The dielectric and conductometric properties of aqueous polyelectrolyte solutions present a very complex phenomenology, not yet completely understood, differing from the properties of both neutral macromolecular solutions and of simple electrolytes. Three relaxations are evident in dielectric spectroscopy of aqueous polyelectrolyte solutions. Near 17 GHz, water molecules relax and hence this highest frequency relaxation gives information on the state of water in the solution. At lower frequencies in the MHz range, free counterions respond to the applied field and polarize on the scale of the correlation length. This intermediate frequency relaxation thus provides information about the effective charge on the polyelectrolyte chains, and the fraction of condensed counterions. However, the presence of polar side chains adds a further polarization mechanism that also contributes in this intermediate frequency range. At still lower frequencies, the condensed counterions polarize in a non-uniform way along the polyelectrolyte chain backbone and dielectric spectroscopy in the kHz range may determine the effective friction coefficient of condensed counterions. In this review, we analyse in detail the dielectric and conductometric behaviour of aqueous polyelectrolyte solutions in the light of recent scaling theories for polyelectrolyte conformation and summarize the state-of-the-art in this field.
The dielectric properties of lysozyme aqueous solutions have been investigated over a wide frequency range, from 1 MHz to 50 GHz, where different polarization mechanisms, at a molecular level, manifest. The dielectric relaxation spectra show a multimodal structure, reflecting the complexity of the protein-water interactions, made even more intricate with the increase of the protein concentration. The deconvolution of the spectra into their different components is not unambiguous and is generally a delicate process which requires caution. We have analyzed the whole relaxation region, on the basis of the sum of simple Debye-type relaxation functions, considering three main contributions. Particular attention has been payed to the δ-dispersion, intermediate between the β-dispersion (rotational dynamics of the protein) and the γ-dispersion (orientational polarization of the water molecules). This intermediate contribution to the dielectric spectrum is attributed to the orientational polarization of water molecules in the immediate vicinity of the protein surface (hydration water). Our measurements clearly demonstrate that, at least at high protein concentrations, the δ-dispersion has a bimodal structure associated with two kinds of hydration water, i.e., tightly bound and loosely bound hydration water. In the concentration range investigated, the existence of a three-modal δ-dispersion, as recently suggested, is not supported, on the basis of statistical tests, by the analysis of the dielectric relaxations we have performed and a bimodal dispersion is accurate enough to describe the experimental data. The amount of the hydration water has been evaluated both from the dielectric parameters associated with the δ-dispersion and from the decrement of the loss peak of the γ-dispersion. The relative weight of tightly bound and loosely bound hydration water is briefly discussed.
With the growing interest in the applications of gold nanoparticles in biotechnology and their physiological effects, possible toxicity of gold nanoparticles is becoming an increasingly important issue. A large number of studies carried out over the past few years under a variety of experimental conditions and following different protocols have produced conflicting results, leading to divergent views about the actual safety of gold nanoparticles in human applications.This work is intended to provide an overview of the most recent experimental results and thereby summarize current state-of-the-art. Rather than presenting a comprehensive review of the available literature in this field, which would be impractically broad, we have selected representative examples of both in vivo and in vitro studies, which clearly demonstrate the need for urgent and rigorous standardization of experimental protocols. Despite their significant potential, the safety of gold nanoparticles is highly controversial at this time, and important concerns have been raised that need to be properly addressed. Factors such as shape, size, surface charge, coating, and surface functionalization are expected to influence the interactions of particles with biological systems to a different extent, resulting in different outcomes and influencing the potential of gold nanoparticles for biomedical applications.Moreover, despite continuous attempts to establish a correlation between structure of the particles and their interactions with biological systems, we are still far from elucidating the toxicological profile of gold nanoparticles in an indisputable manner. This review is intended to contribute towards this goal, offering a number of suggestions on how to achieve the systematization of data on the most relevant physico-chemical parameters, which govern and control the toxicity of gold nanoparticles at cellular and whole-organism levels.
This review focuses on some recent advances made in the field of gas sensors based on polyaniline [PANI], a conducting polymer with excellent electronic conductivity and electrochemical properties. Conducting polymers represent an important class of organic materials with an enhanced resistivity towards external stimuli. Among them, PANI polymers have attracted wide interest because of the versatility in their use, combined with the easy of synthesis, high yield and good environmental stability, together with a favorable response to guest molecules at room temperature. Moreover, PANI can be shaped into various structures with different morphologies and the possibility of obtaining nanofibers, in addition to thin films, has opened a rapid development of ultrasensitive chemical sensors, with improved processability and functionality. This review provides a brief description of the current status of gas chemiresistive sensors based on polyaniline and highlights the properties and applications of these devices in diverse range of application
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