In the last decades, plasmonic nanocrystals (NCs) have been subject of intense research due to their strong optical response. Indeed, the electric field of light induces a coherent oscillation of conduction electrons, known as "Local Surface Plasmon Resonance" (LSPR), which leads to a strong absorption peak typically in the UV-Vis - near IR (NIR) regions [1,2]. Among plasmonic NCs, degenerately doped semiconductors are particularly interesting for infrared plasmonics. In these NCs conduction electrons are generated by introducing aliovalent dopants. Among this class of materials, Tin-doped Indium Oxide (ITO) is an n-type semiconductor in which the aliovalent doping consists in the partial substitution of In3+ cations in the bixbyite In2O3 crystal structure with Sn4+. ITO NCs show a resonant peak in the NIR region, tunable by varying the dopant content (Sn%) [3]. Thanks to their infrared plasmonic properties, ITO NCs have been proposed in many different fields such as magnetoplasmonics and smart materials activated by NIR light [4,5]. The correlation between free electron parameters and the presence of dopant-related structural defects is an important task in the rationalization of the optical properties of these materials, and it is still far from being completely understood. Solid State NMR (SSNMR) appears particularly attractive for this scope [6-8], as the presence of free electrons affects several NMR properties of the nuclei. In this work, we present a SSNMR investigation on ITO NCs stabilized with oleic acid, containing an increasing amount of Sn. 119Sn SSNMR spectra and spin-counting experiments allowed us to identify different Sn species, correlated with different electronic properties. Further information was obtained by measuring 119Sn spin-lattice relaxation times (T1) at different temperatures. Optical and magneto-optical spectroscopies were also employed to extract free electrons par

Bone cancer and bone metastases are usually associated with severe bone pain and osteolysis, the latter being also accompanied by increased bone fragility and susceptibility to fracture. Nowadays, chemotherapy and/or radiotherapy represent the main treatments able to block the metastases progression. However, these treatments inhibit cell division without distinction between healthy and cancer cells, thus inducing many side effects in patients. Hence the need for developing innovative treatments able to inhibit metastases progression and, at the same time, to promote the formation of new tissue. In this contribution we present innovative organic-inorganic hybrid injectable materials designed to have the dual function of inhibiting cancer cells proliferation and inducing new bone tissue formation/mineralization [1, 2]. In particular we will show the results of a multinuclear Solid State Nuclear Magnetic Resonance investigation [3, 4] that allowed the phase behaviour and the structural features of the hybrid materials, before and after mineralization, to be characterized in detail. This research was funded by the Italian Ministry of Universities and Research (MUR), grant PRIN 'ACTION' 2017SZ5WZB.

Solid porous materials find widespread domestic and industrial applications, including construction and building, gas separation and storage, filtration and purification, ion exchange, energy storage, and heterogeneous catalysis. This class of materials encompasses fully inorganic or organic systems and organic/inorganic hybrid systems, with both crystalline and amorphous structure. The macroscopic behaviour of porous materials is strongly related to the structural and dynamic properties of their building units at molecular level, as well as to the interactions of the porous matrix with guest molecules. Solid-state NMR (SSNMR) spectroscopy and NMR relaxometry represent very powerful techniques for characterizing microscopic properties over wide space and time scales and drawing structure-properties relationships in porous materials. Thanks to the possibility of exploiting many different NMR-active nuclei and a variety of nuclear observables, the application of NMR methods allows molecular and supramolecular structure and motions of specific moieties of the porous materials to be investigated. In addition, information can be acquired on the dynamics of gaseous or liquid guests hosted in the porous matrix, as well as on host-guest interactions. In this lecture, the applicability of SSNMR spectroscopy and relaxometry experiments for looking inside porous materials will be discussed presenting several examples taken from the recent research work of the Pisa SSNMR group. In particular, the lecture will focus on structural properties and hydration of innovative cements characterized by multinuclear SSNMR [1,2] and 1H relaxometry [3,4] and on structural and dynamic properties and host-guest interactions of metal organic frameworks (MOFs) [5] and polymers of intrinsic microporosity (PIMs) for CO2 capture investigated by multinuclear SSNMR. Acknowledgements PRIN MUR (DOMINO project n. 2020P9KBKZ) is acknowledged for partially financing the research. References [1] M. Tonelli, F. Martini, L. Calucci, E. Fratini, M. Geppi, F. Ridi, S. Borsacchi, P. Baglioni, Dalton Trans., 2016, 45, 3294. [2] F. Martini, M. Tonelli, E. Fratini, M. Geppi, F. Ridi, S. Borsacchi, L. Calucci, Cem. Concr. Res., 2017, 102, 60-67. [3] F. Martini, S. Borsacchi, M. Geppi, M. Tonelli, F. Ridi, L. Calucci, Micropor. Mesopor. Mater., 2018, 269, 26-30. [4] F. Martini, S. Borsacchi, M. Geppi, C. Forte, L. Calucci, J. Phys. Chem. C 2017, 121, 26851-26859. [5] M. Cavallo, C. Atzori, M. Signorile, F. Costantino, D. Morelli Venturi, A. Koutsianos, K.A. Lomachenko, L. Calucci, F. Martini, A. Giovanelli, M. Geppi, V. Crocellà, M. Taddei, J. Mater. Chem. A, 2023, 11, 5568.

In recent years, metal halide perovskites (MHPs) have aroused a lot of enthusiasm in the materials science community due to their unique tunability, which allows a fine regulation of the desired properties. CsPbBr3 perovskite nanocrystals (Fig. 1) have shown highly attractive light emitting properties, thanks to their narrow emission bandwidths, high quantum-yield values, and the possibility to perform a fine tune of the emission wavelength by controlling the size of the nanocrystals [1]. In the last few years, Solid-State NMR spectroscopy (SSNMR) has emerged as one of the main techniques for an in-depth structural and dynamic characterization of MHPs [2-3]. In this work, a multinuclear SSNMR approach was adopted for a structural study of cubic CsPbBr3 nanoparticles stabilized with oleic acid and oleylamine. In particular, the surface ligands and their interactions with the nanocubes surface were investigated by 1H and 13C NMR experiments, while the structural investigation of the perovskite nanocubes was addressed by exploiting 207Pb and 133Cs spectral properties in comparison with bulk CsPbBr3. Static 207Pb NMR spectra indicated a possible contribution of chemical shift anisotropy from the 207Pb nuclei of the outer layer. The 133Cs NMR spectra showed signals with different chemical shifts for cesium atoms in at least three regions of the nanocubes, from the inner core to the surface, which were interpreted in terms of cubic layers with different distances from the surface using a simple geometrical model. This interpretation was also supported by 133Cs longitudinal relaxation time measurements [4]. Fig. 1. Structure of CsPbBr3 perovskite References [1] T.J.N. Hooper, Y. Fang, A.A.M. Brown, S.H. Pu, T.J. White. Nanoscale, 13, 15770 (2021) [2] D.J. Kubicki, S.D. Stranks, C.P. Grey, L. Emsley. Nat. Rev. Chem., 5, 624-645 (2021) [3] L. Piveteau, V. Morad, M.V. Kovalenko. J. Am. Chem. Soc., 142, 19413-19437 (2020) [4] A. Scarperi et al. Pure Appl. Chem. (2023) https://doi.org/10.1515/pac-2023-0110

Bone cancer and bone metastases are usually associated with severe bone pain and osteolysis, the latter being also accompanied by increased bone fragility and susceptibility to fracture. Nowadays, chemotherapy and/or radiotherapy represent the main treatments able to block the metastases progression. However, these treatments inhibit cell division without distinction between healthy and cancer cells, thus inducing many side effects in patients. Hence the need for developing innovative treatments able to inhibit metastases progression and, at the same time, to promote the formation of new tissue. In this contribution we present innovative organic-inorganic hybrid injectable materials designed to have the dual function of inhibiting cancer cells proliferation and inducing new bone tissue formation/mineralization [1, 2]. In particular we will show the results of a multinuclear Solid State Nuclear Magnetic Resonance investigation [3, 4] that allowed the phase behaviour and the structural features of the hybrid materials, before and after mineralization, to be characterized in detail. This research was funded by the Italian Ministry of Universities and Research (MUR), grant PRIN 'ACTION' 2017SZ5WZB. References [1] I. Fasolino, A. Soriente, L. Ambrosio, M.G. Raucci Nanomaterials 10, 1743, 1-15 (2020) [2] A. Fiorati, C. Linciano, C. Galante, M.G. Raucci, L. Altomare Materials 14, 4511 (2021) [3] R. Gelli, F. Martini, M. Geppi, S. Borsacchi, F. Ridi, P. Baglioni J. Colloid. Interf. Sci. 594, 802-811 (2021) [4] M. Geppi, S. Borsacchi, G. Mollica, C. A. Veracini Appl. Spectrosc. Rev. 44, 1-89 (2009)

Porous materials have attracted considerable scientific and technological interest due to their critical applications in many fields, such as membrane-based gas separation, building materials, adsorption and storage, catalysis, ion exchange, nanotechnology, etc. From a chemical and structural point of view, the definition of "porous materials" encompasses a wide variety of systems, including inorganic, hybrid organic-inorganic, and polymeric materials. Solid state NMR spectroscopy (ssNMR) has been showing its tremendous potential to clarify the often-intricate behavior of this class of materials at a molecular and nanometric level. Indeed, it provides a wide variety of tools, relying on the observation of different nuclei and the measurement of different spectral and relaxation properties, which can reveal information on structural and dynamic features on wide spatial and time scales, respectively [1,2]. This lecture will cover a selection of ssNMR studies aimed at unravelling these features, and especially the dynamic aspects, on different classes of porous materials. In particular, the case studies presented will concern microporous polymers for solid-state gas separation and ion-exchange membranes, 1D coordination polymers devised to sequester volatile organic compounds, Ce-based metal organic frameworks with potential applications in the field of CO2 capture, and Mg- and Ca-based cement pastes. The main focus will be put on the detailed description of motional processes of polymeric chains and organic ligands and on the interactions and dynamic behavior of adsorbed water and other guest molecules. It will be shown how, depending on the type of material, on the available nuclei, on the desired detail of the information, and on the time scale of the motion, different experimental approaches can be used, combined with different analyses of the nuclear parameters measured in terms of suitable theoretical models. The experiments employed include static and Magic Angle Spinning as well as high- and low-field techniques, and in particular they rely on: 1H and 19F on-resonance FID analysis; 1H, 19F and 13C spin-lattice relaxation times in the laboratory frame and of 1H spin-lattice relaxation times in the rotating frame; 13C chemical shift anisotropy; 2H quadrupolar interaction. References [1] K. Mu?ller, and M. Geppi Solid State NMR: Principles, Methods, and Applications, Wiley ed. (2021). [2] S. Li et al. Adv. Mater. 32, 2002879 (2020).

In the past years, Lead Halide Perovskites (LHPs), with general formula APbX3 (A = methylammonium MA+, formamidinium FA+, Cs+; X = Cl-, Br-, I-), have received great levels of attention due to their remarkable optoelectronic properties, easy processability, abundant constituent elements, and wide compositional tunability [1]. Recent progress is mainly attributed to the exploration of various crystal engineering strategies (i.e. compositional and dimensional engineering) aimed at pushing the efficiencies higher, tuning properties, and overcoming stability issues. In 3-dimensional (3D) perovskites, the use of mixed-ion structures, obtained by introducing dopants into the perovskite structure, results in higher perovskite solar cell performance. Lowering the dimensionality of perovskites from 3D to 2D (by sandwiching organic cations, called spacers, between perovskite conductor layers) improves ambient stability, although at the expense of efficiency. Similarly, all-inorganic perovskite nanocrystals (where A is usually Cs+) show higher thermal stability and higher photoluminescence quantum yields with respect to bulk perovskites, although efficiency in solar cells is lower. Solid-State Nuclear Magnetic Resonance (SSNMR) stands out as characterization technique for LHPs for its ability to study ion dynamics, compositional variations and ion incorporation, chemical interactions, and degradation mechanisms, and can therefore be used to advance our understanding of these multifaceted materials [2]. In this study, a multiple-cation lead mixed-halide perovskite Cs0.05FA0.81MA0.14PbI2.55Br0.45[3], 2D Ruddlesden-Popper phases containing butylammonium (BA) as spacer (BA2MAn-1PbnI3n+1 with n=1-4, Figure 1), and CsPbBr3 nanocubes [4] were investigated by a range of multinuclear SSNMR techniques. 133Cs, 207Pb, 1H, and 13C spectra were recorded under Magic Angle Spinning and static conditions; variable temperature measurements of 13C and 1H spin-lattice relaxation times (T1) allowed dynamic properties of the organic cations in the series of samples to be investigated. The obtained structural and dynamic features of these systems have been compared with those of 3D pure MAPbI3 and discussed in relation to very recent literature. References: [1] J. Y. Kim, et al., Chem. Rev., 120, 7867 (2020). [2] D. J. Kubicki, et al., Nat. Rev. Chem., 5, 624-645 (2021). [3] N. Landi, et al., J. Phys. Chem. Lett.,13, 9517-9525 (2022). [4] A. Scarperi, et al., Pure Appl. Chem., 0 (2023).

Alessandro Volta e l'elettrochimica come volano per un futuro sostenibile: Un evento IUPAC italiano per l'International Year of Basic Sciences for Sustainable Development

Cesium lead bromide perovskite (CsPbBr3) nanocrystals have raised impressive interest as efficient and stable optoelectronic materials. Size and morphology play important roles in the final performances of these materials and advanced characterization studies are needed to elucidate structural and surface properties. In this work, CsPbBr3 cubic nanocrystals were obtained by colloidal synthesis and characterized by multinuclear Solid State NMR (SSNMR), complemented by X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and optical spectroscopy. The multinuclear NMR approach allowed the different components of the nanocubes to be separately observed. In particular, the surface ligands and their interactions with the nanocubes surface were investigated by H-1 and C-13 NMR experiments, while the structural investigation of the perovskite nanocubes was addressed by exploiting Pb-207 and Cs-133 spectral properties in comparison with bulk CsPbBr3. Static Pb-207 NMR spectra indicated a possible contribution of chemical shift anisotropy from the Pb-207 nuclei of the outer layer. The Cs-133 NMR spectra showed signals with different chemical shifts for cesium atoms in at least three regions of the nanocubes, from the inner core to the surface, which were interpreted in terms of cubic layers with different distances from the surface using a simple geometrical model. This interpretation was also supported by Cs-133 longitudinal relaxation time measurements.

Composting, vermicomposting, and anaerobic digestion are three commonly applied processes for the transformation of organic waste into valuable products for soil amendment. The application of compost, vermicompost, and digestate to soil requires specific properties, such as maturity and stability, strongly related to the composition of organic matter. 13C solid-state Nuclear Magnetic Resonance (SSNMR) has often been applied to follow the transformation of organic matter during waste treatment processes, as well as to assess the quality of the produced amendments and the effectiveness of the treatments. Thanks to the possibility of associating the 13C chemical shift to different functional groups of biomacromolecules present in the waste feedstocks and in the final products, thorough characterizations of organic matter have been performed exploiting 13C cross-polarization magic angle spinning experiments, and semiquantitative descriptions of the evolution of the different groups during composting, vermicomposting and anaerobic digestion have been reported. Here, these studies are reviewed with the aim of highlighting the potential of the application of 13C SSNMR to these complex materials, as well as the critical issues and perspectives.

Hypothesis Sodium oleate (NaOL) self-aggregates in water forming rodlike micelles with different length depending on NaOL concentration; when KCl is added wormlike micelles form, which entangle giving rise to a viscoelastic dispersion. It is expected that aggregates with different size and shape exhibit different internal and overall molecular motions and collective dynamics. Experiments Two low viscosity NaOL/water and two viscoelastic NaOL/KCl/water formulations with different NaOL concentration (0.23 and 0.43 M) were investigated by 1H fast field cycling NMR relaxometry over broad temperature and Larmor frequency ranges, after a first screening by 1H and 13C NMR spectroscopy at high frequency. Findings The analysis of the collected data indicated that fast conformational isomerization and rotation of NaOL about its long molecular axis and lateral diffusion of NaOL around the axis of the cylindrical aggregates are slightly affected by the aggregate shape and length. On the other hand, fluctuations of the local order director are quite different in the fluid and viscoelastic systems, reflecting the shape and size of the aggregates. Quantitative information was obtained on activation energy for fast internal and overall motions, correlation times and activation energy for lateral diffusion, and coherence length for collective order fluctuations.

Nell'ambito dell'accordo di collaborazione tra CNR e Scapigliato S.r.l. sulla ottimizzazione del processo di trattamento del sottovaglio del TMB e del digestato mediante sistemi di lombricoltura, a inizio 2022 è stata intrapresa una sperimentazione a livello di laboratorio sul vermicompostaggio di sottovaglio da trattamento meccanico dei rifiuti solidi urbani (RSU) e di digestato anaerobico (D) e loro miscele, anche con altri materiali quali scarto verde e letame. Il processo di vermicompostaggio è stato monitorato dal 22 marzo al 26 luglio 2022.

Elastomers are polymeric materials extensively used in the tire industry. These materials are obtained by vulcanization of one (or more) polydiene polymer(s) in the presence of sulfur and other additives (accelerators, activators, plasticizers, fillers, etc.). During this process, chemical crosslinks are formed between the polymeric chains, providing the final product's elasticity and durability. Depending on the formulation and the vulcanization conditions, other mechanical properties can be obtained. Importantly, such properties are strongly related to the microscopic structure of the polymeric network [1]. Consequently, the investigation of microscopic and macroscopic properties giving access to information on the network structure in relation to the vulcanization conditions is fundamental for the design of optimized elastomeric materials. In this context, 1H time-domain NMR (TD-NMR) represents a valuable tool to gain insights into the molecular dynamics of the polymeric chains. This technique allows to measure NMR observables (1H T1 and T2 relaxation times and 1H-1H residual dipolar couplings (Dres)), which depend on the modulation of 1H-1H dipolar couplings by segmental motions. These motions are quite fast in elastomers above the glass transition temperature, but are anisotropic, resulting in residual 1H-1H dipolar interactions, which depend on the amount and distribution of topological constraints in the polymeric network [2]. In this work, natural and isoprene rubbers vulcanized at different curing temperatures and different sulfur contents have been investigated by exploiting 1H TD-NMR techniques, including 1H multiple-quantum experiments for the measurements of Dres, Carr-Purcell-Meiboom-Gill pulse sequence for the evaluation of 1H T2 relaxation times, and field cycling NMR relaxometry for the measurements of 1H T1 relaxation times on a wide range of Larmor frequencies (10 kHz-35 MHz). The NMR observables were compared with the crosslink density or macroscopic properties of the material that depend on this quantity, obtained using routinely employed methods in industrial analyses, allowing to gain insight into the effects of the formulation and the vulcanization conditions on the structure and dynamics of the polymeric networks [3]. References [1] S. P. O. Danielsen, H. K. Beech, S. Wang, B. M. El-Zaatari, X. Wang, L. Sapir, T. Ouchi, Z. Wang, P. N. Johnson, Y. Hu, D. J. Lundberg, G. Stoychev, S. L. Craig, J. A. Johnson, J. A. Kalow, B. D. Olsen and M. Rubinstein Chem. Rev. 121, 5042-5092 (2021) [2] K. Saalwächter Rubber Chem. Technol. 85, 350-386 (2012) [3] F. Nardelli, L. Calucci, E. Carignani, S. Borsacchi, M. Cettolin, M. Arimondi, L. Giannini, M. Geppi and F. Martini Polymers 14, 767 (2022)

In the fast-developing research of improved and sustainable materials for optoelectronics, 2D Lead Halide Perovskites (LHP) have attracted considerable attention because they offer the possibility of tunable band gap and enhanced environmental stability with respect to the corresponding 3D perovskites. 2D Ruddlesden-Popper (RP) perovskites can be prepared by adding a large organic mono ammonium cation, L+, in the precursor solution. In this way the 3D structure of corner-sharing octahedra (ABX3) is disrupted and a structure with a bilayer of spacer cations between metal halide sheets is formed (L2An-1BnX3n+1). For example, butylammonium (BA+) is a suitable organic cation to force the archetypical perovskite MAPbI3 into 2D RP perovskites BA2MAn-1PbnI3n+1 (Figure 1), which are the object of the present study. The layer thickness of metal halide sheets is specified by n and can be adjusted by tuning precursor stoichiometry. Solid-State NMR stands out as characterization technique for LHP for its ability to study ion dynamics, compositional variations and ion incorporation, chemical interactions, and degradation mechanisms [1,3]. In this work, the 2D RP perovskites BA2MAn-1PbnI3n+1 with n=1-4 have been characterized by 207Pb, 1H, and 13C Solid-State NMR, both under Magic Angle Spinning and static conditions. The structural features of these systems have been compared with those of 3D MAPbI3 and discussed in relation to very recent literature [3]. [1] W. M. J. Franssen, A. P. M. Kentgens, Solid State Nucl. Magn. Reson., 100 (2019) 36-44 [2] L. Piveteau, V. Morad, M. V. Kovalenko, J. Am. Chem. Soc. 142 (2020) 19413-19437 [3] D. J. Kubicki, S. D. Stranks, C. P. Grey, L. Emsley Nat Rev Chem 5 (2021) 624-645 [4] J. Lee, W. Lee, K. Kang, T. Lee, S. K. Lee, Chem. Mater., 33 (2021) 370-377

Elastomers are polymeric materials extensively used for manufacturing a wide range of products for industrial applications, especially in the tire industry. These materials are obtained by vulcanization of one (or more) polydiene polymer(s) in the presence of sulfur and other additives (accelerators, activators, plasticizers, reinforcing fillers, etc.). During this process, chemical crosslinks are formed between the polymeric chains, which provide elasticity and durability to the final product. Furthermore, depending on the formulation and the vulcanization conditions, other mechanical properties required for industrial applications can be obtained. Importantly, such macroscopic properties are strongly related to the microscopic structure of the polymeric network [1]. Consequently, the investigation of microscopic and macroscopic properties giving access to information on the network structure in relation to the vulcanization conditions is fundamental for the optimization of processing and performance of elastomeric materials. In this context, 1H time-domain NMR (TD-NMR) represents a valuable tool to gain insights into the molecular dynamics of the polymeric chains. In fact, this technique allows to measure NMR observables (1H T1 and T2 relaxation times and 1H-1H residual dipolar couplings (Dres)), which depend on the modulation of 1H-1H dipolar couplings by segmental motions. These motions are quite fast in elastomers above glass transition temperature, but are anisotropic, resulting in residual 1H-1H dipolar interactions, which depend on the amount and distribution of topological constraints in the polymeric network [2]. In this work, natural and isoprene rubbers vulcanized at different curing temperatures and different sulfur contents have been investigated by exploiting 1H TD-NMR techniques, including 1H multiple-quantum experiments for the measurements of Dres, Carr-Purcell-Meiboom-Gill pulse sequence for the evaluation of 1H T2 relaxation times, and field cycling NMR relaxometry for the measurements of T1 relaxation times on a wide range of Larmor frequencies (10 kHz-35 MHz). The NMR observables were compared with the crosslink density or macroscopic properties of the material that depend on this quantity, obtained using routinely employed methods in industrial analyses, allowing to gain insight into the effects of the formulation and the vulcanization conditions on the structure and dynamics of the polymeric networks [3]. [1] S. P. O. Danielsen et al., Chem. Rev. 121 (2021) 5092 [2] K. Saalwächter, Rubber Chem. Technol. 85 (2012) 350 [3] F. Nardelli et al., Polymers 14 (2022) 767

Elastomers are polymeric materials extensively used for manufacturing a wide range of products for industrial applications, especially in the tire industry. These materials are obtained by vulcanization of one (or more) polydiene polymer(s) in the presence of sulfur and other additives (accelerators, activators, plasticizers, reinforcing fillers, etc.). During this process, chemical crosslinks are formed between the polymeric chains, which provide elasticity and durability to the final product. Furthermore, depending on the formulation and the vulcanization conditions, other mechanical properties required for industrial applications can be obtained. Importantly, such macroscopic properties are strongly related to the microscopic structure of the polymeric network [1]. Consequently, the investigation of microscopic and macroscopic properties giving access to information on the network structure in relation to the vulcanization conditions is fundamental for the optimization of processing and performance of elastomeric materials. In this context, 1H time-domain NMR (TD-NMR) represents a valuable tool to gain insights into the molecular dynamics of the polymeric chains. In fact, this technique allows to measure NMR observables (1H T1 and T2 relaxation times and 1H-1H residual dipolar couplings (Dres)), which depend on the modulation of 1H-1H dipolar couplings by segmental motions. These motions are quite fast in elastomers above glass transition temperature, but are anisotropic, resulting in residual 1H-1H dipolar interactions, which depend on the amount and distribution of topological constraints in the polymeric network [2]. In this work, natural and isoprene rubbers vulcanized at different curing temperatures and different sulfur contents have been investigated by exploiting 1H TD-NMR techniques, including 1H multiple-quantum experiments for the measurements of Dres, Carr-Purcell-Meiboom-Gill pulse sequence for the evaluation of 1H T2 relaxation times, and field cycling NMR relaxometry for the measurements of T1 relaxation times on a wide range of Larmor frequencies (10 kHz-35 MHz). The NMR observables were compared with the crosslink density or macroscopic properties of the material that depend on this quantity, obtained using routinely employed methods in industrial analyses, allowing to gain insight into the effects of the formulation and the vulcanization conditions on the structure and dynamics of the polymeric networks [3]. [1] S. P. O. Danielsen et al., Chem. Rev. 121 (2021) 5092 [2] K. Saalwächter, Rubber Chem. Technol. 85 (2012) 350 [3] F. Nardelli et al., Polymers 14 (2022) 767

Elastomers are polymeric materials extensively used for manufacturing a wide range of products for industrial applications, especially in the tire industry. These materials are obtained by vulcanization of one (or more) polydiene polymer(s) in the presence of sulfur and other additives (accelerators, activators, plasticizers, reinforcing fillers, etc.). During this process, chemical crosslinks are formed between the polymeric chains, which provide elasticity and durability to the final product. Furthermore, depending on the formulation and the vulcanization conditions, other mechanical properties required for industrial applications can be obtained. Importantly, such macroscopic properties are strongly related to the microscopic structure of the polymeric network [1]. Consequently, the investigation of microscopic and macroscopic properties giving access to information on the network structure in relation to the vulcanization conditions is fundamental for the optimization of processing and performance of elastomeric materials. In this context, 1H time-domain NMR (TD-NMR) represents a valuable tool to gain insights into the molecular dynamics of the polymeric chains. In fact, this technique allows to measure NMR observables (1H T1 and T2 relaxation times and 1H-1H residual dipolar couplings (Dres)), which depend on the modulation of 1H-1H dipolar couplings by segmental motions. These motions are quite fast in elastomers above glass transition temperature, but are anisotropic, resulting in residual 1H-1H dipolar interactions, which depend on the amount and distribution of topological constraints in the polymeric network [2]. In this work, natural and isoprene rubbers vulcanized at different curing temperatures and different sulfur contents have been investigated by exploiting 1H TD-NMR techniques, including 1H multiple-quantum experiments for the measurements of Dres, Carr-Purcell-Meiboom-Gill pulse sequence for the evaluation of 1H T2 relaxation times, and field cycling NMR relaxometry for the measurements of T1 relaxation times on a wide range of Larmor frequencies (10 kHz-35 MHz). The NMR observables were compared with the crosslink density or macroscopic properties of the material that depend on this quantity, obtained using routinely employed methods in industrial analyses, allowing to gain insight into the effects of the formulation and the vulcanization conditions on the structure and dynamics of the polymeric networks [3]. [1] S. P. O. Danielsen et al., Chem. Rev. 121 (2021) 5092 [2] K. Saalwächter, Rubber Chem. Technol. 85 (2012) 350 [3] F. Nardelli et al., Polymers 14 (2022) 767

Mixed-cation lead mixed-halide perovskites are the best candidates for perovskite-based photovoltaics, thanks to their higher efficiency and stability compared to the single-cation single-halide parent compounds. TripleMix (Cs0.05MA0.14FA0.81PbI2.55Br0.45 with FA = formamidinium and MA = methylammonium) is one of the most efficient and stable mixed perovskites for single-junction solar cells. The microscopic reasons why triple-cation perovskites perform so well are still under debate. In this work, we investigated the structure and dynamics of TripleMix by exploiting multinuclear solid-state nuclear magnetic resonance (SSNMR), which can provide this information at a level of detail not accessible by other techniques. 133Cs, 13C, 1H, and 207Pb SSNMR spectra confirmed the inclusion of all ions in the perovskite, without phase segregation. Complementary measurements showed a peculiar longitudinal relaxation behavior for the 1H and 207Pb nuclei in TripleMix with respect to single-cation single-halide perovskites, suggesting slower dynamics of both organic cations and halide anions, possibly related to the high photovoltaic performances.

This work unravels for the first time the concentration dependent retarding effect of borax on tri-magnesium phosphate-based cements by studying the hydration and the phases formed in the set cements, exploiting multiple characterization techniques. In the presence of borax, the hydration was found to be slower and less exothermic, leading to the formation of struvite without newberyite, with no effect on cement's strength. The observed boron species allowed us to ascribe the retardation to the complexation of NH4+ and Mg2+ by borate and polyborate anions.