Optical Nanoimpacts of Dielectric and Metallic Nanoparticles on Gold Surface by Reflectance Microscopy: Adsorption or Bouncing?

International audienceOptical modeling coupled to experiments show that a microscope operating in reflection mode allows imaging, through solutions or even a microfluidic cover, various kinds of nanoparticles, NPs, over a (reflecting) sensing surface, here a gold (Au) surface. Optical modeling suggests that this configuration enables the interferometric imaging of single NPs which can be characterized individually from local change in the surface reflectivity. The interferometric detection improves the optical limit of detection compared to classical configurations exploiting only the light scattered by the NPs. The method is then tested experimentally, to monitor in situ and in real time, the collision of single Brownian NPs, or optical nanoimpacts, with an Au-sensing surface. First, mimicking a microfluidic biosensor platform, the capture of 300 nm FeOx maghemite NPs from a convective flow by a surface-functionalized Au surface is dynamically monitored. Then, the adsorption or bouncing of individual dielectric (100 nm polystyrene) or metallic (40 and 60 nm silver) NPs is observed directly through the solution. The influence of the electrolyte on the ability of NPs to repetitively bounce or irreversibly adsorb onto the Au surface is evidenced. Exploiting such visualization mode of single-NP optical nanoimpacts is insightful for comprehending single-NP electrochemical studies relying on NP collision on an electrode (electrochemical nanoimpacts)

Combining Electrodeposition and Optical Microscopy for Probing Size-Dependent Single-Nanoparticle Electrochemistry

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Effect of the driving force on nanoparticles growth and shape: an opto-electrochemical study

International audienceMost protocols developed to synthesize nanoparticles (NPs) and to control their shape are inspired from nucleation and growth theories. However, to rationalize the mechanisms of the shape-selective synthesis of NPs, experimental strategies allowing to probe in situ the growth of NPs are meant. Herein, metal Au or Ag nanoparticles (NPs) are produced by reaction of a metallic ion precursor with a reversible redox reducer. The process is explored by an oxidative electrosynthesis strategy using a sacrificial Au or Ag ultramicroelectrode to both trigger the metallic ion generation and control the local concentrations of the different reactants. The effect of the driving force for the metallic ions reduction over metal NP growth dynamics is inspected in situ and in real time at the single NP level by high-resolution optical microscopy from the tracking of the Brownian trajectories of the growing NPs in solution. The NPs reductive growth/oxidative etching thermodynamics, and consequently the NPs shape, are shown to be controlled electrochemically by the reversible redox couple, while the intervention of an Au(I) intermediate ion is suggested to account for the formation of gold nanocubes

The promise of antireflective gold electrodes for optically monitoring the electro-deposition of single silver nanoparticles

International audienceThe interest in nano-objects has recently dramatically increased in all fields of science, and electrochemistry is no exception. As a consequence, in situ and operando visualization of electrochemical processes is needed at the nanoscale. Herein, we propose a new interferometric microscopy based on an antireflective thin metal electrode layer. The technique is coupled to electrochemistry in a model example: the electro-deposition of Ag metallic nanoparticles (NPs). This challenges the current opto-electrochemical methods and even those relying on nano-impact detection. Indeed, the sensitivity allows the dynamic in situ visualization of the electrochemical growth and dissolution of individual Ag NPs, whose size was tracked dynamically down to 15 nm in diameter. The use of microelectrodes provides interesting quantitative analysis of the NPs, from optically resolved arrays of single NPs to condensed arrays of (unresolved) NPs. Particularly, the optical analysis of all the individual NPs allows the reconstruction of optical voltammograms similar to the electrochemical ones. Finally, the NP dissolution-redeposition is also investigated

In Situ Optical Monitoring of the Electrochemical Conversion of Dielectric Nanoparticles: From Multistep Charge Injection to Nanoparticle Motion

International audienceBy shortening solid-state diffusion times, the nanoscale size reduction of dielectric materials—such as ionic crystals—has fueled synthetic efforts toward their use as nanoparticles, NPs, in electrochemical storage and conversion cells. Meanwhile, there is a lack of strategies able to image the dynamics of such conversion, operando and at the single NP level. It is achieved here by optical microscopy for a model dielectric ionic nanocrystal, a silver halide NP. Rather than the classical core-shrinking mechanism often used to rationalize the complete electrochemical conversion and charge storage in NPs, an alternative mechanism is proposed here. Owing to its poor conductivity, the NP conversion proceeds to completion through the formation of multiple inclusions. The superlocalization of NP during such heterogeneous multiple-step conversion suggests the local release of ions, which propels the NP toward reacting sites enabling its full conversion

Unsupervised Analysis of Optical Imaging Data for the Discovery of Reactivity Patterns in Metal Alloy

Operando wide-field optical microscopy imaging yields a wealth of information about the reactivity of metal interfaces, yet the data are often unstructured and challenging to process. In this study, we harness the power of unsupervised machine learning (ML) algorithms to analyze chemical reactivity images obtained dynamically by reflectivity microscopy in combination with ex situ scanning electron microscopy to identify and cluster the chemical reactivity of particles in Al alloy. The ML analysis uncovers three distinct clusters of reactivity from unlabeled datasets. A detailed examination of representative reactivity patterns confirms the chemical communication of generated OH- fluxes within particles, as supported by statistical analysis of size distribution and finite element modelling (FEM). The ML procedures also reveal statistically significant patterns of reactivity under dynamic conditions, such as pH acidification. The results align well with a numerical model of chemical communication, underscoring the synergy between data-driven ML and physics-driven FEM approaches

Bispectral Index profile during carotid cross clamping

This study aimed at investigating the Bispectral Index (BIS) profile during carotid cross clamping (CXC). The study involved a pilot group of 10 patients undergoing routine carotid endarterectomy with shunt insertion under total intravenous anesthesia, and a study group of 26 additional patients. In all patients, rates of propofol and remifentanil providing a steady-state level of hypnosis (BIS: 40-60) were maintained constant throughout a recording period ranging from 3 minutes before CXC to shunt insertion. BIS was recorded throughout this period and the internal carotid backflow observed at the time of shunt insertion was graded as good, moderate, or poor. In addition, A-Line Autoregressive Index (AAI) and processed electroencephalogram (EEG) parameters were recorded in patients of the study group. All parameters were averaged over I minute before CXC, at CXC, 1, 2, and 3 minutes after CXC, and at shunt insertion. Statistical analysis was performed using X 2, Friedman, and Spearman correlation tests. For technical reasons, reliable AAI, BIS monitor-derived, and other processed EEG data were obtained in 24, 25, and 18 patients of the study group, respectively. During the first 3 minutes after CXC, BIS increased over 60 [68.8 (6.1)] in 47%, decreased below 40 [34.9 (4.4)] in 25%, and remained in the 40 to 60 range in 28% of all recruited patients. A BIS increase was more frequently observed in patients with moderate or poor than in those with good internal carotid backflow (78, 67, and 29%, respectively). It was significantly correlated to an increase in AAI and EEG amplitude, a decrease in EEG suppression ratio, and a shorter time between induction of anesthesia and CXC. A BIS decrease was significantly correlated to an increase in suppression ratio and a longer time between induction and CXC. In conclusion, during CXC under a constant level of intravenous anesthesia, BIS may increase, decrease, or remain unchanged. The paradoxical BIS increase could be related to borderline ischemia, a change in brain anesthetic agent concentration, or a change in the nociceptive-antinociceptive balance associated with a CXC-elicited painful stimulation. Caution should be used when interpreting BIS value during CXC