Exploring the structure of type V deep eutectic solvents by xenon NMR spectroscopy.

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.

Magnetic-field-driven targeting of exosomes modulates immune and metabolic changes in dystrophic muscle.

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.

Transparent and High-Refractive-Index Titanium Dioxide/Thermoplastic Polyurethane Nanocomposites.

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.

Sensitized Triplet-Triplet Annihilation in Nanostructured Polymeric Scintillators Allows for Pulse Shape Discrimination.

Scintillating materials emit light when exposed to ionizing radiation or particles and are used for the detection of nuclear threats, medical imaging, high-energy physics, and other usages. For some of these applications, it is vital to distinguish neutrons and charged particles from γ-rays. This is achievable by pulse shape discrimination (PSD), a time-gated technique, which exploits that the scintillation kinetics can depend on the nature of the incident radiation. However, it proves difficult to realize efficient PSD with plastic scintillators, which have several advantages over liquid or crystalline scintillating materials, including mechanical robustness and shapeability. It is shown here that sensitive and rapid PSD is possible with nanostructured polymer scintillators that consist of a solid polymer matrix and liquid nanodomains in which an organic dye capable of triplet-triplet annihilation (TTA) is dissolved. The liquid nature of the nanodomains renders TTA highly efficient so that delayed fluorescence can occur at low energy density. The nanostructured polymer scintillators allow discriminating α particles, neutrons, and γ-rays with a time response that is better than that of commercial scintillators. Exploiting that the liquid nanodomains can facilitate energy transfer processes otherwise difficult to realize in solid polymers, an auxiliary triplet sensitizer is incorporated. This approach further increases the scintillator's sensitivity toward α particles and neutrons and other high-energy processes where localized interactions are involved.

PVDF-HFP Based, Quasi-Solid Nanocomposite Electrolytes for Lithium Metal Batteries.

Composite polymer electrolytes are systems of choice for future solid-state lithium metal batteries (LMBs). Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) is among the most interesting matrices to develop new generation quasi-solid electrolytes (QSEs). Here it is reported on nanocomposites made of PVDF-HFP and pegylated SiO2 nanoparticles. Silica-based hybrid nanofillers are obtained by grafting chains of poly(ethylene glycol) methyl ether (PEG) with different molecular weight on the surface of silica nanoparticles. The functionalized nanofiller improves the mechanical, transport and electrochemical properties of the QSEs, which show good ionic conductivity values and high resistance against dendrite penetration, ensuring boosted long and safe device operation. The most promising result is obtained by dispersing 5 wt% of SiO2 functionalized with short PEG chains (PEG750, Mw = 750 g mol-1) in the PVDF-HFP matrix with an ease solvent-casting procedure. It shows ionic conductivity of 0.1 mS cm-1 at 25 °C, more than 250 h resistance to stripping/plating, and impressive results during cycling tests in LMB with LiFePO4 cathode.

Ultrafast and Radiation-Hard Lead Halide Perovskite Nanocomposite Scintillators.

The use of scintillators for the detection of ionizing radiation is a critical aspect in many fields, including medicine, nuclear monitoring, and homeland security. Recently, lead halide perovskite nanocrystals (LHP-NCs) have emerged as promising scintillator materials. However, the difficulty of affordably upscaling synthesis to the multigram level and embedding NCs in optical-grade nanocomposites without compromising their optical properties still limits their widespread use. In addition, fundamental aspects of the scintillation mechanisms are not fully understood, leaving the scientific community without suitable fabrication protocols and rational guidelines for the full exploitation of their potential. In this work, we realize large polyacrylate nanocomposite scintillators based on CsPbBr3 NCs, which are synthesized via a novel room temperature, low waste turbo-emulsification approach, followed by their in situ transformation during the mass polymerization process. The interaction between NCs and polymer chains strengthens the scintillator structure, homogenizes the particle size distribution and passivates NC defects, resulting in nanocomposite prototypes with luminescence efficiency >90%, exceptional radiation hardness, 4800 ph/MeV scintillation yield even at low NC loading, and ultrafast response time, with over 30% of scintillation occurring in the first 80 ps, promising for fast-time applications in precision medicine and high-energy physics. Ultrafast radioluminescence and optical spectroscopy experiments using pulsed synchrotron light further disambiguate the origin of the scintillation kinetics as the result of charged-exciton and multiexciton recombination formed under ionizing excitation. This highlights the role of nonradiative Auger decay, whose potential impact on fast timing applications we anticipate via a kinetic model.

Epoxy Resins for Flooring Applications, an Optimal Host for Recycling Deactivated Cement Asbestos.

Cement asbestos slates, commonly known as Eternit® and still abundant in private and public buildings, were deactivated through a thermal process. The resulting deactivated cement asbestos powder (DCAP), a mixture of Ca-Mg-Al silicates and glass, was compounded with Pavatekno Gold 200 (PT) and Pavafloor H200/E (PF), two different epoxy resins (bisphenol A epichlorohydrin) for flooring applications. The addition of the DCAP filler to the PF samples causes a slight but acceptable decrease in the relevant mechanical properties (compressive, tensile, and flexural strengths) upon increasing DCAP content. The addition of the DCAP filler to pure epoxy (PT resin) causes a slight decrease in the tensile and flexural strengths with increasing DCAP content, while the compressive strength is almost unaffected, and the Shore hardness increases. The main mechanical properties of the PT samples are significantly better than those of the filler-bearing sample of normal production. Overall, these results suggest that DCAP can be advantageously used as filler in addition to, or in substitution for, commercial barite. In particular, the sample with 20 wt% of DCAP is the best performing in terms of compressive, tensile, and flexural strengths, whereas the sample with 30 wt% of DCAP shows the highest Shore hardness, which is an important property to be considered in flooring applications.

Porosity of Molecularly Imprinted Polymers Investigated by 129Xe NMR Spectroscopy.

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.

Unveiling the Role of PEO-Capped TiO2 Nanofiller in Stabilizing the Anode Interface in Lithium Metal Batteries.

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).

Heparin-Superparamagnetic Iron Oxide Nanoparticles for Theranostic Applications.

In this study, superparamagnetic iron oxide nanoparticles (SPIONs) were engineered with an organic coating composed of low molecular weight heparin (LMWH) and bovine serum albumin (BSA), providing heparin-based nanoparticle systems (LMWH@SPIONs). The purpose was to merge the properties of the heparin skeleton and an inorganic core to build up a targeted theranostic nanosystem, which was eventually enhanced by loading a chemotherapeutic agent. Iron oxide cores were prepared via the co-precipitation of iron salts in an alkaline environment and oleic acid (OA) capping. Dopamine (DA) was covalently linked to BSA and LMWH by amide linkages via carbodiimide coupling. The following ligand exchange reaction between the DA-BSA/DA-LMWH and OA was conducted in a biphasic system composed of water and hexane, affording LMWH@SPIONs stabilized in water by polystyrene sulfonate (PSS). Their size and morphology were investigated via dynamic light scattering (DLS) and transmission electron microscopy (TEM), respectively. The LMWH@SPIONs' cytotoxicity was tested, showing marginal or no toxicity for samples prepared with PSS at concentrations of 50 µg/mL. Their inhibitory activity on the heparanase enzyme was measured, showing an effective inhibition at concentrations comparable to G4000 (N-desulfo-N-acetyl heparin, a non-anticoagulant and antiheparanase heparin derivative; Roneparstat). The LMWH@SPION encapsulation of paclitaxel (PTX) enhanced the antitumor effect of this chemotherapeutic on breast cancer cells, likely due to an improved internalization of the nanoformulated drug with respect to the free molecule. Lastly, time-domain NMR (TD-NMR) experiments were conducted on LMWH@SPIONs obtaining relaxivity values within the same order of magnitude as currently used commercial contrast agents.

The Sensitization of Scintillation in Polymeric Composites Based on Fluorescent Nanocomplexes.

The sensitization of scintillation was investigated in crosslinked polymeric composite materials loaded with luminescent gold clusters aggregates acting as sensitizers, and with organic dye rhodamine 6G as the emitting species. The evolution in time of the excited states population in the systems is described by a set of coupled rate equations, in which steady state solution allowed obtainment of an expression of the sensitization efficacy as a function of the characteristic parameters of the employed luminescent systems. The results obtained indicate that the realization of sensitizer/emitter scintillating complexes is the strategy that must be pursued to maximize the sensitization effect in composite materials.

Block Copolymer Stabilized Liquid Nanodroplets Facilitate Efficient Triplet Fusion-Based Photon Upconversion in Solid Polymer Matrices.

Sensitized triplet-triplet annihilation-based photon upconversion is a photophysical process that affords anti-Stokes-shifted emission after annihilation of two metastable triplet excitons of an emitter dye and the formation of a fluorescent singlet state. While this process readily occurs in solutions under conditions where the mobility of the dye molecules is high, particular architectures are required to facilitate efficient energy transfers in solid polymers. One possibility is to incorporate liquid upconverting domains into solid polymer matrices. Another possibility is to reduce the intermolecular distance between the dyes below the Dexter radius, allowing exciton migration via triplet hopping. We introduce herein nanostructured materials that combine both of these features. These glassy nanostructured polymer systems contain liquid upconverting nanodroplets that are stabilized with a block copolymer surfactant and are fabricated under ambient conditions in a facile one-step protocol. The dyes concentrate in the nanostructured liquid domains, and this enables hopping-mediated ET and TTA between the dyes and leads to an upconversion efficiency of ∼20%.

Xenon Diffusion in Ionic Liquids with Blurred Nanodomain Separation.

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 129 Xe 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 [Cn C1 im][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.

A physico-chemical investigation of highly concentrated potassium acetate solutions towards applications in electrochemistry.

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).

Xenon Dynamics in Ionic Liquids: A Combined NMR and MD Simulation Study.

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.

Optimizing PEGylation of TiO2 Nanocrystals through a Combined Experimental and Computational Study.

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.

On the structural origin of free volume in 1-alkyl-3-methylimidazolium ionic liquid mixtures: a SAXS and 129Xe NMR study.

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.

Surface Characterization of TiO2 Polymorphic Nanocrystals through 1H-TD-NMR.

Nanocrystals (NCs) surface characterization is a fundamental step for understanding the physical and chemical phenomena involved at the nanoscale. Surface energy and chemistry depend on particle size and composition, and, in turn, determine the interaction of NCs with the surrounding environment, their properties and stability, and the feasibility of nanocomposites. This work aims at extracting more information on the surface of different titanium dioxide polymorphs using 1H-TD-NMR of water. Taking advantage of the interaction between water molecules and titanium dioxide NCs, it is possible to correlate the proton transverse relaxation times ( T2) as the function of the concentration and the specific surface area (δp· Cm) and use it as an indicator of the crystal phase. Examples of three different crystals phase, rutile, anatase, and brookite, have been finely characterized and their behavior in water solution have been studied with TD-NMR. The results show a linear correlation between relaxivity ( R2) and their concentration Cm. The resulting slopes, after normalization for the specific surface, represent the surface/water interaction and range from 1.28 g m-2 s-1 of 50 nm rutile nanocrystals to 0.52 for similar sized brookite. Even higher slopes (1.85) characterize smaller rutile NCs, in qualitative accordance with the trends of surface energy. Thanks to proton relaxation phenomena that occur at the NCs surface, it is possible to differentiate the crystal phase and the specific surface area of titanium dioxide polymorphs in water solution.

Local Order and Dynamics of Nanoconstrained Ethylene-Butylene Chain Segments in SEBS.

Subtle alterations in the mid-block of polystyrene-b-poly (ethylene-co-butylene)-b-polystyrene (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.

Photocatalytic Water-Splitting Enhancement by Sub-Bandgap Photon Harvesting.

Upconversion is a photon-management process especially suited to water-splitting cells that exploit wide-bandgap photocatalysts. Currently, such catalysts cannot utilize 95% of the available solar photons. We demonstrate here that the energy-conversion yield for a standard photocatalytic water-splitting device can be enhanced under solar irradiance by using a low-power upconversion system that recovers part of the unutilized incident sub-bandgap photons. The upconverter is based on a sensitized triplet-triplet annihilation mechanism (sTTA-UC) obtained in a dye-doped elastomer and boosted by a fluorescent nanocrystal/polymer composite that allows for broadband light harvesting. The complementary and tailored optical properties of these materials enable efficient upconversion at subsolar irradiance, allowing the realization of the first prototype water-splitting cell assisted by solid-state upconversion. In our proof-of concept device the increase of the performance is 3.5%, which grows to 6.3% if concentrated sunlight (10 sun) is used. Our experiments show how the sTTA-UC materials can be successfully implemented in technologically relevant devices while matching the strict requirements of clean-energy production.