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Erionite is a zeolite representing a well-known health hazard. In fact, exposure of humans to its fibers has been unequivocally associated with occurrence of malignant mesothelioma. For this reason, a multi-methodological approach, based upon field investigation, morphological characterization, scanning electron microscopy (SEM)/energy-dispersive spectroscopy (EDS) chemical analysis, and structure refinement through X-ray powder diffraction (XRPD), was applied to different samples of potentially carcinogenic erionite from Northern Italy. The studied crystals have a chemical composition ranging from erionite-Ca to erionite-Na and display variable morphologies, varying from prismatic, through acicular and fibrous, to extremely fibrous asbestiform habits. The fibrous samples were characterized by an unusual preferred partition of aluminum (Al) at tetrahedral site T1 instead of tetrahedral site T2. Further, a mismatch between the a-parameter of erionite-Ca and levyne-Ca that are intergrown in the asbestiform sample was detected. This misfit was coupled to a relevant micro-strain to maintain structure coherency at the boundary. Erionite occurs in 65% of the investigated sites, with an estimated quantity of 10 to 40 vol% of the associated minerals. The presence of this mineral is of concern for risk to human health, especially if one considers the vast number of quarries and mining-related activities that are operating in the zeolite host rocks. The discovery of fibrous and asbestiform erionite in Northern Italy suggests the need for a detailed risk assessment in all Italian areas showing the same potential hazard, with specific studies such as a quantification of the potentially respirable airborne fibers and targeted epidemiological surveillance.
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Carcinógenos/toxicidade , Exposição Ambiental , Zeolitas/toxicidade , Animais , Carcinógenos/análise , Monitoramento Ambiental , Geologia , Humanos , Itália , Medição de Risco , Zeolitas/análiseRESUMO
We present an exhaustive computational study on the effect of high pressure on normal alcohols with alkyl chains with lengths of three-to-eight carbon atoms. 1-Propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, and 1-octanol were studied by using classical molecular dynamics simulations and applying pressures in the range of 1 to 104 â bar. The results of our calculations show that high-pressure values affect the structure significantly. In particular, we have observed a marked difference in behavior for alcohols with chain lengths below six and those with more than six or seven carbon atoms, with hexanol and heptanol being boundary cases. We have named the model with the most shrunk alkyl chains as the Asclepius form inspired by the Rod of Asclepius, the universally known symbol of medicine, in which a snake is coiled around a rod.
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In this paper, small angle X-ray scattering has been used to study a series of ionic liquids, alkylammonium alkanoates ([N0 0 0 n][CmCO2]), with varying alkyl chain lengths in the cation and the anion. We investigate the behaviour and the structure of such ionic liquids in their neat state, and in binary mixtures with water. To the best of our knowledge, this is the first structural study dealing with the behaviour of propylammonium propanoate [N0 0 0 3][C2CO2], butylammonium propanoate [N0 0 0 4][C2CO2], propylammonium butanoate [N0 0 0 3][C3CO2] and butylammonium butanoate [N0 0 0 4][C3CO2] when mixed in water. Generally, in the ionic liquids containing alkyl chains on both the cation and the anion, the correlation distance and the resulting scattering peak, which signal intermediate range order, are affected equally by both of the chains. The interesting result obtained regarding these systems is that the shift of the pre- and principal peaks with the addition of water depends on the overall molar concentration of the chains and is generally cumulative. Although, for a given sum of cation and anion chain lengths, the shift is reliant on the cation-anion combination in the neat state, it is not the case in their mixtures with water. In some recent papers, it has been reported that with addition of water, the pre-peak position remains constant, but our results show a shift in both pre- and principal Q peaks.
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This study focuses on the dissolution process and surface characterization of amosite fibres following interaction with a mimicked Gamble's solution at a pH of 4.5 and T = 37 °C, up to 720 h. To achieve this, a multi-analytical approach was adopted, and the results were compared to those previously obtained on a sample of asbestos tremolite and UICC crocidolite, which were investigated under the same experimental conditions. Combining surface chemical data obtained by XPS with cation release quantified by ICP-OES, an incongruent behaviour of the fibre dissolution was highlighted for amosite fibres, similarly to asbestos tremolite and UICC crocidolite. In particular, a preferential release of Mg and Ca from the amphibole structure was observed, in agreement with their Madelung site energies. Notably, no Fe release from amosite fibres was detected in our experimental conditions (pH of 4.5 and atmospheric pO2), despite the occurrence of Fe(II) at the M(4) site of the amphibole structure, where cations are expected to be rapidly leached out during mineral dissolution. Moreover, the oxidation of both the Fe centres initially present on the fibre surface and those promoted from the bulk, because of the erosion of the outmost layers, was observed. Since biodurability (i.e., the resistance to dissolution) is one of the most important toxicity parameters, the knowledge of the surface alteration of asbestos possibly occurring in vivo may help to understand the mechanisms at the basis of its long-term toxicity.
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Erionite is a non-asbestos fibrous zeolite classified by the International Agency for Research on Cancer (IARC) as a Group 1 carcinogen and is considered today similar to or even more carcinogenic than the six regulated asbestos minerals. Exposure to fibrous erionite has been unequivocally linked to cases of malignant mesothelioma (MM) and this killer fibre is assumed to be directly responsible for more than 50% of all deaths in the population of the villages of Karain and Tuzköy in central Anatolia (Turkey). Erionite usually occurs in bundles of thin fibres and very rarely as single acicular or needle-like fibres. For this reason, a crystal structure of this fibre has not been attempted to date although an accurate characterization of its crystal structure is of paramount importance for our understanding of the toxicity and carcinogenicity. In this work, we report on a combined approach of microscopic (SEM, TEM, electron diffraction), spectroscopic (micro-Raman) and chemical techniques with synchrotron nano-single-crystal diffraction that allowed us to obtain the first reliable ab initio crystal structure of this killer zeolite. The refined structure showed regular T-O distances (in the range 1.61-1.65â Å) and extra-framework content in line with the chemical formula (K2.63Ca1.57Mg0.76Na0.13Ba0.01)[Si28.62Al7.35]O72·28.3H2O. The synchrotron nano-diffraction data combined with three-dimensional electron diffraction (3DED) allowed us to unequivocally rule out the presence of offretite. These results are of paramount importance for understanding the mechanisms by which erionite induces toxic damage and for confirming the physical similarities with asbestos fibres.
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Amianto , Mesotelioma , Zeolitas , Humanos , Zeolitas/análise , Mesotelioma/epidemiologia , Turquia/epidemiologia , Exposição Ambiental , CarcinógenosRESUMO
The environmental impact of natural occurrences of asbestos (NOA) and asbestos-like minerals is a growing concern for environmental protection agencies. The lack of shared sampling and analytical procedures hinders effectively addressing this issue. To investigate the hazard posed by NOA, a multidisciplinary approach that encompasses geology, mineralogy, chemistry, and toxicology is proposed and demonstrated here, on a natural occurrence of antigorite from a site in Varenna Valley, Italy. Antigorite is, together with chrysotile asbestos, one of the serpentine polymorphs and its toxicological profile is still under debate. We described field and petrographic analyses required to sample a vein and to evaluate the NOA-hazard. A combination of standardized mechanical stress and automated morphometrical analyses on milled samples allowed to quantify the asbestos-like morphology. The low congruent solubility in acidic simulated body fluid, together with the toxicity-relevant surface reactivity due to iron speciation, signalled a bio-activity similar or even greater to that of chrysotile. Structural information on the genetic mechanism of antigorite asbestos-like fibres in nature were provided. Overall, the NOA site was reported to contain veins of asbestos-like antigorite and should be regarded as source of potentially toxic fibres during hazard assessment procedure.
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This study explored the morphological, mineralogical, and physico-chemical features of carcinogenic erionite and other possibly hazardous zeolites, such as mesolite and thomsonite, while also investigating the interacting capability of the mineral surface at the liquid/solid interface. Extremely fibrous erionite is K+ and Ca2+-rich and shows the highest Si/Al ratio (3.38) and specific surface area (8.14 m2/g). Fibrous mesolite is Na+ and Ca2+-rich and displays both a lower Si/Al ratio (1.56) and a smaller specific surface area (1.56 m2/g). The thomsonite composition shows the lowest values of Si/Al ratio (1.23) and specific surface area (0.38 m2/g). Electron paramagnetic resonance data from selected spin probes reveal that erionite has a homogeneous site distribution and interacts well with all spin probes. The surfaces of mesolite and thomsonite are less homogeneous and closer polar sites were found through consequent interaction with the probes. The mesolite surface can also clearly interact but with a lower strength and may represent a potential health hazard for humans, though with a lower degree if compared to erionite. The thomsonite surface is not inert and interacts with the probes with a low-grade capability. We can expect small fragments of thomsonite to interact with the biological environment, though with a low-grade intensity.
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Zeolitas , Carcinógenos , Espectroscopia de Ressonância de Spin Eletrônica , HumanosRESUMO
This study aimed at investigating the surface modifications occurring on amphibole asbestos (crocidolite and tremolite) during leaching in a mimicked Gamble's solution at pH of 4.5 and T = 37 °C, from 1 h up to 720 h. Results showed that the fibre dissolution starts with the release of cations prevalently allocated at the various M- and (eventually) A-sites of the amphibole structure (incongruent dissolution). The amount of released silicon, normalized to fibre surface area, highlighted a leaching faster for the crocidolite sample, about twenty times higher than that of tremolite. Besides, the fast alteration of crocidolite promotes the occurrence of Fe centres in proximity of the fibre surface, or possibly even exposed, particularly in the form of Fe(II), of which the bulk is enriched with respect to the oxidized surface. Conversely, for tremolite fibres the very slow fibre dissolution prevents the underlying cations of the bulk to be exposed on the mineral surface, and the iron oxidation, faster than the leaching process, significantly depletes the surface Fe(II) centres initially present. Results of this work may contribute to unravel possible correlations between surface properties of amphibole asbestos and its long-term toxicity.
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Manganese oxides are important geomaterials, used in a large number of applications. For instance, as pigments in art works or in the treatment and removal of heavy metals from drinking water. Particularly, ramsdellite [Mn4+O2] and groutellite [(Mn0.5 4+,Mn0.5 3+)O1.5(OH)0.5], because of their 2 × 1 frameworks that enable proton diffusion, are very important cathode materials. Manganese oxides commonly occur as crypto-crystalline and very fine mixtures of different Mn-phases, iron oxides, silicates and carbonates. Thus, proper characterization can be a difficult task using XRPD. The lack of Raman data on groutellite and the little and conflicting data on ramsdellite do not allow their proper identification by Raman spectroscopy. In this work we characterize natural mixtures of ramsdellite and groutellite by combining SEM-EDS, XRPD, FT-IR and Raman spectroscopy, to provide reference Raman spectra. Our data show that they have a typical and unmistakable spectra, allowing clear recognition. Moreover, we have investigated their laser-induced degradation. Our data show that groutellite transforms into ramsdellite, by the loss of H+ and the oxidation of Mn3+ to Mn4+, already at a very low laser power. Further increasing the laser power the formation of hausmannite [Mn2+Mn2 3+O4] occurs via the reduction of Mn cations. Our data can be used to study the discharge mechanism in cathodic battery materials, by monitoring the Mn reduction from ramsdellite to groutellite, and finally to groutite [α-Mn3+OOH]. Moreover, Raman mapping allows the study of their distribution in all the investigated samples and, indirectly, those of H+ and Mn3+, which plays a key-role in electrochemical activity of these compounds.
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This study discloses the morphological and chemical-structural modifications that occur during thermal degradation of amphibole asbestos. Low-iron tremolite and iron-rich crocidolite were heated at temperatures ranging from r.t. to 1200 °C. Heating promoted a complex sequence of iron oxidation, migration and/or clustering and, finally, the formation of brittle fibrous pseudomorphs consisting of newly formed minerals and amorphous nanophases. The effects of the thermal modifications on toxicologically relevant asbestos reactivity were evaluated by quantifying carbon- and oxygen-centred, namely hydroxyl (OH), radicals. Heating did not alter carbon radicals, but largely affected oxygen-centred radical yields. At low temperature, reactivity of both amphiboles decreased. At 1200 °C, tremolite structural breakdown was achieved and the reactivity was further reduced by migration of reactive iron ions into the more stable TO4 tetrahedra of the newly formed pyroxene(s). Differently, crocidolite breakdown at 1000 °C induced the formation of hematite, Fe-rich pyroxene, cristobalite, and abundant amorphous material and restored radical reactivity. Our finding suggests that thermally treated asbestos and its breakdown products still share some toxicologically relevant properties with pristine fibre. Asbestos inertization studies should consider morphology and surface reactivity, beyond crystallinity, when proving that a thermally inactivated asbestos-containing material is safe.
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The kinetics of the alpha-PcCu --> beta-PcCu conversion in air has been followed, under isothermal conditions, in situ real-time in the 423-443 K temperature range. Data have been fitted following the JMAK model. The reaction order of the kinetics at 423 K is consistent with a diffusion controlled, deceleratory nucleation rate process for 2D laminar particles, whereas at higher temperatures it is consistent with a phase boundary controlled, deceleratory nucleation rate process for 2D laminar particles. At 423 K, the overall transformation mechanism implies three steps: growth of the alpha-PcCu phase, disordering of adjacent columns of molecules of phthalocyanine, and nucleation and growth of the beta-PcCu phase. The calculated empirical activation energy is of 187 kJ/mol significantly greater than that for the alpha-PcCo --> beta-PcCo conversion. This fact seems to support the reported different structures of alpha-PcCo and alpha-PcCu. Investigation of the thermal behavior of beta-PcCu indicates a strongly anisotropic thermal expansion that follows the alpha(c) >> alpha(a) approximately = alpha(b) trend. Moreover, the beta angle decreases with increasing temperature. Such anisotropy is consistent with the geometry of the very weak N3...H3 hydrogen bond which acts mainly along the c axis.
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First principle calculations of periodic crystal structure were successfully combined with powder X-ray diffraction measures to determine the structure of orotaldehyde monohydrate. This approach was particularly helpful to overcome the inadequacy of powder X-ray diffraction to reliably locate the hydrogen atoms of the intermolecular bond network of the crystal molecules. Density functional calculations were accomplished for the free molecule and its cyclic dimers showing that the most stable centrosymmetric dimer is the building block of the molecular crystal.
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Lightweight multifunctional electromagnetic (EM) absorbing materials with outstanding thermal properties, chemical resistance and mechanical stability are crucial for space, aerospace and electronic devices and packaging. Therefore, 3D porous graphene aerogels are attracting ever growing interest. In this paper we present a cost effective lightweight 3D porous graphene-based aerogel for EM wave absorption, constituted by a poly vinylidene fluoride (PVDF) polymer matrix filled with graphene nanoplatelets (GNPs) and we show that the thermal, electrical, mechanical properties of the aerogel can be tuned through the proper selection of the processing temperature, controlled either at 65 °C or 85 °C. The produced GNP-filled aerogels are characterized by exceptional EM properties, allowing the production of absorbers with 9.2 GHz and 6.4 GHz qualified bandwidths with reflection coefficients below -10 dB and -20 dB, respectively. Moreover, such aerogels show exceptional thermal conductivities without any appreciable volume change after temperature variations. Finally, depending on the process parameters, it is shown the possibility to obtain water repellent aerogel composites, thus preventing their EM and thermal properties from being affected by environmental humidity and allowing the realization of EM absorber with a stable response.
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Novel polymer-based piezoelectric nanocomposites with enhanced electromechanical properties open new opportunities for the development of wearable energy harvesters and sensors. This paper investigates how the dissolution of different types of hexahydrate metal salts affects ß-phase content and piezoelectric response (d33) at nano- and macroscales of polyvinylidene fluoride (PVDF) nanocomposite films. The strongest enhancement of the piezoresponse is observed in PVDF nanocomposites processed with Mg(NO3)2â 6H2O. The increased piezoresponse is attributed to the synergistic effect of the dipole moment associated with the nucleation of the electroactive phase and with the electrostatic interaction between the CF2 group of PVDF and the dissolved salt through hydrogen bonding. The combination of nanofillers like graphene nanoplatelets or zinc oxide nanorods with the hexahydrate salt dissolution in PVDF results in a dramatic reduction of d33, because the nanofiller assumes a competitive role with respect to H-bond formation between PVDF and the dissolved metal salt. The measured peak value of d33 reaches the local value of 13.49 pm/V, with an average of 8.88 pm/V over an area of 1 cm². The proposed selection of metal salt enables low-cost production of piezoelectric PVDF nanocomposite films, without electrical poling or mechanical stretching, offering new opportunities for the development of devices for energy harvesting and wearable sensors.
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Fibrous erionite-Na from Rome (Oregon, USA) was K-exchanged and characterized from the structural point of view. In addition, the modifications experienced after contact with a Fe(II) source were investigated for evaluating if the large potassium ions, blocking off nearly all the erionite cavity openings, might prevent the Fe(II) binding process, which is currently assumed to be one of the reasons of the toxicity of erionite. The K-exchanged sample had a 95% reduction of the BET surface area indicating that it behaves as a mesoporous material. Exchanged K is segregated at K2 and at OW sites commonly occupied by H2O. The latter K cations provide a relevant contribution to the reduction of the surface area. Surprisingly, despite the collapse of its surface area the sample preserves the tendency to bind Fe(II). Therefore, yet in the case of a peculiar and potentially hostile structural environment the Fe(II) ion-exchange process has essentially the same kinetics observed in a typical erionite sample. This is a clear evidence of the very limited effect of the chemical composition of erionite on the Fe(II) binding process and reasonably it does not play a significant role in its toxicity.
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Erionite is a fibrous zeolite significantly more tumorigenic than crocidolite asbestos upon inhalation. In recent years, several papers have been published aimed at characterizing from the crystal-chemical point of view erionite fibres. As their toxicity has been ascribed to Fe acquired within the human body, studies aimed at characterizing the iron topochemistry have also been published, suggesting a possible important role played by the ionic exchange properties and cations mobility of this zeolite on developing carcinogenicity. Here we report the analysis results of the thermal behaviour of erionite-Na, which has been found to deviate significantly from that of erionite-K. This result is in contrast with the current scientific view that differences in weighted ionic potential, Si/Al ratio and size of exchangeable cations result in significantly different thermal behaviours, all those parameters being nearly identical or very similar in both species. The different mobility of the extraframework cations observed in erionite samples with dissimilar chemistry is of particular interest within the frame of the hypothesis that their biological activity could depend, apart from surface interactions, also on bulk effects.
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Nanomaterials are revolutionizing the field of medicine to improve the quality of life due to the myriad of applications stemming from their unique properties, including the antimicrobial activity against pathogens. In this study, the antimicrobial and antibiofilm properties of a novel nanomaterial composed by zinc oxide nanorods-decorated graphene nanoplatelets (ZNGs) are investigated. ZNGs were produced by hydrothermal method and characterized through field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD) techniques. The antimicrobial activity of ZNGs was evaluated against Streptococcus mutans, the main bacteriological agent in the etiology of dental caries. Cell viability assay demonstrated that ZNGs exerted a strikingly high killing effect on S. mutans cells in a dose-dependent manner. Moreover, FE-SEM analysis revealed relevant mechanical damages exerted by ZNGs at the cell surface of this dental pathogen rather than reactive oxygen species (ROS) generation. In addition, inductively coupled plasma mass spectrometry (ICP-MS) measurements showed negligible zinc dissolution, demonstrating that zinc ion release in the suspension is not associated with the high cell mortality rate. Finally, our data indicated that also S. mutans biofilm formation was affected by the presence of graphene-zinc oxide (ZnO) based material, as witnessed by the safranin staining and growth curve analysis. Therefore, ZNGs can be a remarkable nanobactericide against one of the main dental pathogens. The potential applications in dental care and therapy are very promising.
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The exposure of humans to erionite fibres of appropriate morphology and dimension has been unambiguously linked to the occurrence of Malignant Mesothelioma. For this reason, a detailed morpho-structural investigation through Electron Microscopy techniques has been performed on erionite samples collected at two different localities, Durkee (ED) and Rome (ER), Oregon, USA. The sample from Rome has been also investigated after a prolonged leaching with Gamble's solution (ER4G) in order to evaluate the possible occurrence of morpho-structural modifications induced by this Simulated-Lung-Fluid (SLF). Here we report how the micrometric erionite fibres evolve in irregular ribbon- or rod-like bundles as a function of different nano-structural features. The reasons for the observed morphological variability have been explained by considering the structural defects located at ED surface fibrils (bi-dimensional ribbons) and the presence of nontronite, an iron-bearing clay mineral embedding the ER fibrils (mono-dimensional rods). ER4G shows a decrease in width of the rod-like fibres due to their partial digestion by SLF leaching, which synchronously dissolves nontronite. The reported results represent a valuable background toward the full comprehension of the morphological mechanisms responsible for potentially damage of lung tissue through the potential relocation of fibers to extrapulmonary sites, increasing the carcinogenic risk to humans.
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Carcinógenos/química , Microscopia Eletrônica , Nanoestruturas/química , Zeolitas/química , Carcinógenos/toxicidade , Exposição Ambiental , Humanos , Pulmão/efeitos dos fármacos , Pulmão/patologia , Nanoestruturas/toxicidade , Zeolitas/toxicidadeRESUMO
The analysis of the thermal behavior of octyl- (OAC) and decylammonium chloride (DAC) has provided relevant new information. OAC shows a polymorphic phase transition that starts at 308 K and is completed at 313 K, between a monoclinic and a tetragonal structure, which belongs to a space group different from what was observed for other alkylammonium chlorides. At the melting temperature (463 K), the growing of a strong first sharp diffraction peak (FSDP) occurring at a d-spacing of ca. 21.0 Å was observed. DAC is characterized by two phase transitions at 318 (T(d1)) and 323 K (T(d2)). At T(d1), the LT polymorph coexists with a new-formed phase. At T(d2) the LT polymorph is replaced by a further polymorphic modification of DAC that becomes the only one at 328 K. This second phase transition signals the occurrence of a phase, closely related to the LT polymorph of HeAC, that crystallizes in the tetragonal crystal system a = ca. 5.00 Å and c = ca. 28.5 Å, P4/nmm space group. DAC melting starts at 458 K and is accompanied, as in the case of OAC, by the growing of a strong FSDP at a d-spacing of ca. 24.8 Å. A parallel DSC study confirmed the above-mentioned transitions. In addition, the structural properties of OAC/water and DAC/water mixtures were studied using an integrated approach, which combines X-ray diffraction and molecular dynamics (MD) techniques. A very good agreement between theoretical and experimental diffraction patterns has been obtained for both investigated mixtures. A thorough analysis of the MD trajectories shows that strong anion-water interactions are present in the mixtures, where Cl(-) forms a rather unstructured first hydration shell of water molecules bound to the anion in a linear Cl···H-O configuration. Moreover, cations and anions were found to interact with each other, and to form "solvent-shared ion pairs", in which one or more water molecules are shared between Cl(-) and the alkylammonium cation.
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The thermal stability of hexylammonium chloride (HeAC) has been investigated in situ real time by high-temperature X-ray powder diffraction. A phase transition from a low-temperature (LT) tetragonal to a high-temperature (HT) cubic polymorph has been detected at 473 K. A first sharp diffraction peak (FSDP) starts to grow at the same temperature and disappears at 493 K, just before melting starts to occur. The dependence of cell parameters from temperature has been quantified for the LT polymorph and shown to be very anisotropic. In particular, the tetragonal a parameter expands, while the c parameter contracts, and as a net result, the volume increases. The HT polymorph shows features reminiscent of that of plastic phases of molecular crystals and is characterized by a less efficient packing as compared to the LT polymorph as indicated by a volume expansion of ca. 11%. Moreover, the structural properties of HeAC/water mixtures, up to very high dilution, have been investigated by combining MD simulations and X-ray diffraction experiments. By using a Cl-water Lennard-Jones parameter previously refined for a similar system, a very good agreement between the theoretical and experimental diffraction patterns was obtained for all the studied systems. The Cl(-) ions in the mixtures were found to form both a first and second shell of water molecules. Moreover, a complex structural behavior has been highlighted, in which a strong interaction between cations and anions survives also in conditions of very high dilution. As a consequence, cations and anions do not always possess a completely closed hydration shell of their own, but rather solvent-shared ion pairs are formed to some extent in all the investigated mixtures.