Titanium dioxide (TiO2) nanoparticles introduced into subsurface environments may lead to contamination of drinking water supplies and can act as colloidal carriers for sorbed contaminants. A model laboratory system was used to examine the influence of water chemistry on the physicochemical properties of TiO2 nanoparticles and their deposition. Deposition rates of TiO2 particles onto a silica surface were measured over a broad range of solution conditions (pH and ionic strength) using a quartz crystal microbalance with energy dissipation monitoring (QCM-D). Higher particle deposition rates were observed under favorable interaction conditions (i.e., in the presence of attractive electrostatic interactions) in comparison to unfavorable deposition conditions where electrostatic repulsion dominates particle-surface interactions. Nanoparticle sizes were characterized by fluorescence correlation spectroscopy (FCS), dynamic light scattering (DLS), and atomic force microscopy (AFM). These analyses confirmed the nanoscale of the system under study as well as the presence of TiO2 aggregates in some cases. TiO2 deposition behavior onto silica measured using QCM-D was generally found to be in qualitative agreement with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory of colloidal stability.

We show, in this paper that multivalent ferrocyanide anions can penetrate into exponentially growing (PGA/PAH)n multilayer films whatever the nature of the last deposited layer. These ions are not able to diffuse out of the film when it is brought in contact with a pure buffer solution. However, the contact of this film with a poly(allylamine) (PAH) or a poly(L-glutamic acid) (PGA) solution leads to the release of ferrocyanide ions from the multilayer. It is shown that the release of ferrocyanide anions, when the film is in contact with a PGA solution, is due to the diffusion of the PGA chains into the film so that an exchange between ferrocyanide ions and PGA chains takes place inside the film. On the other hand, PAH chains do not diffuse into PGA/PAH multilayers. When the film is then brought in contact with a PAH solution, the PAH chains from the solution are expected to strongly interact with the ferrocyanide ions and thus induce a diffusion mechanism of the multivalent anions out of the film, the film/solution interface playing the role of a sink for these ions. This work thus shows that interactions between multivalent ions and exponentially growing films are much more complex than expected at first sight and that polyelectrolyte multilayers must be seen as dynamic entities in which diffusion and exchange processes can take place.

Heart rate variability (HRV) corresponds to the adaptation of the heart to any stimulus. In fact, among the pathologies affecting HRV the most, there are the cardiovascular diseases and depressive disorders, which are associated with high medical cost in Western societies. Consequently, HRV is now widely used as an index of health.In order to better understand how this adaptation takes place, it is necessary to examine which factors directly influence HRV, whether they have a physiological or environmental origin. The primary objective of this research is therefore to conduct a literature review in order to get a comprehensive overview of the subject.The system of these factors affecting HRV can be divided into the following five categories: physiological and pathological factors, environmental factors, lifestyle factors, non-modifiable factors and effects. The direct interrelationships between these factors and HRV can be regrouped into an influence diagram. This diagram can therefore serve as a basis to improve daily clinical practice as well as help design even more precise research protocols.

Zero-valent iron nanoparticles (nZVI) used in the remediation of contaminated subsurface environments are commonly stabilized using polymer coatings. A bottom-up synthesis approach was used to synthesize carboxymethylcellulose (CMC)-coated nZVI particles with increased colloidal stability. The influence of water chemistry and selected environmental molecules, namely, fulvic acids and rhamnolipids, on the aggregate size and surface charge of the bare and CMC-coated nZVI particles was systematically examined using dynamic light scattering (DLS), nanoparticle tracking analysis (NTA), and laser Doppler velocimetry. A quartz crystal microbalance with energy dissipation monitoring (QCM-D) was used to quantify the deposition rates of bare and CMC-coated nZVI particles onto a silica surface over a broad range of solution ionic strengths and in the presence of naturally occurring molecules. Nanoscale ZVI particle deposition was found to increase with IS for many of the conditions investigated. CMC acted as a better colloidal stabilizer when covalently bound to nZVI particles than when physisorbed onto the nanoparticle surface after particle synthesis. The lowest nanoparticle deposition rates were observed for CMC-coated nZVI in the presence of the rhamnolipid biosurfactant.

Quartz crystal microbalance with dissipation monitoring (QCM-D) is used for real-time in situ detection of cytoskeletal changes in live primary endothelial cells in response to different cytomorphic agents; namely, the surfactant Triton-X 100 (TX-100) and bacterial lipopolysaccharide (LPS). Reproducible dissipation versus frequency (Df) plots provide unique signatures of the interactions between endothelial cells and cytomorphic agents. While the QCM-D response for TX-100 can be described in two steps (changes in the osmotic pressure of the medium prior to observing the expected cell lysis), LPS results in a different single-phase signal. A complementary analysis is carried out to evaluate the possible competitive effects of TX-100 and LPS through the QCM-D response to BAEC stress by analyzing the Df plots obtained. Experiments with non-toxic components (fibronectin or serum) produce a different QCM-D response than that observed for the toxic chemicals, suggesting the use of Df plot signatures for the possible differentiation between cytotoxic or non-cytotoxic effects. Observations obtained by QCM-D signals are confirmed by conducting fluorescence microscopy at the same time. Our results show that a fast (few minutes) sensing response can be obtained in situ and in real-time. The conclusions from this study suggest that QCM-D can potentially be used in biodetection for applications in drug screening tests and diagnosis.

We have investigated the structure of (3-mercaptopropyl)sulfonate (MPS) monolayer self-assembled onto gold surfaces by quartz crystal microbalance with energy dissipation monitoring (QCM-D) and various electrochemical methods. QCM-D experiments show that the MPS monolayer behaves as a thin rigid film with a surfacic mass of 166 ng cm(-2). Interfacial capacitance measurements demonstrate that the MPS monolayer is a rather open structure that can be penetrated by the ionic species of the phosphate buffer electrolyte. From MPS reductive desorption experiments, MPS surface concentration corresponds to 4.6 x 10(-10) mol cm(-2), which represents 60% of the coverage reported for a densely packed thiol monolayer. Despite this low packing density, oxidation of catechol is strongly inhibited leading to voltammograms that are free ofdiffusional contribution. This unique behavior has been exploited to show that the MPS monolayer covers the entire gold surface with a surface coverage at least equal to theta = 0.9981, which means a very low number of MPS-free pinholes and/or defects. Kinetics of electron transfer toward soluble redox species has been studied using catechol as a neutral hydrophilic probe, but also ferrocyanide as hydrophilic anion and ferrocenemethanol as neutral hydrophobic molecule. It is proposed that the MPS monolayer provides a high kinetic barrier toward permeation of these species and that electron transfer mainly occurs by electron tunneling through the MPS monolayer.

Construction and characterization of structural and charge transport properties of electrostatically LbL self-assembled multilayers of gold nanoparticles and a viologen-based redox-active polyelectrolyte is reported.

The use of engineered nanoparticles (ENPs) in commercial products has increased substantially over the last few years. Some research has been conducted in order to determine whether or not such materials are cytotoxic, but questions remain regarding the role that physiological media and sera constituents play in ENP aggregation or stabilization. In this study, several characterization methods were used to evaluate the particle size and surface potential of 6 ENPs suspended in a number of culture media and in the presence of different culture media constituents. Dynamic light scattering (DLS) and fluorescence correlation spectroscopy (FCS) were employed for size determinations. Results were interpreted on the basis of ENP surface potentials evaluated from particle electrophoretic mobilities (EPM). Measurements made after 24h of incubation at 37°C showed that the cell culture medium constituents had only moderate impact on the physicochemical properties of the ENP, although incubation in bovine serum albumin destabilized the colloidal system. In contrast, most of the serum proteins increased colloidal stabilization. Moreover, the type of ENP surface modification played a significant role in ENP behavior whereby the complexity of interactions between the ENPs and the medium components generally decreased with increasing complexity of the particle surface. This investigation emphasizes the importance of ENP characterization under conditions that are representative of cell culture media or physiological conditions for improved assessments of nanoparticle cytotoxicity.