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Hydrophobic non-ionic (type V) deep eutectic solvents (DESs) have recently emerged as a new class of sustainable materials that have shown unique properties in several applications. In this study, type V DESs thymol : camphor, menthol : thymol and eutectic mixtures (EMs) based on menthol : carboxylic acids with variable chain length, are experimentally investigated using xenon NMR spectroscopy, with the aim to clarify the peculiar nanostructure of these materials. The results, obtained from the analysis of the 129Xe chemical shifts and of the longitudinal relaxation times, reveal a correlation between the deviation from ideality of the DESs and their structure free volume. Furthermore, the effect of varying the composition of DESs and EMs on the liquid structure is also studied.

Transparent nanocomposite films made of surface-modified titanium dioxide nanoparticles and thermoplastic polyurethane are prepared via film casting approach showing enhanced refractive indexes and mechanical properties. Two different sets of composites were prepared up to 37.5 wt % of inorganic nanoparticles with a diameter <15 nm, one set using particles capped only with oleic acid and a second one with a bimodal system layer made of oleic acid and mPEO-5000 as coating agents. All of the composites show significantly enhanced refractive index and mechanical properties than the neat polymeric matrix. The transparency of nanocomposite films shows the excellent dispersion of the inorganic nanoparticles in the polymeric matrix avoiding aggregation and precipitation phenomena. Our study provides a facile and feasible route to produce transparent nanocomposite films with tunable mechanical properties and high refractive indices for various applications.

Exosomes are promising therapeutics for tissue repair and regeneration to induce and guide appropriate immune responses in dystrophic pathologies. However, manipulating exosomes to control their biodistribution and targeting them in vivo to achieve adequate therapeutic benefits still poses a major challenge. Here we overcome this limitation by developing an externally controlled delivery system for primed annexin A1 myo-exosomes (Exomyo). Effective nanocarriers are realized by immobilizing the Exomyo onto ferromagnetic nanotubes to achieve controlled delivery and localization of Exomyo to skeletal muscles by systemic injection using an external magnetic field. Quantitative muscle-level analyses revealed that macrophages dominate the uptake of Exomyo from these ferromagnetic nanotubes in vivo to synergistically promote beneficial muscle responses in a murine animal model of Duchenne muscular dystrophy. Our findings provide insights into the development of exosome-based therapies for muscle diseases and, in general, highlight the formulation of effective functional nanocarriers aimed at optimizing exosome biodistribution

Heterogeneous catalysis is an essential aspect for actual industrialization of chemical processes. Here a TiO2-based powder, typically used in photocatalysis, is exploited for the first time for visible-light-regulated Photoinduced Electron/Energy (PET)-reversible addition–fragmentation chain-transfer (RAFT). Titania is a non-toxic, low-cost, and heterogeneous catalyst that can offer several advantages in terms of sustainable polymerization and photocatalyst (PC) recovery. In this work, we aim not only at unraveling the mechanism of photopolymerization and the important interactions involved, but also at red-shifting the absorption region to achieve vis-light polymerization. The combination of the experimental investigation with Density Functional Theory (DFT) calculations provides new insights into the interactions between the chain transfer agents (CTAs) and the TiO2 surface, unveiling their pivotal role on the reaction rate and polymerization control. Moreover, to shift the polymerization under the less energetic blue light, high-surface area N-doped TiO2 nanoparticles are employed, avoiding the CTA degradation often observed with UV irradiation and increasing the overall sustainability of the process.

The reversible gelation of aqueous methylcellulose (MC)solutionsat high temperature is followed stepwise with low-field time-domainnuclear magnetic resonance (LF-TD-NMR). The gel transition does notinfluence the self-diffusion coefficient of water but is associatedwith a decrease of proton transverse relaxation times H-1 T (2) by more than 60%. The effect ofmolecular weight and concentration of polysaccharide chains on transitiontemperature and gel strength is probed on several MCs with the samedegree of substitution. The measured trends connect the NMR relaxationwith macroscopic observables and agree with literature results frommore demanding techniques like small-angle X-ray and neutron scattering(SAXS and SANS). These findings support the idea of a network structureof disorderly arranged fibrils, with an inhomogeneous mesh size atleast on the order of tens of microns, which is in accord with theopaque appearance of these hydrogels. Magic sandwich echo (MSE) NMRmeasurements performed at 80 degrees C by substituting water with D2O also reveal the appearance with thermogelation of a rigidfraction involving about 25% of MC. This is consistent with the formationof fibrils mostly constituted by an amorphous matrix strongly permeatedby water and strengthened by well-dispersed MC crystallites.

Retrieving the starting monomers from polymers synthesized by reversible deactivation radical polymerization has recently emerged as an efficient way to increase the recyclability of such materials and potentially enable their industrial implementation. To date, most methods have primarily focused on utilizing high temperatures (typically from 120 °C to 180 °C) to trigger an efficient depolymerization reaction. In this work, we show that, in the presence of Eosin Y under light irradiation, a much faster depolymerization of polymers made by reversible addition-fragmentation chain-transfer (RAFT) polymerization can be triggered even at a lower temperature (i.e. 100 °C). For instance, green light, in conjunction with ppm amounts of Eosin Y, resulted in the accelerated depolymerization of poly(methyl methacrylate) from 16% (thermal depolymerization at 100 °C) to 37% within 1 hour, and finally 80% depolymerization after 8 hours, as confirmed by both 1H-NMR and SEC analyses. The enhanced depolymerization rate was attributed to the activation of a macroCTA by Eosin Y, thus resulting in a faster macroradical generation. Notably, this method was found to be compatible with different wavelengths (e.g. blue, red and white light irradiation), solvents, and RAFT agents, thus highlighting the potential of light to significantly improve current depolymerization approaches.

Porous materials are ubiquitous systems with a large variety of applications from catalysis to polymer science, from soil to life science, from separation to building materials. Many relevant systems of biological or synthetic origin exhibit a hierarchy, defined as spatial organization over several length scales. Their characterization is often elusive, since many techniques can only be employed to probe a single length scale, like the nanometric or the micrometric levels. Moreover, some multiscale systems lack tridimensional order, further reducing the possibilities of investigation.129 Xe nuclear magnetic resonance (NMR) provides a unique and comprehensive description of multiscale porous materials by exploiting the adsorption and diffusion of xenon atoms. NMR parameters like chemical shift, relaxation times, and diffusion coefficient allow the probing of structures from a few angstroms to microns at the same time. Xenon can evaluate the size and shape of a variety of accessible volumes such as pores, layers, and tunnels, and the chemical nature of their surface. The dynamic nature of the probe provides a simultaneous exploration of different scales, informing on complex features such as the relative accessibility of different populations of pores. In this review, the basic principles of this technique will be presented along with some selected applications, focusing on its ability to characterize multiscale materials.

We present an experimental approach to studying the kinetics of polymer nanoparticle formation using molecular rotor molecules as fluorescence probes. By combining fluorescence lifetime analysis and fluorescence correlation spectroscopy, it is possible to simultaneously monitor the evolution of the local environment in the nanoparticles and their size. To assess the generality of the method, we select two common but very different methods for nanoparticle preparation: emulsion-solvent evaporation and miniemulsion polymerization. In both cases, three stages of the nanoparticle formation process were identified on the basis of their polymer content. In the initial stage of the process, the polymer content is low. Then it increases rapidly because of solvent evaporation or polymerization during the second stage. Finally, it reaches a plateau value. Furthermore, significant heterogeneities in the final nanoparticles were found that can be attributed to remaining solvent or monomer and the spatial variation of the polymer-free volume.

The localization of the rubber vulcanization reaction close to the silica filler surface was investigated in isoprene rubber composites (IR NCs): the main goal was to highlight the role of curing agents’ dispersion and filler surface features on the spatial propagation of the rubber cross-links and the resulting mechanical behavior of the material. The study was realized by tailoring the morphology of the curing activator, i.e. by vulcanizing IR NCs with Zn@SiO2 double function filler, composed of Zn(II) single sites anchored on SiO2 filler, in comparison to silica filled IR NCs vulcanized with microcrystalline ZnO. The microscopic cross-links distribution was measured by Transmission Electron Microscopy for network visualization (NVTEM) and Time Domain Nuclear Magnetic Resonance (TD-NMR). Besides the NCs mechanical behavior was characterized both at small strain and at fracture. In the presence of Zn@SiO2, higher cross-link density in proximity to SiO2 particles was evidenced, which gradually spreads from the filler surface to the bulk, induced by localization of the Zn(II) centers. IR NCs with Zn@SiO2 resulted stiffer (+45%) and with a lower fracture toughness (less than one third), compared to m-ZnO based NCs, which shows a quite homogeneous structure of the rubber cross-links network. The results highlighted the correlation between the composites structural features and their macroscopic behavior, paving the way to modulating the mechanical properties of elastomeric materials by tuning the nature of the curing agents.

A photocatalytic RAFT-controlled radical depolymerization method is introduced for precisely conferring temporal control under visible light irradiation. By regulating the deactivation of the depropagating chains and suppressing thermal initiation, an excellent temporal control was enabled, exemplified by several consecutive “on” and “off” cycles. Minimal, if any, depolymerization could be observed during the dark periods while the polymer chain-ends could be efficiently re-activated and continue to depropagate upon re-exposure to light. Notably, favoring deactivation resulted in the gradual unzipping of polymer chains and a stepwise decrease in molecular weight over time. This synthetic approach constitutes a simple methodology to modulate temporal control during the chemical recycling of RAFT-synthesized polymers while offering invaluable mechanistic insights.

The liquid structure of dihalomethanes (CH2X2, X = Cl, Br, I) loaded with xenon gas was investigated both experimentally, by 129Xe NMR Spectroscopy, and computationally, by molecular dynamics (MD) simulations and relativistic DFT calculations. The chemical shifts of xenon have been measured in a wide range of temperatures; in addition, the spin-lattice relaxation times, T1, and the diffusion coefficients of dissolved xenon were also determined. The MD simulations of the three dihalomethanes with xenon dissolved were used to generate a collection of clusters, representing xenon with its first solvation shell, which was subsequently submitted to the relativistic DFT calculation of the 129Xe NMR shielding constant. This was finally averaged over the trajectory to obtain the corresponding chemical shift at various temperatures. The experimental data were then rationalized in terms of the density of the bulk phase and the average orientation of the halogens with respect to the xenon atom. Diffusion coefficients were also obtained from the MD simulations and compared with the experimental values, showing a good agreement.

The porous topology of Type II Porous Liquids (PLs), prepared using Noria-OEt as an empty molecular host dissolved in 15-crown-5 solvent, is investigated with 129Xe NMR Spectroscopy. Xenon NMR parameters, such as chemical shifts and T1 relaxation times, measured in PLs solutions prepared at various Noria-OEt concentrations, are related to the intrinsic microporous structure of the material. The experimental data are interpreted on the basis of a multiple-site model for xenon atoms within the multiple PLs cavities. Diffusion NMR experiments show a similar mobility of xenon in PLs compared with the pure solvent.

Water-in-salt solutions, i.e. solutions in which the amount of salt by volume or weight is larger than that of the solvent, are attracting increasing attention in electrochemistry due to their distinct features that often include decomposition potentials much higher than those of lower concentration solutions. Despite the high solubility of potassium acetate (KAC) in water at room temperature (up to 25 moles of salt per kg of solvent), the low cost, and the large availability, the use of highly concentrated KAC solutions is still limited to a few examples in energy storage applications and a systematic study of their physical-chemical properties is lacking. To fill this gap, we have investigated the thermal, rheological, electrical, electrochemical, and spectroscopic features of KAC/water solutions in the compositional range between 1 and 25 mol kg-1. We show the presence of a transition between the "salt-in-solvent"and "solvent-in-salt"regimes in the range of 10-15 mol kg-1. Among the explored compositions, the highest concentrations (20 and 25 mol kg-1) exhibit good room temperature conductivity values (55.6 and 31 mS cm-1, respectively) and a large electrochemical potential window (above 2.5 V).

The formation of block copolymer nanoparticles is commonly obtained by switching solvent quality from good solvent for both blocks to a selective solvent for one block. The effect of the selective solvent on particle dimension, shape and inner structure has been analyzed in detail, instead less attention has been focused on the role of the common solvent. Poly(ethylene oxide)-block-poly(lactic acid) (PEO-b-PLA) is widely used for the preparation of nanometric drug delivery systems and the control of the particle morphology has relevant effects on bioactivity. In this work we investigate the effect of using different common solvents (acetone, dioxane, tetrahydrofuran, dimethylformamide) on the self-assembly behavior of narrowly dispersed PEO-b-PLA copolymers, synthesized by metal free ring-opening polymerization, with large variation of molecular weight of the hydrophobic block (from 65 to 1300 lactic units). Dynamic light scattering (DLS) and cryo-electron microscopy (cryo-EM) analyses of PEO-b-PLA nanoparticles reveal that their size and shape are strongly dependent on the hydrogen bonding ability of the common solvent used in the self-assembly process. As consequence of these variations, also the cytoxicity of the nanoparticles is affected.

The development of mulch films from wastes of vegetables represents a sustainable alternative to the traditionally used polyethylene ones that follow the principles of circular economy. In this work, we obtained films based on two different industrial vegetable wastes, orange peels (OP) and spinach stems (SS), using hydrolysis at different times (6, 16, and 24 h) and temperatures (30, 50, and 70 °C). Hydrolysis carried out at 30 °C and 24 h has led to films with the best mechanical properties, while high temperatures (70 °C) combined with prolonged treatment times (16 and 24 h) led to materials with lower mechanical resistance and darker coloration. The films' characterization by X-ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), and uniaxial tensile tests elucidated their chemical structure and physicochemical properties. Additionally, the materials' interaction with water was evaluated and significantly improved by adding a carnauba wax coating. Optical properties, micro and macronutrient content and biodegradation in the soil of selected bioplastics were also determined. Results showed that the proposed materials present fast in-soil biodegradation, good potentiality for weed prevention and improvement of plant growth via soil fertilization.

The industrial processing of avocados annually generates more than 1.2 million tons of avocado peels (APs) and avocado seeds (ASs) that have great potential in the production of active bioplastics, although they have never been considered for this aim until now. Separately, the APs and ASs, as well as a combination of avocado peels and seeds (APSs), were evaluated here for the first time for the preparation of antioxidant films, with application in food packaging. Films were prepared by casting, after their processing by three different methods: (1) hydrolysis in acid media, (2) hydrolysis followed by plasticization, and (3) hydrolysis and plasticization followed by blending with pectin polymers in different proportions (25 and 50 wt %). The results indicate that the combination of hydrolysis, plasticization, and pectin blending is essential to obtain materials with competitive mechanical properties, optical clarity, excellent oxygen barrier properties, high antioxidant activity, biodegradability, and migration of components in TENAX suitable for food contact applications. In addition, the materials prepared with APSs are advantageous from the point of view of the industrial waste valorization, since the entire avocado wastes are used for the production of bioplastics, avoiding further separation processes for their valorization.

Developing new materials for the separation of gas mixtures is a key subject in setting up a circular economy. In this work, we report the synthesis and application of novel polymeric membranes, based on polymerized ionic liquids (PILs), to be used for CO2 separation from different gas pairs. Phosphonium-based PILs have been copolymerized within an original acrylate formulation that allowed the development of dense membranes able to overcome some of the main limitations related to ionic liquid membranes. Thereby, a collection of phosphonium ionic liquids has been investigated by evaluating the influence of the alkyl chain length and anion type on membrane structure and properties by employing a series of different chemo-physical characterization techniques. The membranes showed a marked preference toward CO2 permeation in the wet state, which simulates the conditions occurring with many CO2-containing gas streams, with two of the studied membranes exceeding the Robeson upper bound for the CO2/H2 gas pair.

The dynamics of xenon gas, loaded in a series of 1-alkyl-3-methylimidazolium based ionic liquids, probes the formation of increasingly blurred polar/apolar nanodomains as a function of the anion type and the cation chain length. Exploiting 129Xe NMR spectroscopy techniques, like Pulse Gradient Spin Echo (PGSE) and inversion recovery (IR), the diffusion motion and relaxation times are determined for 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [CnC1im][TFSI]. A correlation between the ILs nano-structure and both xenon diffusivity and relaxation times, as well as chemical shifts, is outlined. Interestingly, comparison with previous results of the same properties in the homologous imidazolium chlorides and hexafluorophospate shows an opposite trend with the alkyl chain length. Classical molecular dynamics (MD) simulations are used to calculate the xenon and cation and anion diffusion coefficients in the same systems, including imidazolium cations with longer chains (n=4, 6, 8 ... 20). An almost quantitative agreement with the experiments validates the MD simulations and, at the same time, provides the necessary structural and dynamic microscopic insights on the nano-segregation and diffusion of xenon in bistriflimide, chloride and hexafluorphosphate salts allowing to observe and rationalize the shaping effect of the cation in the nanostructure.

The design and development of contrast agents (CAs) for magnetic resonance imaging (MRI) in clinical analysis is expected to improve the image spatial resolution and to increase the detection sensitivity, especially regarding neurological disorders and cancer disease. In particular, advanced CAs for T1-weighted images are investigated to achieve the sensitive detection of early-stage primary tumors or brain metastases. In this study, we present a strategy toward diagnostic T1 CAs for MRI, based on polymer-modified MnO nanoparticles (NPs). Two different nanosystems were synthesized, consisting of (1) colloidal MnO nanocrystals wrapped by a multidentate amphiphilic polymer and (2) MnO nanocrystals embedded within poly(lactic-co-glycolic acid) (PLGA) NPs. These nanosystems were compared in terms of their MRI contrast power and biological safety. The latter system combines the excellent biocompatibility of PLGA with the unique magnetic properties of MnO NPs and allows sustained contrast enhancement over time. Longitudinal relaxivities of both MnO composite nanomaterials proved to be higher than those of commercial Gd-based CAs and Teslascan, both in phosphate-buffered saline and in plasma, also exhibiting low cytotoxicity. The high relaxation rates achieved with these contrast enhancers are promising toward future application in in vivo imaging.

The possibility to use the macromolecules present in vegetable biomass, with minimal processing, as alternative materials to produce new green bioplastics for packaging is very appealing. This strategy can help to mitigate environmental issues due to broad usage of conventional plastics. Since a large variety of vegetable waste, in terms of chemical composition and supramolecular organization, is produced by the food industry, many different bioplastics can be produced with the same protocol. Bioplastics films from carrot pomace, cocoa shells, spinach stems and orange peels will be characterized in terms of thermomechanical properties and biodegradability. The mechanical properties will be correlated with the composition and morphology as determined by means of a combination of techniques (solid-state NMR, SEM and confocal microscopy). The biodegradability of the films will be characterized in terms of Biochemical Oxygen Demand as function of time during 30 days of incubation in seawater.

Membrane modification is becoming ever more relevant for mitigating fouling phenomena within wastewater treatment applications. Past research included a novel low-fouling coating using polymerizable bicontinuous microemulsion (PBM) induced by UV-LED polymerization. This additional cover layer deteriorated the filtration capacity significantly, potentially due to the observed high pore intrusion of the liquid PBM prior to the casting process. Therefore, this work addressed an innovative experimental protocol for controlling the viscosity of polymerizable bicontinuous microemulsions (PBM) before casting on commercial ultrafiltration (UF) membranes. Prior to the coating procedure, the PBM viscosity modulation was carried out by controlled radical polymerization (CRP). The regulation was conducted by introducing the radical inhibitor 2,2,6,6-tetramethylpiperidine 1-oxyl after a certain time (CRP time). The ensuing controlled radical polymerized PBM (CRP-PBM) showed a higher viscosity than the original unpolymerized PBM, as confirmed by rheological measurements. Nevertheless, the resulting CRP-PBM-cast membranes had a lower permeability in water filtration experiments despite a higher viscosity and potentially lower pore intrusion. This result is due to different polymeric structures of the differently polymerized PBM, as confirmed by solid-state nuclear magnetic resonance (NMR) investigations. The findings can be useful for future developments in the membrane science field for production of specific membrane-coating layers for diverse applications.

The possibility to use vegetable biomass, with minimal processing, as new green bioplastic for packaging is very appealing to mitigate environmental issues due to broad usage of conventional plastics. Here we developed vegetable bioplastic films from carrot pomace with good mechanical properties and glass transition temperature function of humidity, with a lowest value of −60 °C when highly hydrated. These properties were exploited to set-up scalable and green fabrication techniques for the production of macroscopic objects with elaborate shapes and detailed features at the micro scale. By means of a combination of techniques (FTIR, NMR, DSC and DMTA) we provide a comprehensive picture of the material structure and how the absorbed water changes the macromolecules’ structure, finally explaining the source of the glass transition of the material.

Molecularly imprinted polymers (MIPs) display intriguing recognition properties and can be used as sensor recognition elements or in separation. In this work, we investigated the formation of hierarchical porosity of compositionally varied MIPs using 129Xe Nuclear Magnetic Resonance (NMR) and 1H Time Domain Nuclear Magnetic Resonance (TD-NMR). Variable temperature 129Xe NMR established the morphological variation with respect to the degree of cross-linking, supported by 1H TD-NMR determination of polymer chain mobility. Together, the results indicate that a high degree of cross-linking stabilizes the porous structure: highly cross-linked samples display a significant amount of accessible mesopores that instead collapse in less structured polymers. No significant differences can be detected due to the presence of templated pores in molecularly imprinted polymers: in the dry state, these specific shapes are too small to accommodate xenon atoms, which, instead, probe higher levels in the porous structure, allowing their study in detail. Additional resonances at a high chemical shift are detected in the 129Xe NMR spectra. Even though their chemical shifts are compatible with xenon dissolved in bulk polymers, variable temperature experiments rule out this possibility. The combination of 129Xe and TD-NMR data allows attribution of these resonances to softer superficial regions probed by xenon in the NMR time scale. This can contribute to the understanding of the surface dynamics of polymers.

Lithium metal batteries (LMBs) will be a breakthrough in automotive applications, but they require the development of next-generation solid-state electrolytes (SSEs) to stabilize the anode interface. Polymer-in-ceramic PEO/TiO2 nanocomposite SSEs show outstanding properties, allowing unprecedented LMBs durability and self-healing capabilities. However, the mechanism underlying the inhibition/delay of dendrite growth is not well understood. In fact, the inorganic phase could act as both a chemical and a mechanical barrier to dendrite propagation. Combining advanced in situ and ex situ experimental techniques, we demonstrate that oligo(ethylene oxide)-capped TiO2, although chemically inert toward lithium metal, imparts SSE with mechanical and dynamical properties particularly favorable for application. The self-healing characteristics are due to the interplay between mechanical robustness and high local polymer mobility which promotes the disruption of the electric continuity of the lithium dendrites (razor effect).

The synthesis of hydrogels that are based on poly-hydroxyethyl methacrylate, p(HEMA), network semi-interpenetrated with linear polyvinylpyrrolidone (PVP) was optimized in order to allow both a fast preparation and a high cleaning effectiveness of artistic surfaces. For this purpose, the synthesis parameters of the gel with PVP having a high molecular weight (1300 kDa) that were reported in the literature, were modified in terms of temperature, time, and crosslinker amount. In addition, the gel composition was modified by using PVP with different molecular weights, by changing the initiator and by adding maleic anhydride. The modified gels were characterized in terms of equilibrium water content (EWC), water uptake, conversion grade, and thermal properties by differential scanning calorimetry (DSC). The cleaning effectiveness of the gels was studied through the removal of copper salts from laboratory-stained specimens. Cleaning materials were characterized by electron paramagnetic resonance (EPR) spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, and inductively-coupled plasma-mass spectrometry (ICP-MS). Cleaning was assessed on marble specimens by color variation measurements. The gel synthesis is accelerated by using PVP 360 kDa. The addition of maleic anhydride in the p(HEMA)/PVP network allows the most effective removal of copper salt deposits from marble since it acts as a chelator towards copper ions.

Photon upconversion based on sensitized triplet-triplet annihilation (sTTA) is considered as a promising strategy for the development of light-managing materials aimed to enhance the performance of solar devices by recovering unused low-energy photons. Here, we demonstrate that, thanks to the fast diffusion of excitons, the creation of triplet pairs in metal-organic framework nanocrystals (nMOFs) with size smaller than the exciton diffusion length implies a 100% TTA yield regardless of the illumination condition. This makes each nMOF a thresholdless, single-unit annihilator. We develop a kinetic model for describing the upconversion dynamics in a nanocrystals ensemble, which allows us to define the threshold excitation intensity Ith box required to reach the maximum conversion yield. For materials based on thresholdless annihilators, Ith box is determined by the statistical distribution of the excitation energy among nanocrystals. The model is validated by fabricating a nanocomposite material based on nMOFs, which shows efficient upconversion under a few percent of solar irradiance, matching the requirements of real life solar technologies. The statistical analysis reproduces the experimental findings, and represents a general tool for predicting the optimal compromise between dimensions and concentration of nMOFs with a given crystalline structure that minimizes the irradiance at which the system starts to fully operate.

Highly controlled polymers and nanostructures are increasingly translated from the lab to the industry. Together with the industrialization of complex systems from renewable sources, a paradigm change in the processing of plastics and rubbers is underway, requiring a new generation of analytical tools. Here, we present the recent developments in time domain NMR (TD-NMR), starting with an introduction of the methods. Several examples illustrate the new take on traditional issues like the measurement of crosslink density in vulcanized rubber or the monitoring of crystallization kinetics, as well as the unique information that can be extracted from multiphase, nanophase and composite materials. Generally, TD-NMR is capable of determining structural parameters that are in agreement with other techniques and with the final macroscopic properties of industrial interest, as well as reveal details on the local homogeneity that are difficult to obtain otherwise. Considering its moderate technical and space requirements of performing, TD-NMR is a good candidate for assisting product and process development in several applications throughout the rubber, plastics, composites and adhesives industry.

Ionic liquid (IL) mixtures enable the design of fluids with finely tuned structural and physicochemical properties for myriad applications. In order to rationally develop and design IL mixtures with the desired properties, a thorough understanding of the structural origins of their physicochemical properties and the thermodynamics of mixing needs to be developed. To elucidate the structural origins of the excess molar volume within IL mixtures containing ions with different alkyl chain lengths, 3 IL mixtures containing 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ILs have been explored in a joint small angle X-ray scattering (SAXS) and 129Xe NMR study. The apolar domains of the IL mixtures were shown to possess similar dimensions to the largest alkyl chain of the mixture with the size evolution determined by whether the shorter alkyl chain was able to interact with the apolar domain. 129Xe NMR results illustrated that the origin of excess molar volume in these mixtures was due to fluctuations within these apolar domains arising from alkyl chain mismatch, with the formation of a greater number of smaller voids within the IL structure. These results indicate that free volume effects for these types of mixtures can be predicted from simple considerations of IL structure and that the structural basis for the formation of excess molar volume in these mixtures is substantially different to IL mixtures formed of different types of ions.

Photochemistry has attracted great interest in the last decades in the field of polymer and material science for the synthesis of innovative materials. The merging of photochemistry and reversible-deactivation radical polymerizations (RDRP) provides good reaction control and can simplify elaborate reaction protocols. These advantages open the doors to multidisciplinary fields going from composite materials to bio-applications. Photoinduced Electron/Energy Transfer Reversible Addition-Fragmentation Chain-Transfer (PET-RAFT) polymerization, proposed for the first time in 2014, presents significant advantages compared to other photochemical techniques in terms of applicability, cost, and sustainability. This review has the aim of providing to the readers the basic knowledge of PET-RAFT polymerization and explores the new possibilities that this innovative technique offers in terms of industrial applications, new materials production, and green conditions.

The translational dynamics of xenon gas dissolved in room-temperature ionic liquids (RTILs) is revealed by 129Xe NMR and molecular dynamics (MD) simulations. The dynamic behavior of xenon gas loaded in 1-alkyl-3-methylimidazolium chloride, [CnC1im]Cl (n = 6, 8, 10), and hexafluorophosphate, [CnC1im][PF6] (n = 4, 6, 8, 10) has been determined by measuring the 129Xe diffusion coefficients and NMR relaxation times. The analysis of the experimental NMR data demonstrates that, in these representative classes of ionic liquids, xenon motion is influenced by the length of the cation alkyl chain and anion type. 129Xe spin-lattice relaxation times are well described with a monoexponential function, indicating that xenon gas in ILs effectively experiences a single average environment. These experimental results can be rationalized based on the analysis of classical MD trajectories. The mechanism described here can be particularly useful in understanding the separation and adsorption properties of RTILs.

Diels-Alder chemistry has been used for the thermoreversible cross-linking of furan-functionalized ethylene/propylene (EPM) and ethylene/vinyl acetate (EVM) rubbers. Both furan-functionalized elastomers were successfully cross-linked with bismaleimide to yield products with a similar cross-link density. NMR relaxometry and SAXS measurements both show that the apolar EPM-g-furan precursor contains phase-separated polar clusters and that cross-linking with polar bismaleimide occurs in these clusters. The heterogeneously cross-linked network of EPM-g-furan contrasts with the homogeneous network in the polar EVM-g-furan. The heterogeneous character of the cross-links in EPM-g-furan results in a relatively high Young's modulus, whereas the more uniform cross-linking in EVM-g-furan results in a higher tensile strength and elongation at break.

Polymeric networks, especially rubbers and hydrogels, are ubiquitous materials. The determination of their structure-property relationships is fundamental for their rational design. Low Field (LF) Time Domain (TD) Nuclear Magnetic Resonance (NMR) is a powerful technique to probe molecular-level dynamics, analysing 1H relaxation times T1 e T2. That becomes very useful when it is necessary to monitor time-dependent processes. Thermo-gelation has been investigated on methyl-cellulose (MC) gels (1) with the study of T2 variation with temperature. T2 increases with temperature until a sudden drop, associated to the gel point, which is concentration dependent. The reversibility of the process, the formation of a metastable phase and the associated hysteresis phenomena can be observed, obtaining analogous results to rheological tests (Fig.1a,1b). TD-NMR can also measure residual dipolar couplings (Dres), which are linearly proportional to the crosslinks density (CLD), according to the equation CLD=rac{D_{res}}{4pi A} (2). This has been applied to evaluate the increasing number of crosslinks during the vulcanization process in a commercial rubber compound, with the concurrent reduction in the number of uncoupled chains with progression of the curing (Fig.1c). That reflected also on the more homogeneous distribution of crosslinks at end of the curing process. Even the effect of overcuring at high temperatures in reversion conditions on network morphology can be monitored (Fig.1d). The overcuring induces a drastic change in the morphology with a relevant, but homogeneous, reduction in the CLD respect to the highest CLD accessible at that temperature. Moreover, a peak at even higher Dres appears for the overcured sample, indicating the formation of a much more inhomogeneous network, whose causes could be attributed either to the formation of clusters of monosulfidic bonds or to the association of freed chains to the surface of filler particles.

PEGylation of metal oxide nanoparticles is the common approach to improve their biocompatibility and in vivo circulation time. In this work, we present a combined experimental and theoretical study to determine the operating condition that guarantee very high grafting densities, which are desirable in any biomedical application. Moreover, we present an insightful conformational analysis spanning different coverage regimes and increasing polymer chain lengths. Based on 13C NMR measurements and molecular dynamics simulations, we show that classical and popular models of polymer conformation on surfaces fail in determining the mushroom-to-brush transition point and prove that it actually takes place only at rather high grafting density values.

Reversible addition-fragmentation chain transfer polymerization of chloroprene on the surface of silica nanoparticles was performed to obtain polychloroprene-grafted-silica nanoparticles (PCP-g-SiO 2 NPs). These particles were dispersed in a commercial polychloroprene matrix to obtain PCP nanocomposites with different silica core loadings (1, 5, 10, and 25 wt%). Two different chain graft densities were studied (“low,” 0.022 ch/nm 2 and “high,” 0.21 ch/nm 2 ) as a function of the grafted polymer molecular mass. The cured samples showed significant improvement in the mechanical properties of the PCP rubber nanocomposites as compared to the unfilled PCP as measured by standard tensile and dynamic mechanical analysis even with low silica content. The mechanical properties of the nanocomposites were notably enhanced when the graft density was low and grafted molecular masses were high. Transmission electron microscopy (TEM) and Small-Angle X-ray Scattering (SAXS) were used to analyze the dispersion states of the grafted nanoparticles which confirmed the correlation between high grafted chain lengths and improved dispersion states and mechanical properties

Subtle alterations in the mid-block of polystyrene-b-poly (ethylene-co-butylene)-bpolystyrene (SEBS) have a significant impact on the mechanical properties of the resulting microphase separated materials. In samples with high butylene content, the ethylene-co-butylene (EB) phase behaves as a rubber, as seen by differential scanning calorimetry (DSC), time domain (TD) and Magic Angle Spinning (MAS) NMR, X-ray scattering at small (SAXS), and wide (WAXS) angles. In samples where the butylene content is lower-but still sufficient to prevent crystallization in bulk EB-the DSC thermogram presents a broad endothermic transition upon heating from 221 to 300 K. TD NMR, supported by WAXS and dielectric spectroscopy measurements, probed the dynamic phenomena of EB during this transition. The results suggest the existence of a rotator phase for the EB block below room temperature, as a result of nanoconfinement.