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3D-epitaxy of the {010} pinacoid of deposited gypsum (CaSO4·2H2O) on the substrate {10.4} calcite rhombohedron is described, in order to give a theoretical background to the replacement of calcite with gypsum both in the laboratory and by weathering in nature. 2D-lattice coincidences are geometrically obtained from the matching of periodic bond chains (PBCs) running within the elementary slices facing towards the substrate/deposit interfaces. The epitaxy in the third dimension, perpendicular to the interfaces, has been verified as well, to establish if ad/absorption occurs (anomalous mixed crystals) at the calcite/gypsum contact. This research represents the reticular part of a wider program extended to the epi-interaction among the gypsum/calcite, gypsum/bassanite (CaSO4·1/2H2O) and gypsum/anhydrite (CaSO4) couples. [ABSTRACT FROM AUTHOR]

The theoretical equilibrium shape (ES) of the monoclinic hydroxyapatite (HAp) crystal is revised, having taken into account, for the first time, a new set of {h0l} pinacoids: {101¯}, {102} and {1¯04}. The corresponding surface profiles are determined by applying the morphological Hartman–Perdok method. Surface energy values (γh0l) are evaluated at 0 K, with respect to the vacuum. Crystal surfaces are simulated by using the 2D periodic slab model and the ab initio CRYSTAL14 code. Calculations are performed at the DFT (density functional theory) level: the B3LYP Hamiltonian was adopted. From the comparison between the set of the γh0l values previously obtained for the pinacoids: {100}, {001} and {1¯02} and those calculated in this work, a completely new ES is obtained. This striking result brings into question: (i) the geometrical laws of the growth twins; (ii) the predicted growth shape of HAp in pure aqueous solutions; (iii) the habit change of HAp crystals growing in aqueous solutions and doped with impurities that could make 2D-epitaxies on selected crystal faces. [ABSTRACT FROM AUTHOR]

The whole series of the face-centered cubic (f.c.c.) alkali halides, from LiF to RbI, has been crystallized from aqueous solutions in the presence of variable amounts of formamide (HO–C–NH2). Scanning electron microscope images show that the corresponding morphology of the grown crystals is not homogeneous within the whole crystal series, and that the {111} octahedron does appear and compete with the {100} cube only in three separated crystal domains: (NaF), (LiBr, RbF, NaCl) and (KCl, NaI, RbCl, KBr). Starting from our preceding finding about the formation of NaCl/formamide anomalous mixed crystals and recollecting the peculiar {100} + {111} habit change of NaCl growing from pure aqueous solution, we propose that formamide can be adsorbed as a 2D epitaxial layer on the {111} surfaces of the f.c.c. alkali halides according to a three-modal distribution. [ABSTRACT FROM AUTHOR]

KCl f.c.c. crystals generally exhibit a {100} habit when growing from pure aqueous solutions, a richer {100} + {111} morphology being obtained only under well-defined growth temperature and supersaturation. When increasing amounts (less than 2000 ppm) of Pb are put in a supersaturated solution, the KCl growth morphology undergoes a progressive change: {100} → {100} + {111} → {111}. Detailed growth patterns have been investigated by means of SEM and AFM, while EDS and XRF analyses allowed us to ascertain that Pb is not only adsorbed on the growing KCl surfaces but also selectively absorbed within the {111} growth sectors. Starting from recent and analogous findings, we tried to interpret the morphological change by means of a geometric and structural model of epitaxy between the {100} and the {111} forms of KCl and the most important forms of those compounds that could be adsorbed on them: PbCl2 (cotunnite), PbCl(OH) (laurionite–paralaurionite) and KCl·PbCl2 (challacolloite). Excellent lattice coincidences have been found, thus proving that the {111} KCl octahedron is largely privileged for adsorption/absorption to occur with respect to the {100} KCl cube. Based on this ground, simple kinetic considerations can be proposed to satisfactorily explain the observed morphology change. [ABSTRACT FROM AUTHOR]

Gypsum twins are frequently observed in nature, triggered by a wide array of impurities that are present in their depositional environments and that may exert a critical role in the selection of different twin laws. Identifying the impurities able to promote the selection of specific twin laws has relevance for geological studies aimed at interpreting the gypsum depositional environments in ancient and modern deposits. Here, the effect of calcium carbonate (CaCO 3 ) on gypsum (CaSO 4 ·2H 2 O) growth morphology has been investigated by performing temperature-controlled laboratory experiments with and without the addition of carbonate ions. The precipitation of twinned gypsum crystals has been achieved experimentally (101 contact twin law) by adding carbonate to the solution, and the involvement of rapidcreekite (Ca 2 SO 4 CO 3 ·4H 2 O) in selecting the 101 gypsum contact twin law was supported, suggesting an epitaxial mechanism. Moreover, the occurrence of 101 gypsum contact twins in nature has been suggested by comparing the natural gypsum twin morphologies observed in evaporitic environments with those obtained in experiments. Finally, both orientations of the primary fluid inclusions (of the negative crystal shape) with respect to the twin plane and the main elongation of sub-crystals that form the twin are proposed as a fast and useful method (especially in geological samples) to distinguish between the 100 and 101 twin laws. The results of this study provide new insights into the mineralogical implications of twinned gypsum crystals and their potential as a tool to better understand natural gypsum deposits., (© Andrea Cotellucci et al. 2023.)

2D and 3D epitaxies of the main {010}, {001} and {100} forms of deposited bassanite (CaSO 4 ·0.5H 2 O) on {10.4} calcite (CaCO 3 ) as a substrate are described to provide a theoretical crystallographic background for the replacement of calcite by bassanite both in nature and in the laboratory and by weathering linked to cultural heritage. First, epitaxy in the third dimension, perpendicular to the investigated interfaces, has been verified in order to establish whether adsorption/absorption can occur (as anomalous mixed crystals) at the bassanite/calcite epi-contacts. Secondly, and by applying the Hartman-Perdok method, 2D lattice coincidences have been obtained from the physical-geometric matches of bonds running in the common directions within the elementary slices facing the substrate/deposit interfaces. This research represents the second and more detailed part of a wider program extended to the epi-interactions between the following pairs: (i) {010}-gypsum/{10.4}-calcite (just published); (ii) bassanite/{10.4}-calcite (the present work); and (iii) anhydrite (CaSO 4 )/{10.4}-calcite (coming soon)., (© Dino Aquilano et al. 2022.)

In this study the absorption of glycine, α-alanine and β-alanine amino acids into the pores of the synthetic zeolite Na-mordenite was investigated with the aim of: (i) evaluating the effectiveness of the MOR framework type in amino acid adsorption ( via vapor and aqueous loading); (ii) understanding the host-guest and guest-guest interactions to possibly design a tailor made material and a loading procedure able to maximize the amino acid adsorption; (iii) studying the effect of pressure on the adsorbed amino acids such as, for instance, possible amino acid condensation. The structural characterization, carried out with the combination of diffractometric and infrared spectroscopy analyses, shows that MOR can adsorb amino acids, which are found both in protonated/deprotonated (possibly also generating zwitterions) form. Vapor loading is ineffective for α-alanine, while it is effective in β-alanine and glycine adsorption, even if using different loading degrees. The shape and size of MOR channels make this zeolite suitable to accommodate a peptide. In a glycine loaded sample some molecules condensate to form cyclic dimers, while linear oligomers are detected only in a β-alanine MOR hybrid. The sample loaded with α-L-alanine from aqueous solution does not show the presence of amide bond signals, indicating that the molecules are mostly hosted in zwitterionic form in Na-MOR channels. The application of external baric stimuli does not induce substantial modifications in the structure of the glycine loaded zeolite; this result may be explained by the low number of molecules hosted in the channels. The amino acid amount within the zeolite pores is the most important reactivity parameter and an increased loading could induce chemical modifications.

Sonodynamic therapy (SDT) is an innovative anticancer approach, based on the excitation of a given molecule (usually a porphyrin) by inertial acoustic cavitation that leads to cell death via the production of reactive oxygen species (ROS). This study aims to prepare and characterize nanosystems based on porphyrin grafted carbon nanotubes (SWCNTs), to understand some aspects of the mechanisms behind the SDT phenomenon. Three different porphyrins have been covalently linked to SWCNTs using either Diels-Alder or 1,3-dipolar cycloadditions. ROS production and cell viability have been evaluated upon ultrasound irradiation. Despite the low porphyrin content linked on the SWCNT, these systems have shown high ROS production and high tumour-cell-killing ability. The existence of a PET (photoinduced electron transfer)-like process would appear to be able to explain these observations. Moreover, the demonstrated ability to absorb light limits the impact of side effects due to light-excitation., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The increase in the amount of carbon dioxide (CO 2 ) emissions related to many anthropic activities is a persistent and growing problem. During the last years, many solutions have been set out, none of them being the ultimate one. Investigators agree on the need of a synergic approach to the problem, in terms of many complementary methods of sequestration that, combined with the reduction of production, will be able to decrease the concentration of the CO 2 in the atmosphere. In this work, we explore the use of a green reaction to trap the CO 2 into a stable crystalline phase (weddellite) resorting to a multidisciplinary approach. CO 2 is reduced and precipitated as calcium oxalate through vitamin C as a sacrificial reductant. Calcium oxalate crystals obtained show a startling good quality that increases their already great stability over a wide chemical and physical conditions' range., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The aim of this study is twofold: (i) characterization of the bottom ashes from the Incinerator plant of the city of Turin (northern Italy), in terms of their chemical/phase compositions and capacity to release heavy metals in leachates, as a function of particle size; (ii) investigation of thermal treatments' efficacy to promote inertization of the same bottom ashes, exploring time-temperature ranges with t ≤ 6 h and T ≤ 1000 °C. Special attention is paid to macro-sampling techniques in order to have samples that are representative of the average bottom ashes production. Micro-XRF, ICP-OES, SEM-EDS, Ion Chromatography and X-ray powder diffraction were used to investigate bottom ashes and leachates. Bottom ashes are mainly constituted by an amorphous phase, ∼66-97 wt%, regardless of particle size; the remaining phases are quartz, calcite, Fe-oxides, melilite and other minor crystalline materials. The amorphous phase exhibits a relevant dependence on particle size, and undergoes dissolution in water up to 20 wt%, thus being the most important component in affecting chemical species release. The smaller the bottom ashes' particle size, the more the heavy metals (major species: Zn, Cu, Ti, Pb) and calcium contents increase, whereas silicon's decreases. Electrolytic current observations in combination with phase/chemical composition and metals release as a function of particle size, suggest that bottom ashes partition into two classes, i.e. ≥1 and <1 mm, for inertization purposes. Thermal treatments exhibit partial efficacy to curb heavy metals mobility: whilst they reduce Cu release, they lead to a inverse effect in the case of Cr., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Background: Exposure to some - but not all - quartz particles is associated to silicosis, lung cancer and autoimmune diseases. What imparts pathogenicity to any single quartz source is however still unclear. Crystallinity and various surface features are implied in toxicity. Quartz dusts used so far in particle toxicology have been obtained by grinding rocks containing natural quartz, a process which affects crystallinity and yields dusts with variable surface states. To clarify the role of crystallinity in quartz pathogenicity we have grown intact quartz crystals in respirable size., Methods: Quartz crystals were grown and compared with a fractured specimen obtained by grinding the largest synthetic crystals and a mineral quartz (positive control). The key physico-chemical features relevant to particle toxicity - particle size distribution, micromorphology, crystallinity, surface charge, cell-free oxidative potential - were evaluated. Membranolysis was assessed on biological and artificial membranes. Endpoints of cellular stress were evaluated on RAW 264.7 murine macrophages by High Content Analysis after ascertaining cellular uptake by bio-TEM imaging of quartz-exposed cells., Results: Quartz crystals were grown in the submicron (n-Qz-syn) or micron (μ-Qz-syn) range by modulating the synthetic procedure. Independently from size as-grown quartz crystals with regular intact faces did not elicit cellular toxicity and lysosomal stress on RAW 264.7 macrophages, and were non-membranolytic on liposome and red blood cells. When fractured, synthetic quartz (μ-Qz-syn-f) attained particle morphology and size close to the mineral quartz dust (Qz-f, positive control) and similarly induced cellular toxicity and membranolysis. Fracturing imparted a higher heterogeneity of silanol acidic sites and radical species at the quartz surface., Conclusions: Our data support the hypothesis that the biological activity of quartz dust is not due to crystallinity but to crystal fragmentation, when conchoidal fractures are formed. Besides radical generation, fracturing upsets the expected long-range order of non-radical surface moieties - silanols, silanolates, siloxanes - which disrupt membranes and induce cellular toxicity, both outcomes associated to the inflammatory response to quartz.

This work describes the design of a modified porphyrin that bears four furan rings linked by 1,2-bis-(2-aminoethoxy)ethane spacers. This unit is a well-suited scaffold for a Diels-Alder reaction with commercial reduced-graphene oxide, which is also described in this paper. A new hybrid material is obtained, thanks to efficient grafting under microwave irradiation, and fully characterized in terms of structure (UV, TGA, Raman) and morphology (HR-TEM and AFM). Potential applications in photo- and sonodynamic therapy are envisaged., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Cyclodextrin-based nanosponges (NS) are solid nanoparticles, obtained from the cross-linking of cyclodextrins that have been proposed as delivery systems for many types of drugs. Various NS derivatives are currently under investigation in order that their properties might be tuned for different applications. In this work, new carboxylated cyclodextrin-based nanosponges (Carb-NS) carrying carboxylic groups within their structure were purposely designed as novel Acyclovir carriers. TEM measurements revealed their spherical shape and size of about 400 nm. The behaviour of Carb-NS, with respect to the incorporation and delivery of Acyclovir, was compared to that of NS, previously investigated as a drug carrier. DSC, XRPD and FTIR analyses were used to investigate the two NS formulations. The results confirm the incorporation of the drug into the NS structure and NS-Acyclovir interactions. The Acyclovir loading into Carb-NS was higher than that obtained using NS, reaching about 70% (w/w). In vitro release studies showed the release kinetics of Acyclovir from Carb-NS to be prolonged in comparison with those observed with NS, with no initial burst effect. The NS uptake into cells was evaluated using fluorescent Carb-NS and revealed the nanoparticle internalisation. Enhanced antiviral activity against a clinical isolate of HSV-1 was obtained using Acyclovir loaded in Carb-NS., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Camptothecin (CAM), a plant alkaloid and a potent antitumor agent, has a limited therapeutic utility because of its poor aqueous solubility, lactone ring instability and serious side effects. Cyclodextrin-based nanosponges (NS) are a novel class of cross-linked derivatives of cyclodextrins. They have been used to increase the solubility of poorly soluble actives, to protect the labile groups and control the release. This study aimed at formulating complexes of CAM with three types of beta-cyclodextrin NS obtained with different cross-linking ratio (viz. 1:2, 1:4 and 1:8 on molar basis with the cross-linker) to protect the lactone ring from hydrolysis and to prolong the release kinetics of CAM. Crystalline (F(1:2), F(1:4) and F(1:8)) and paracrystalline NS formulations were prepared. XRPD, DSC and FTIR studies confirmed the interactions of CAM with NS. XRPD showed that the crystallinity of CAM decreased after loading. CAM was loaded as much as 21%, 37% and 13% w/w in F(1:2), F(1:4) and F(1:8), respectively while the paracrystalline NS formulations gave a loading of about 10% w/w or lower. The particle sizes of the loaded NS formulations were between 450 and 600nm with low polydispersity indices. The zeta potentials were sufficiently high (-20 to -25mV) to obtain a stable colloidal nanosuspension. The in vitro studies indicated a slow and prolonged CAM release over a period of 24h. The NS formulations protected the lactone ring of CAM after their incubation in physiological conditions at 37 degrees C for 24h with a 80% w/w of intact lactone ring when compared to only around 20% w/w of plain CAM. The cytotoxicity studies on HT-29 cells showed that the CAM formulations were more cytotoxic than plain CAM after 24h of incubation., (Copyright (c) 2009 Elsevier B.V. All rights reserved.)

Alkylcarbonates of gamma-cyclodextrins were produced and their inclusion complexes with four poorly water-soluble drugs of different structures and solubilities were prepared. The alkylcarbonates and the alkylcarbonate drug complexes were characterized by DSC and XRPD; the physical mixtures were used as control. Solubility capacities were evaluated by phase solubility studies. The effect of alkyl chain length on the complexation and release behaviour was investigated as well. The XRPD patterns of alkylcarbonates showed that the derivatives lose the original crystallinity of gamma-cyclodextrins. The series of alkylcarbonates formed inclusion complexes with the drugs considered. Both XRPD and DSC analyses did not show neither the reflections of the crystalline structures nor the melting peaks of the drugs, respectively. These gamma-cyclodextrin derivatives can improve drug solubility and influence the drug release rates while the alkyl chain length may affect these properties.