A structural comparison of halloysite nanotubes of different origin by Small-Angle Neutron Scattering (SANS) and Electric Birefringence
The structure of halloysite nanotubes (Hal) from different mines was investigated by Small-Angle Neutron Scattering (SANS) and Electric Birefringence (EBR) experiments. The analysis of the SANS curves allowed us to correlate the sizes and polydispersity and the specific surfaces (obtained by a Porod analysis of the SANS data) of the nanotubes with their specific geological setting. Contrast matching measurements were performed on patch Hal (from Western Australia) in order to determine their experimental scattering length density for a more precise analysis. Further characterization of the mesoscopic structure of Hal was carried out by Electric Birefringence (EBR), which allowed to study th…
PyDSC: a simple tool to treat differential scanning calorimetry data
AbstractHerein, we describe an open-source, Python-based, script to treat the output of differential scanning calorimetry (DSC) experiments, called pyDSC, available free of charge for download at https://github.com/leonardo-chiappisi/pyDSC under a GNU General Public License v3.0. The main aim of this program is to provide the community with a simple program to analyze raw DSC data. Key features include the correction from spurious signals, and, most importantly, the baseline is computed with a robust, physically consistent approach. We also show that the baseline correction routine implemented in the script is significantly more reproducible than different standard ones proposed by propriet…
Effect of the supramolecular interactions on the nanostructure of halloysite/biopolymer hybrids: A comprehensive study by SANS, fluorescence correlation spectroscopy and electric birefringence
The structural properties of halloysite/biopolymer aqueous mixtures were firstly investigated by means of combining different techniques, including small-angle neutron scattering (SANS), electric birefringence (EBR) and fluorescence correlation spectroscopy (FCS). Among the biopolymers, non-ionic hydroxypropylcellulose and polyelectrolytes (anionic alginate and cationic chitosan) were selected. On this basis, the specific supramolecular interactions were correlated to the structural behavior of the halloysite/biopolymer mixtures. SANS data were analyzed in order to investigate the influence of the biopolymer adsorption on the halloysite gyration radius. In addition, a morphological descript…
On the effect of the nature of counterions on the self-assembly of polyoxyethylene alkyl ether carboxylic acids
In this contribution, we investigate the effect of the type of counterion on the properties of dilute solutions of polyoxyethylene alkyl ether carboxylic acids. Two different surfactants, presenting an oleic acid alkyl chain and on-average five and nine ethylene oxide units, and terminated by a weakly anionic carboxymethyl group were studied. The surfactants were gradually ionized with sodium hydroxide, arginine, and choline hydroxide. The solutions properties were probed by light scattering, electrophoretic mobility, density and sound velocity measurements, as well as by small-angle neutron scattering. To our initial surprise, no specific effect arising from the nature of the counterion co…
Quantitative description of temperature induced self-aggregation thermograms determined by differential scanning calorimetry
A novel thermodynamic approach for the description of differential scanning calorimetry (DSC) experiments on self-aggregating systems is derived and presented. The method is based on a mass action model where temperature dependence of aggregation numbers is considered. The validity of the model was confirmed by describing the aggregation behavior of poly(ethylene oxide)-poly(propylene oxide) block copolymers, which are well-known to exhibit a strong temperature dependence. The quantitative description of the thermograms could be performed without any discrepancy between calorimetric and van 't Hoff enthalpies, and moreover, the aggregation numbers obtained from the best fit of the DSC exper…
Effect of Polymer Length on the Adsorption onto Aluminogermanate Imogolite Nanotubes
This study evidences the adsorption of model nonionic polymers onto aluminogermanate imogolite nanotubes, attractive porous nanofillers with potential molecular loading and release applications. We resolve the underlying mechanisms between nanotubes and polyethylene glycols with different molecular weights by means of nanoisothermal titration calorimetry. The analysis of the results provides a direct thermodynamic characterization, allowing us to propose a detailed description of the energetics involved in the formation of polymer/imogolite complexes. The affinity toward the nanotube surface is enthalpy-driven and strongly depends on the polymer chain length, which significantly affects the…
Cyclodextrin/surfactant inclusion complexes: An integrated view of their thermodynamic and structural properties
Cyclodextrins (CDs) play an important role in self-assembly systems of amphiphiles. The structure of CDs provides distinguished physicochemical properties, including the ability to form host-guest complexes. The complexation affects the properties of guest molecules and can produce supramolecular aggregates with desirable characteristics for fundamental and practical applications. Surfactants are particularly attractive host molecules due to their wide variety, availability, responsiveness to different stimuli, and high relevance in different fields, e.g. medical, cosmetic, pharmaceutical, and food industries. The tendency of organization in higher-order supramolecular aggregates arises the…
Chitosan-based smart hybrid materials: a physico-chemical perspective.
Chitosan is one of the most studied cationic polysaccharides. Due to its unique characteristics of being water soluble, biocompatible, biodegradable, and non-toxic, this macromolecule is highly attractive for a broad range of applications. In addition, its complex behavior and the number of ways it interacts with different components in a system result in an astonishing variety of chitosan-based materials. Herein, we present recent advances in the field of chitosan-based materials from a physico-chemical perspective, with focus on aqueous mixtures with oppositely charged colloids, chitosan-based thin films, and nanocomposite systems. In this review, we focus our attention on the physico-che…