Heavy Metals Content and Health Risk Assessment in Airborne Particulate from the Calabria Region, Southern Italy.

This study is focused on the determination of the heavy metals content in airborne particulate matter (PM) with a diameter lower than 10 µm (PM10) deposited on quartz microfiber filters and collected in four representative selected sites of the Calabria region, southern Italy. In particular, data on the content of Cd, Ni, and Pb in PM10 (i.e., those metals whose limit values, in terms of concentration, are reported in the Italian Legislation) were obtained through inductively coupled plasma mass spectrometry (ICP-MS) measurements after acid extraction with microwaves and filtration. Results showed that the average concentration of investigated metals decreases as Ni > Pb > Cd for all analyzed samples, and concentration values are lower than the limit values reported in the Italian legislation in all cases. Moreover, in order to assess the health risk related to their presence in the environment, the potential non-carcinogenic hazard for the investigated heavy metals was evaluated by calculating the hazard index (HI) for children and adults. Results indicated that the calculated HI values were lower than the safety limit in all cases, thus indicating a negligible non-carcinogenic health risk. In addition, the potential carcinogenic hazard for the investigated metals was estimated through the total cancer risk index (Risktotal). Obtained results were also lower than the limit value for children and adults in this case, and, therefore, the carcinogenic health risk caused by heavy metals in the analyzed PM10 samples could be considered to be unremarkable.

Natural Radioactivity in Raw Building Materials for Underground Parking Lots and Assessment of Radiological Health Risk for the Population.

This article reports the results of an investigation into the activity concentration of natural radionuclides in raw building materials for underground parking lots, together with the assessment of the radiation hazard for the public related to exposure to ionizing radiations. To this purpose, high-purity germanium (HPGe) γ-ray spectrometry was employed in order to quantify the average specific activity of 226Ra, 232Th, and 40K natural radioisotopes. With the aim to assess any possible radiological health risk for the population, the absorbed γ-dose rate (D), the annual effective dose equivalent outdoor (AEDEout) and indoor (AEDEin), the activity concentration index (I), and the alpha index (Iα) were also estimated, resulting in values that were lower than the maximum recommended ones for humans. Finally, the extent of the correlations existing between the observed radioactivity and radiological parameters and of these parameters with the analyzed samples was quantified through statistical analyses, including Pearson's correlation, a principal component analysis (PCA), and a hierarchical cluster analysis (HCA). As a result, three clusters of the investigated samples were recognized based on their chemical composition and mineralogical nature. Noteworthily, this paper covers a certain gap in science since its topic does not appear in literature in this form. Thus, the authors underline the importance of this work to global knowledge in the environmental research and public health fields.

Multivariate Statistics, Mineralogy, and Radiological Hazards Assessment Due to the Natural Radioactivity Content in Pyroclastic Products from Mt. Etna, Sicily, Southern Italy.

In this article, an investigation of the natural radioactivity content of pyroclastic products from Mt. Etna, eastern Sicily, Southern Italy, was carried out. In particular, the assessment of the average activity concentration of the investigated radionuclides, related to the mineralogical phase composition of the analyzed samples, and the radiological health risk for the population, was performed. High Purity Germanium (HPGe) gamma-ray spectrometry was employed in order to quantify the average specific activity of 226Ra, 232Th, and 40K natural radioisotopes. The absorbed gamma dose rate (D), the radium equivalent activity (Raeq), the hazard indices (Hin and Hex), the annual effective dose equivalent outdoor (AEDEout), and the excess lifetime cancer risk (ELCR) were also estimated in order to assess any possible radiological hazard for the population. In our case, they were found to be lower than the maximum recommended values for the population members, thus reasonably excluding radiological hazard effects. Moreover, the identification of the source of the aforementioned naturally occurring radionuclides was attempted by X-ray Diffraction (XRD) and Micro-Raman Scattering (MRS), thereby recognizing the main radioisotope-bearing minerals present in the investigated pyroclastic products. Finally, Pearson correlation, Principal Component Analysis (PCA), and Hierarchical Cluster Analysis (HCA) were performed by processing observed radioactivity and radiological parameters in order to determine their correlation with the sampling locations.

Assessment of the Radiological Health Risk Due to the 226Ra Content in Drinking Water from the Calabria Region, Southern Italy.

In this article, the authors report experimental results obtained for the assessment of the 226Ra content in 80 drinking water samples from the Calabria region, Southern Italy. The activity concentration, measured with the Perkin Elmer Tricarb 4910 TR Liquid Scintillation Counter (LSC) setup, was compared with the reference values reported in the Italian Legislative Decree 28/2016 in order to evaluate any possible radiological health hazards for the population in terms of 226Ra content due to the ingestion of the investigated drinking water. The obtained results put in evidence that the average 226Ra specific activity is lower than the LSC minimum detectable activity (MDA) in all cases, thus, excluding any radiological risk. They also represent the main reference for the investigated area and can be used as a baseline to extend this investigation to the whole region.

Chitosan-Hyaluronan Nanoparticles for Vinblastine Sulfate Delivery: Characterization and Internalization Studies on K-562 Cells.

In the present study, we developed chitosan/hyaluronan nanoparticles (CS/HY NPs) for tumor targeting with vinblastine sulfate (VBL), that can be directed to the CD44 transmembrane receptor, over-expressed in cancer cells. NPs were prepared by coating with HY-preformed chitosan/tripolyphosphate (CS/TPP) NPs, or by polyelectrolyte complexation of CS with HY. NPs with a mean hydrodynamic radius (RH) of 110 nm, 12% polydispersity index and negative zeta potential values were obtained by a direct complexation process. Transmission Electron Microscopy (TEM) images showed spherical NPs with a non-homogeneous matrix, probably due to a random localization of CS and HY interacting chains. The intermolecular interactions occurring between CS and HY upon NPs formation were experimentally evidenced by micro-Raman (µ-Raman) spectroscopy, through the analysis of the spectral changes of characteristic vibrational bands of HY during NP formation, in order to reveal the involvement of specific chemical groups in the process. Optimized NP formulation efficiently encapsulated VBL, producing a drug sustained release for 20 h. In vitro studies demonstrated a fast internalization of labeled CS/HY NPs (within 6 h) on K-562 human myeloid leukemia cells. Pre-saturation of CD44 by free HY produced a slowing-down of NP uptake over 24 h, demonstrating the need of CD44 for the internalization of HY-based NPs.

Multi-Technique Diagnostic Analysis of Plasters and Mortars from the Church of the Annunciation (Tortorici, Sicily).

Plasters and mortars of the Church of the Annunciation (Tortorici, Sicily) were characterized, for the first time, both at the elemental and molecular levels, by means of portable X-ray fluorescence (XRF) and Raman spectroscopy, to achieve information on the "state of health" of the whole structure. The understanding of their degradation mechanisms and the identification of consequent degradation patterns can define the environmental factors responsible for interpreting the potential pathological forms that can impact the general building vulnerability. In this sense, the results obtained in this article provide relevant information to identify and address both the characterization of building materials and the fundamental causes of their deterioration. At the same time, if coupled with the attempt to supply a chronological order of the major restoration interventions carried out on the investigated site, they provide new insights to calibrate the models for building vulnerability studies.

Multitechnique diagnostic analysis and 3D surveying prior to the restoration of St. Michael defeating Evil painting by Mattia Preti.

In this study, a multimethodological analysis involving optical and physical/chemical diagnostic techniques and 3D photogrammetric survey was successfully applied, for the first time, on the large oil on canvas St. Michael defeating Evil painting by Mattia Preti, located inside the Church of the Immaculate Conception of Sarria (Floriana) in Malta. Pigmenting agents, binder media, and raw materials were first characterized, both at elemental and molecular scales, through X-ray fluorescence spectroscopy (XRF), optical stereo microscopy (SM), scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX), Fourier transform infrared spectroscopy (FT-IR), and gas chromatography coupled with mass spectrometry (GC-MS). The main goal was to properly identify the execution technique of this famous painter, the artist's palette, and possible nondocumented interventions. The 3D photogrammetric survey, on the other side, allowed us to noninvasively evaluate the extension of the areas that experienced restorations, and to properly map the domains of the different canvasses observed. The joints between canvasses suggested that the painting was folded and rolled up. In addition, the employment of a thermal camera gave evidence of the different consolidating material injection points used during the restoration to strengthen the painting. The obtained results offer useful information for the development of optimized restoration and conservation strategies to be applied and provide, at the same time, answers to open questions related to provenance and dating of the investigated artwork.

Radioactivity, Metals Pollution and Mineralogy Assessment of a Beach Stretch from the Ionian Coast of Calabria (Southern Italy).

In the present article, a case study is reported regarding an investigation carried out in order to assess radioactivity concentration, heavy metals pollution and mineralogy of a beach stretch extending from Soverato to Squillace municipalities of the Ionian coast of Calabria, South of Italy, a popular tourist destination, especially in summer. The analysis of radionuclides contents was performed by using a High Purity Germanium (HPGe) gamma-ray detector, in order to quantify the average specific activity of 226Ra, 232Th and 40K natural radionuclides and 137Cs anthropogenic radioisotope. The absorbed dose rate and the annual effective dose equivalent radiological hazard indices were also estimated. Furthermore, X-ray Fluorescence (XRF) spectrometry measurements were carried out for the quantitative elemental analysis of the sand, in order to investigate any possible chemical pollution by heavy metals. For this aim, different indices such as Enrichment Factor (EF), Geoaccumulation Index (Igeo), Contamination Factor (CF) and Pollution Load Index (PLI) were applied to estimate the level of toxicity imposed on the ecosystem by the detected heavy metals. Finally, in order to identify the crystalline mineral components of the investigated sand samples, X-ray Diffraction (XRD) and Micro-Raman Scattering (MRS) measurements were carried out.

Temperature-Dependent Dynamical Evolution in Coum/SBE-ß-CD Inclusion Complexes Revealed by Two-Dimensional FTIR Correlation Spectroscopy (2D-COS).

A combination of Fourier transform infrared spectroscopy in attenuated total reflectance geometry (FTIR-ATR) and 2D correlation analysis (2D-COS) was applied here for the first time in order to investigate the temperature-dependent dynamical evolution occurring in a particular type of inclusion complex, based on sulfobutylether-ß-cyclodextrin (SBE-ß-CD) as hosting agent and Coumestrol (7,12-dihydorxcoumestane, Coum), a poorly-soluble active compound known for its anti-viral and anti-oxidant activity. For this purpose, synchronous and asynchronous 2D spectra were calculated in three different wavenumber regions (960-1320 cm-1, 1580-1760 cm-1 and 2780-3750 cm-1) and over a temperature range between 250 K and 340 K. The resolution enhancement provided by the 2D-COS offers the possibility to extract the sequential order of events tracked by specific functional groups of the system, and allows, at the same time, the overcoming of some of the limits associated with conventional 1D FTIR-ATR analysis. Acquired information could be used, in principle, for the definition of an optimized procedure capable to provide high-performance T-sensitive drug carrier systems for different applications.

New insights into the structure and function of the prokaryotic communities colonizing plastic debris collected in King George Island (Antarctica): Preliminary observations from two plastic fragments.

In Antarctic regions, the composition and metabolic activity of microbial assemblages associated with plastic debris ("plastisphere") are almost unknown. A macroplastic item from land (MaL, 30 cm) and a mesoplastic from the sea (MeS, 4 mm) were collected in Maxwell Bay (King George Island, South Shetland) and analyzed by Fourier transform infrared spectroscopy in attenuated total reflectance geometry (FTIR-ATR), which confirmed a polystyrene foam and a composite high-density polyethylene composition for MaL and MeS, respectively. The structure and function of the two plastic-associated prokaryotic communities were studied by complementary 16S ribosomal RNA gene clone libraries, total bacterioplankton and culturable heterotrophic bacterial counts, enzymatic activities of the whole community and enzymatic profiles of bacterial isolates. Results showed that Gamma- and Betaproteobacteria (31% and 28%, respectively) dominated in MeS, while Beta- and Alphaproteobacteria (21% and 13%, respectively) in MaL. Sequences related to oil degrading bacteria (Alcanivorax,Marinobacter) confirmed the known anthropogenic pressure in King George Island. This investigation on plastic-associated prokaryotic structure and function represents the first attempt to characterize the ecological role of plastisphere in this Antarctic region and provides the necessary background for future research on the significance of polymer type, surface characteristics and environmental conditions in shaping the plastisphere.

Rutin-Loaded Solid Lipid Nanoparticles: Characterization and In Vitro Evaluation.

This study was aimed at preparing and characterizing solid lipid nanoparticles loading rutin (RT-SLNs) for the treatment of oxidative stress-induced diseases. Phospholipon 80H® as a solid lipid and Polysorbate 80 as surfactant were used for the SLNs preparation, using the solvent emulsification/diffusion method. We obtained spherical RT-SLNs with low sizes, ranging from 40 to 60 nm (hydrodynamic radius) for the SLNs prepared starting from 2% and 5% (w/w) theoretical amount. All prepared formulations showed negative zeta-potential values. RT was efficiently encapsulated within SLNs, obtaining high encapsulation efficiency and drug content percentages, particularly for SLNs prepared with a 5% theoretical amount of RT. In vitro release profiles and analysis of the obtained data applying different kinetic models revealed Fickian diffusion as the main mechanism of RT release from the SLNs. The morphology of RT-SLNs was characterized by scanning electron microscopy (SEM), whereas the interactions between RT and the lipid matrix were investigated by Raman spectroscopy, evidencing spectral modifications of characteristic bands of RT due to the establishment of new interactions. Finally, antioxidant activity assay on human glioblastoma astrocytoma (U373) culture cells showed a dose-dependent activity for RT-SLNs, particularly at the highest assayed dose (50 µM), whereas the free drug showed the lesser activity.

2D Correlation Spectroscopy (2DCoS) Analysis of Temperature-Dependent FTIR-ATR Spectra in Branched Polyethyleneimine/TEMPO-Oxidized Cellulose Nano-Fiber Xerogels.

Fourier transform infrared spectroscopy in attenuated total reflectance geometry (FTIR-ATR), combined with a 2D correlation analysis, was here employed to investigate temperature-induced spectral changes occurring in a particular type of novel cellulosic-based nano-material prepared using 2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO) oxidized and ultra-sonicated cellulose nano-fibers (TOUS-CNFs) as three-dimensional scaffolds, and branched polyethyleneimine (bPEI) as cross-linking agent. The aim was to highlight the complex sequential events involving the different functional groups of the polymeric network, as well as to gain insight into the interplay between the amount of bPEI and the resulting sponge-like material, upon increasing temperature. In this framework, synchronous and asynchronous 2D spectra were computed and analyzed in three wavenumber regions (900-1200 cm-1, 1500-1700 cm-1 and 2680-3780 cm-1), where specific vibrational modes of the cellulosic structure fall, and over a T-range between 250 K and 340 K. A step-by-step evolution of the different arrangements of the polymer functional groups was proposed, with particular regard to how the cooperativity degree of inter- and intramolecular hydrogen bonds (HBs) changes upon heating. Information acquired can be useful, in principle, in order to develop a next-generation, T-sensitive novel material to be used for water remediation applications or for drug-delivery nano-vectors.

In situ diagnostic analysis of the XVIII century Madonna della Lettera panel painting (Messina, Italy).

The scientific investigation of the techniques employed by the artist, such as composition of the paints, color palette, and painting style represents a fundamental pre-requisite in order to develop proper conservation and restoration strategies. In this context, the combined use of non-destructive, non-invasive in situ image and chemical analyses was here successfully employed for the investigation of the XVIII century Madonna della Lettera panel painting from the ancient Basilian abbey of Santa Maria di Bordonaro in Messina (Italy). The used techniques were visible, infrared (IR) and false-color infrared (FCIR) photography, X-ray radiography, X-ray fluorescence (XRF) and Raman spectroscopy. The goal was to obtain accurate information on materials and techniques originally used and possible later interventions, with particular regard to the nature of the painting materials. From the results, details of the artwork useful for restoration and conservation procedures were revealed. The identification of most of the artist's palette was also achieved: Prussian blue for blue color, lead white for white, umber for the brown, cinnabar for the red, and carbon black for the black color. The composition of different preparatory substrates was also investigated. The obtained results, other than constituting a crucial step for future restoration works, can be at the same time useful for the dating of the painting, that does not report the date and the artist's signature.

Physicochemical Characterization and Antioxidant Activity Evaluation of Idebenone/Hydroxypropyl-ß-Cyclodextrin Inclusion Complex †.

Idebenone (IDE) is an antioxidant drug active at the level of the central nervous system (CNS), whose poor water solubility limits its clinical application. An IDE/2-hydroxypropyl-ß-cyclodextrin (IDE/HP-ß-CD) inclusion complex was investigated by combining experimental methods and theoretical approaches. Furthermore, biological in vitro/ex vivo assays were performed. Phase solubility studies showed an AL type diagram, suggesting the presence of a 1:1 complex with high solubility. Scanning electron microscopy (SEM) allowed us to detect the morphological changes upon complexation. The intermolecular interactions stabilizing the inclusion complex were experimentally characterized by exploring the complementarity of Fourier-transform infrared spectroscopy in attenuated total reflectance geometry (FTIR-ATR) with mid-infrared light, Fourier-transform near-infrared (FT-NIR) spectroscopy, and Raman spectroscopy. From the temperature evolution of the O-H stretching band of the complex, the average enthalpy ΔHHB of the hydrogen bond scheme upon inclusion was obtained. Two-dimensional (2D) rotating frame Overhauser effect spectroscopy (ROESY) analysis and computational studies involving molecular modeling and molecular dynamics (MD) simulation demonstrated the inclusion of the quinone ring of IDE inside the CD ring. In vitro/ex vivo studies evidenced that complexation produces a protective effect of IDE against the H2O2-induced damage on human glioblastoma astrocytoma (U373) cells and increases IDE permeation through the excised bovine nasal mucosa.

Do plastics serve as a possible vector for the spread of antibiotic resistance? First insights from bacteria associated to a polystyrene piece from King George Island (Antarctica).

The retrieval of a polystyrene macro-plastic piece stranded on the shores in King George Island (South Shetlands, Antarctica) gave the opportunity to explore the associated bacterial flora. A total of 27 bacterial isolates were identified by molecular 16s rRNA gene sequencing and 7 strains were selected and screened for their ability to produce biofilm and antibiotic susceptibility profiles. All the bacterial isolates were able to produce biofilm. The Kirby-Bauer disk diffusion susceptibility test to 34 antibiotics showed multiple antibiotic resistances against the molecules cefuroxime and cefazolin (belonging to cephalosporins), cinoxacin (belonging to quinolones) and ampicillin, amoxicillin + clavulanic acid, carbenicillin and mezlocillin (belonging to beta-lactams). The obtained results suggest that plastics can serve as vectors for the spread of multiple resistances to antibiotics across Antarctic marine environments and underline the relevance of future studies on this topic.

Physicochemical properties of inclusion complexes of highly soluble ß-cyclodextrins with highly hydrophobic testosterone propionate.

Hydroxypropyl-ß-cyclodextrin (HP-ß-CyD) and sulfobutyl ether-ß-cyclodextrin (SBE-ß-CyD) were used to generate hydrophilic complexes of the poorly water-soluble drug testosterone propionate (TP). The inclusion complexes were obtained by freeze-drying, and then analyzed at both liquid and solid states. Phase solubility studies, performed according to the type-AL solubility diagrams of TP in presence of both CyDs, suggested the formation of water-soluble complexes at 1:1 molar ratio. These results were confirmed by continuous variation method (Job's plot). Both CyDs increased water-solubility of TP 100-fold as compared to the native drug. The host-guest arrangement of CyD complexes in a water solution was further investigated by one- and two-dimensional NMR spectroscopy, highlighting the insertion of the tetracyclic ring of TP into the CyD cavity, and the interaction of the pending ester chain of drug with the primary hydroxyl groups of CyDs at the narrow end of the toroid structure. In solid phase, FTIR-ATR spectroscopy showed that the CO stretching mode of the TP vibrational spectrum changed if the complex between the drug and CyDs occurred. This change is temperature-dependent, and its evolution, accounted for by deconvolution procedures, provided the thermodynamic parameters explaining the mechanisms involved in the formation of inclusion complexes.

Tuning structural parameters for the optimization of drug delivery performance of cyclodextrin-based nanosponges.

INTRODUCTION: In light of the recent development of new soft materials, nanostructured self-assembled systems have attracted attention in a variety of technological fields of high social impact. Cyclodextrin nanosponges (CDNS) represent a new and highly versatile class of cross-linked cyclodextrin (CD)-based nanoporous polymers. Their intriguing properties, including safety, biodegradability, negligible toxicity, marked swelling behavior, superior inclusion capability with respect to native CD, are the bases for potential for applications in drug delivery, tissue engineering and regenerative medicine. Areas covered: We report on the state-of-art concerning a detailed characterization of structural and dynamical features of CDNS explored by the combined use of different and complementary techniques, such as Fourier transform infrared absorption in attenuated total reflectance geometry (FTIR-ATR) and Raman spectroscopies, and high resolution magic angle spinning (HR-MAS) NMR spectroscopy. The ambitious objective is to furnish an exhaustive survey of the role played by hydrophobic and hydrophilic groups within the cross-linked network, in dry and swollen states, in determining the macroscopic functional features of CDNS. Expert opinion: The reported results may significantly contribute in the rational design and optimization of new stimuli-responsive systems exhibiting tunable inclusion/release properties, adapted to the therapeutic demands of pathology.

Solute-Solvent Interactions in Aqueous Solutions of Sulfobutyl Ether-ß-cyclodextrin As Probed by UV-Raman and FTIR-ATR Analysis.

A vibrational study by means of UV-Raman and FTIR-ATR measurements has been performed on sulfobutyl ether ß-cyclodextrin (SBE-ß-CD)-water solutions, as a function of concentration and temperature, with the aim to provide a molecular-scale explanation of the enhanced performances as carrier agent exhibited by this modified macrocycle with respect to natural cyclodextrin. The attention has been mainly paid to the modifications induced on the vibrational band assigned to the O-H stretching intramolecular mode, in turn related to the dynamical rearrangement occurring in the hydrogen bonding (HB) network of water molecules. The results of our measurements clearly showed a characteristic "structure-breaker" effect on the tetrahedral HB arrangements induced on water molecules by increasing of both temperature and solute concentration, allowing us to also extract thermodynamic parameters. These results could be a key step for a clearer understanding of the connection between the dynamical properties of hydration water and the complexing ability of this cyclodextrin derivative.

Toward an understanding of the thermosensitive behaviour of pH-responsive hydrogels based on cyclodextrins.

The molecular mechanism responsible for the thermosensitive behaviour exhibited by pH-responsive cyclodextrin-based hydrogels is explored here with the twofold aim of clarifying some basic aspects of H-bond interactions in hydrogel phases and contributing to a future engineering of cyclodextrin hydrogels for targeted delivery and release of bioactive agents. The degree of H-bond association of water molecules entrapped in the gel network and the extent of intermolecular interactions involving the hydrophobic/hydrophilic moieties of the polymer matrix are probed by UV Raman and IR experiments, in order to address the question of how these different and complementary aspects combine to determine the pH-dependent thermal activation exhibited by these hydrogels. Complementary vibrational spectroscopies are conveniently employed in this study with the aim of safely disentangling the spectral response arising from the two main components of the hydrogel systems, i.e. the polymer matrix and water solvent. The experimental evidence suggests that the dominant effects in the mechanism of solvation of cyclodextrin-based hydrogels are due to the changes occurring, upon increasing of temperature, in the hydrophobicity character of specific chemical moieties of the polymer, as triggered by pH variations. The achievements of this work corroborate the potentiality of the UV Raman scattering technique, in combination with more conventional IR experiments, to provide a "molecular view" of complex macroscopic phenomena exhibited in hydrogel phases.

Thermal fluctuations in chemically cross-linked polymers of cyclodextrins.

The extent and nature of thermal fluctuations in the innovative class of cross-linked polymers called cyclodextrin nanosponges (CDNS) are investigated, on the picosecond time scale, through elastic and quasielastic neutron scattering experiments. Nanosponges are complex 3D polymer networks where covalent bonds connecting different cyclodextrin (CD) units and intra- and inter-molecular hydrogen-bond interactions cooperate to define the molecular architecture and fast dynamics of the polymer. The study presented here aims to clarify the nature of the conformational rearrangements activated by increasing temperature in the nanosponge polymer, and the constraints imposed by intra- and inter-molecular hydrogen-bond patterns on the internal dynamics of the macromolecule. The results suggest a picture, in which conformational rearrangements involving the torsion of the OH groups around the C-O bonds dominate the internal dynamics of the polymer over the picosecond time scale. Moreover, the estimated values of mean square displacements reveal that the motions of the hydrogen atoms in the nanosponges are progressively hampered as the cross-linking degree of the polymer is increased. Finally, the study of the molecular relaxations suggests a dynamical rearrangement of the hydrogen-bond networks, which is characterized by a jump diffusion motion of the more mobile hydrogen atoms belonging to the OH groups of the CD units. All these findings add further contribution to the rational comprehensive view of the dynamics of these macromolecules, which may be particularly beneficial in designing new drug-delivery systems with tuneable inclusion/release properties.