodified: independence from imaging parameters and dependence on ligand shell chemical composition. The paper report observations on our STM images; none is a sufficient condition to prove that our images are artifacts. We thoroughly addressed issues related to STM artifacts throughout our microscopy work. Stirling et al. provide guidelines for what they consider good STM images of nanoparticles, such images are indeed present in our literature. They conclude that the evidences we provided to date are insufficient, this is a departure from one of the authors' previous article which concluded that our images were composed of artifacts. Given that four independent laboratories have reproduced our measurements and that no scientifically rigorous argument is presented to invalidate our STM images, and also given that Stirling et al. do not contest the quality of our recent STM images, we re-affirm that specific binary mixture of ligands spontaneously form features in their ligand shell that we describe as stripe-like domains ~1 nm in width.

Comparative STM studies of mixed ligand monolayers on gold nanoparticles in air and in 1-phenyloctane.

Scanning tunnelling microscopy (STM) studies have found stripe-like domains on gold nanoparticles (NPs) coated with certain binary mixtures of ligand molecules. The majority of these NPs' properties have been investigated for particles in solvents. Yet, most STM studies are for NPs in a dry state. Images of the same particles in air and liquid have not been obtained yet. In this work, a judicious choice of ligand molecules led to NPs with close-to-ideal STM imaging conditions in air and in 1-phenyloctane (PO). Large datasets under both conditions were acquired and rapidly evaluated through power spectral density (PSD) analysis. The result is a quantitative comparison of stripe-like domains in air and PO on the same NPs. PSD analysis determines a characteristic length-scale for these domains of ~1.0 nm in air and in PO showing persistence of striped domains in these two media. A length scale of ~0.7 nm for homoligand NPs was found.

High-resolution scanning tunneling microscopy characterization of mixed monolayer protected gold nanoparticles.

Gold nanoparticles protected by a binary mixture of thiolate molecules have a ligand shell that can spontaneously separate into nanoscale domains. Complex morphologies arise in such ligand shells, including striped, patchy, and Janus domains. Characterization of these morphologies remains a challenge. Scanning tunneling microscopy (STM) imaging has been one of the key approaches to determine these structures, yet the imaging of nanoparticles' surfaces faces difficulty stemming from steep surface curvature, complex molecular structures, and the possibility of imaging artifacts in the same size range. Images obtained to date have lacked molecular resolution, and only domains have been resolved. There is a clear need for images that resolve the molecular arrangement that leads to domain formation on the ligand shell of these particles. Herein we report an advance in the STM imaging of gold nanoparticles, revealing some of the molecules that constitute the domains in striped and Janus gold nanoparticles. We analyze the images to determine molecular arrangements on parts of the particles, highlight molecular "defects" present in the ligand shell, show persistence of the features across subsequent images, and observe the transition from quasi-molecular to domain resolution. The ability to resolve single molecules in the ligand shell of nanoparticles could lead to a more comprehensive understanding of the role of the ligand structure in determining the properties of mixed-monolayer-protected gold nanoparticles.

The Role of Frozen Spins in the Exchange Anisotropy of Core-Shell Fe@Fe(3)O(4) Nanoparticles.

Core-shell Fe@Fe(3)O(4) nanoparticles exhibit substantial exchange bias at low temperatures, mediated by unidirectionally aligned moments at the core-shell interface. These spins are frozen into magnetic alignment with field cooling, and are depinned in a temperature-dependent manner. The population of such frozen spins has a direct impact on both coercivity (H(C)) and the exchange-bias field (H(E)), which are modulated by external physical parameters such as the strength of the applied cooling field and the cycling history of magnetic field sweeps (training effect). Aging of the core-shell nanoparticles under ambient conditions results in a gradual decrease in magnetization but overall retention of H(C) and H(E), as well as a large increase in the population of frozen spins. These changes are accompanied by a structural evolution from well-defined core-shell structures to particles containing multiple voids, attributable to the Kirkendall effect. Energy-filtered and high-resolution transmission electron microscopy both indicate further oxidation of the shell layer, but the Fe core is remarkably well preserved. The increase in frozen spin population with age is responsible for the overall retention of exchange bias, despite void formation and other oxidation-dependent changes. The exchange-bias field becomes negligible upon deliberate oxidation of Fe@Fe(3)O(4) nanoparticles into yolk-shell particles, with a nearly complete physical separation of core and shell.