Does Electrical Conductivity of Linear Polyelectrolytes in Aqueous Solutions Follow the Dynamic Scaling Laws? A Critical Review and a Summary of the Key Relations

In this review, we focus on the electrical conductivity of aqueous polyelectrolyte solutions in the light of the dynamic scaling laws, recently proposed by Dobrynin and Rubinstein, to take into account the polymer conformations in different concentration regimes, both in good and poor solvent conditions. This approach allows us to separate contributions due to polymer conformation from those due to the ionic character of the chain, and offers the possibility to extend the validity of the Manning conductivity model to dilute and semidilute regimes. The electrical conductivity in the light of the scaling approach compares reasonably well with the observed values for different polyelectrolytes in aqueous solutions, over an extended concentration range, from the dilute to the semidilute regime

How toxic are gold nanoparticles? The state-of-the-art.

With the growing interest in biotechnological applications of gold nanoparticles and their effects exerted on the body, the possible toxicity is becoming an increasingly important issue. Numerous investigations carried out, in the last few years, under different experimental conditions, following different protocols, have produced in part conflicting results which have leaded to different views about the effective gold nanoparticle safety in human applications. This work is intended to provide an overview on the most recent experimental results in order to summarize the current state-of-the-art. However, rather than to present a comprehensive review of the available literature in this field, that, among other things, is really huge, we have selected some representative examples of both in vivo and in vitro investigations, with the aim of offering a scenario from which clearly emerges the need of an urgent and impelling standardization of the experimental protocols. To date, despite the great potential, the safety of gold nanoparticles is highly controversial and important concerns have been raised with the need to be properly addressed. Factors such as shape, size, surface charge, surface coating and surface functionalization are expected to influence interactions with biological systems at different extents, with different outcomes, as far as gold nanoparticle potentiality in biomedical applications is concerned. Moreover, despite the continuous attempt to establish a correlation between structure and interactions with biological systems, we are still far from assessing the toxicological profile of gold nanoparticles in an unquestionable manner. This review is intended to provide a contribution in this direction, offering some suggestions in order to reach the systematization of data over the most relevant physico-chemical parameters, which govern and control toxicity, at different cellular and organismal levels

Chemiresistive polyaniline-based gas sensors: a mini review

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 applications. © 2015 Elsevier B.V. All rights reserved

influence of localized surface charge distributions on the dielectric relaxation spectra of spherical colloidal particles in aqueous solution

The influence of localized charge distributions at the interfaces of spherical colloidal particles in aqueous suspension is discussed in the light of the effective medium approximation theory of heterogeneous systems. The approach is shown to give analytical results in the case of shelled particles with the presence of two distinct interfaces. The whole dielectric response of the system gives rise to different relaxation contributions, falling in different frequency regions and attributed to different polarization mechanisms, at a molecular level. In particular, the number and the strength of the dielectric relaxations associated with the presence of localized charges is discussed

Core shell hybrids based on noble metal nanoparticles and conjugated polymers: synthesis and characterization

Noble metal nanoparticles of different sizes and shapes combined with conjugated functional polymers give rise to advanced core shell hybrids with interesting physical characteristics and potential applications in sensors or cancer therapy. In this paper, a versatile and facile synthesis of core shell systems based on noble metal nanoparticles (AuNPs, AgNPs, PtNPs), coated by copolymers belonging to the class of substituted polyacetylenes has been developed. The polymeric shells containing functionalities such as phenyl, ammonium, or thiol pending groups have been chosen in order to tune hydrophilic and hydrophobic properties and solubility of the target core shell hybrids. The Au, Ag, or Pt nanoparticles coated by poly(dimethylpropargylamonium chloride), or poly(phenylacetylene-co-allylmercaptan). The chemical structure of polymeric shell, size and size distribution and optical properties of hybrids have been assessed. The mean diameter of the metal core has been measured (about 10-30 nm) with polymeric shell of about 2 nm

Transient anomalous diffusion MRI measurement discriminates porous polymeric matrices characterized by different sub-microstructures and fractal dimension

Considering the current development of new nanostructured and complex materials and gels, it is critical to develop a sub-micro-scale sensitivity tool to quantify experimentally new parameters describing sub-microstructured porous systems. Diffusion NMR, based on the measurement of endogenous water’s diffusion displacement, offers unique information on the structural features of materials and tissues. In this paper, we applied anomalous diffusion NMR protocols to quantify the subdiffusion of water and to measure, in an alternative, non-destructive and non-invasive modality, the fractal dimension dw of systems characterized by micro and sub-micro geometrical structures. To this end, three highly heterogeneous porous-polymeric matrices were studied. All the three matrices composed of glycidylmethacrylate-divynilbenzene porous monoliths obtained through the High Internal Phase Emulsion technique were characterized by pores of approximately spherical symmetry, with diameters in the range of 2–10 μm. Pores were interconnected by a plurality of window holes present on pore walls, which were characterized by size coverings in the range of 0.5–2 μm. The walls were characterized by a different degree of surface roughness. Moreover, complementary techniques, namely Field Emission Scanning Electron Microscopy (FE-SEM) and dielectric spectroscopy, were used to corroborate the NMR results. The experimental results showed that the anomalous diffusion α parameter that quantifies subdiffusion and dw = 2/α changed in parallel to the specific surface area S (or the surface roughness) of the porous matrices, showing a submicroscopic sensitivity. The results reported here suggest that the anomalous diffusion NMR method tested may be a valid experimental tool to corroborate theoretical and simulation results developed and performed for describing highly heterogeneous and complex systems. On the other hand, non-invasive and non-destructive anomalous subdiffusion NMR may be a useful tool to study the characteristic features of new highly heterogeneous nanostructured and complex functional materials and gels useful in cultural heritage applications, as well as scaffolds useful in tissue engineering

Polyion-induced aggregation of oppositely charged liposomes and charged colloidal particles: The many facets of complex formation in low-density colloidal systems

This review focusses on recent developments in the experimental study of polyion-induced charged colloidal particle aggregation, with particular emphasis on the formation of cationic liposome clusters induced by the addition of anionic adsorbing polyions. These structures can be considered, under certain points of view, a new class of colloidal systems, with intriguing properties that opens interesting and promising new opportunities in various biotechnological applications. Lipidic structures of different morphologies and different structural complexities interacting with oppositely charged polyions give rise to a rich variety of self-assembled structures that present various orders of hierarchy in the sense that, starting from a basic level, for example a lipid bilayer, they arrange themselves into superstructures as, for example, multilamellar stacks or liquid-crystalline structures. These structures can be roughly divided into two classes according to the fact that the elementary structure, involved in building a more complex one, keeps or does not keeps its basic arrangement. To the first one, belong those aggregates composed by single structures that maintain their integrity, for example, lipidic vesicles assembled together by an appropriate external agent. The second one encompasses structures that do not resemble the ones of the original objects which form them, but, conversely, derive from a deep restructuring and rearrangement process, where the original morphology of the initial constitutive elements is completely lost. In this review, I will only briefly touch on higher level hierarchy structures and I will focus on the assembling processes involving preformed lipid bilayer vesicles that organize themselves into clusters, the process being induced by the adsorption of oppositely charged polyions. The scientific interest in polyion-induced liposome aggregates is two-fold. On the one hand, in soft-matter physics, they represent an interesting colloidal system, governed by a balance between long-range electrostatic repulsion and short-range attraction, resulting in relatively large, equilibrium clusters, whose size and overall charge can be continuously tunable by simple environmental parameters. These structures present a variety of behaviors with a not yet completely understood phenomenology. On the other hand, the resulting structures possess some peculiar properties that justify their employment as drug delivery systems. Bio-compatibility, stability and ability to deliver various bio-active molecules and, moreover, their environmental responsiveness make liposome-based clusters a versatile carrier, with possibility of efficient targeting to different organs and tissues. Among the different structures made possible by the aggregating mechanism (cationic particles stuck together by anionic polyions or conversely anionic particles stuck together by cationic polyions), I will review the main experimental evidences for the existence of cationic liposome clusters. Especial attention is paid to our own work, mainly aimed at the characterization of these novel structures from a physical point of view. © 2008 Elsevier Ireland Ltd. All rights reserved

Dielectric and conductometric properties of highly heterogeneous colloidal systems

This review focuses on the behavior of highly heterogeneous colloidal systems under the influence of an external, frequency-dependent, electric field. Heterogeneous systems, which lie between bulk and molecularly dispersed systems, consist, in a simple meaning of the word, of a, dispersed phase distributed uniformly in a Finely divided state in a dispersion medium and represent a class of materials characterized by an extremely large surface-to-volume ratio. In these systems, the nanoscopic or mesoscopic size of the components leads to a situation Where their original properties can be only partially important; or may be even completely lost, and, on the contrary, where the effects associated to the interface dominate. Moreover, at least in the most relevant. systems both from a theoretical and practical point of view, the interfaces are often charged. This makes dielectric spectroscopy methods, which probe the charge distribution in the different regions of the system, particularly suitable to investigate the electrical properties of this class of materials. We shall limit ourselves to a discussion of relatively simple heterogeneous systems, such as polymeric colloidal particles dispersed in an electrolyte solution, biological cell suspensions and, finally, microemulsions. Each of these systems represents a family of colloids used as an example to outline some of their most important characteristics and to evidentiate a number of phenomena that are directly linked to the presence of a huge surfaces. For each of the above-stated systems, we will review the complex phenomenology they present, giving particular emphasis to the effects totally or partially induced by the presence of a large interface

Dielectric properties of soft-particles in aqueous solutions

In this review, we present a summary of the recent theoretical approaches developed in the last few years examining the dielectric and conductometric properties of soft colloidal particles in aqueous solution. Whereas the electrokinetic properties, concerning the movement of soft particles (electrophoretic mobility), have been extensively investigated and rather sophisticated theoretical models have been developed, much less attention has been addressed to the electrical polarization mechanisms induced in these systems by an external electric field, even though the rich phenomenology they present and the chances they offer in the study of their structure and functionality deserve much more interest. We analyze the recent progress achieved in the dielectric and conductometric properties of this kind of colloidal particle aqueous suspensions in the light of the electrokinetic standard model and we discuss in some detail how the structure of the polymer layer might alter the dielectric response of the system, seen as a highly heterogeneous colloidal system. In particular, the limits and the benefits of the soft particle electrokinetic formalism in the understanding the electrostatic features of these systems will be illustrated