Curcumin-loaded zeolite as anticancer drug carrier: Effect of curcumin adsorption on zeolite structure

In this work we used a combination of different techniques to investigate the adsorption properties of curcumin by zeolite type A for potential use as an anticancer drug carrier. Curcumin is a natural water-insoluble drug that has attracted great attention in recent years due to its potential anticancer effect in suppressing many types of cancers, while showing a synergistic antitumor effect with other anticancer agents. However, curcumin is poorly soluble in aqueous solutions leading to the application of high drug dosage in oral formulations. Zeolites, inorganic crystalline aluminosilicates with porous structure on the nano- and micro-scale and high internal surface area, can be useful as pharmaceutical carrier systems to encapsulate drugs with intrinsic low aqueous solubility and improve their dissolution. Here, we explore the use of zeolite type A for encapsulation of curcumin, and we investigate its surface properties and morphology, before and after loading of the anticancer agent, using scanning electron microscopy (SEM), powder X-ray diffraction (XRD), differential scanning calorimetry (DSC), and UV-vis spectroscopy. Results are used to assess the loading efficiency of zeolite type A towards curcumin and its structural stability after loading

Thermally induced behavior of the K-exchanged erionite. A further step in understanding the structural modifications of the erionite group upon heating

Fibrous erionite is a naturally occurring zeolite considered to be highly carcinogenic upon inhalation, even more than crocidolite. Since no iron is typically present in erionite, its toxicity has been attributed to ion-exchanged Fe participating in Fenton chemistry. Recently, a study aimed at investigating possible fiber inactivation routes surprisingly showed that, despite having completely occluded all available pores with K ions, the erionite-Na sample preserved the property to upload Fe (II) within the structure. In this work, the thermal behavior of the K-exchanged erionite-Na was investigated by TG/ DSC and in situ XRPD analyses in order to provide relevant information for modeling the thermally induced behavior of the erionite group. Rietveld refinement results evidenced a general trend of cell parameters and volume with temperature similar to that observed for erionite-K from Rome (Oregon, USA). However, the dependence of Tdehydrand Tbreakfrom Si/Si+Al ratio observed in zeolites (high Si content favours a lower Tdehydrand a higher Tbreak) is not observed, possibly due to the effect of the relevant amount of large K ions dispersed within the erionite cage, acting as reinforcing blocks for the framework. Heating produces a progressive emptying of the Ca sites, common effect previously observed in erionite samples showing different chemistry. In addition, K1 s.s. remains unchanged evidencing the absence of any “internal ion exchange” process, whereas s.s. at K2 increases in the range 438-573 K and then slowly decreases in the range 700-1218 K. Both Rietveld and DSC data suggest the motion of K ions from OW sites toward the walls of the erionite cavity during dehydration

The crystal structure of sacrofanite, the 74 Å phase of the cancrinite–sodalite supergroup

Sacrofanite, a = 12.903(2) Å, c = 74.284(8) Å, space group View the MathML source, belongs to the cancrinite–sodalite supergroup of minerals, and displays a 28-layer stacking sequence along the c axis. Its stacking sequence is ABCABACACABACBACBACABABACABC…, where A, B and C stand for the positions of six-member rings of tetrahedra in each layer. It corresponds to the Zhdanov symbol |12(8)21|12(8)21|, and gives rise to a framework with topological symmetry P63/mmc. The ordering of Si and Al in the tetrahedral sites reduces the symmetry to View the MathML source. The members of this supergroup of minerals belong to the wider ABC-6 family, where also double rings of tetrahedra may occur. They share many structural features with zeolites, showing structural cages hosting extra-framework ions as well as H2O molecules. The crystal structure of sacrofanite has been modelled on the basis of High Resolution Transmission Electron Microscopy (HRTEM) images. The resulting model has been successfully refined by using both single-crystal synchrotron radiation and laboratory data. The refinements converged to R = 0.083 for 4228 unique reflections, and to R = 0.096 for 15,795 unique reflections, respectively. The resulting framework is formed by eight cancrinite and four sodalite cages superimposed along [0, 0, z], whereas one cancrinite, four sodalite, two losod, and one liottite cages occur along [1/3, 2/3, z] and [2/3, 1/3, z]. The structural formula of sacrofanite, as obtained from the refinement and by crystal chemical considerations, is (Na61K19Ca32)∑=112(Si84Al84O336)(SO4)26Cl2F6·2H2O

Crystal structure of afghanite, the eight-layer member of the cancrinite-group: Evidence for long-range Si,Al ordering

Afghanite, ideally [(Na,K)(22)Ca-10][Si24Al24O96](SO4)(6)Cl-6, is the eight-layer member of the cancrinite-group (ABABACAC stacking sequence). Its structure was refined in the P31c space group to R = 4.5% by means of single-crystal X-ray diffraction data. The cell parameters are a = 12.8013(7) Angstrom, c = 21.4119(18) Angstrom. The P6(3)mc space group proposed in a previous structure refinement is not consistent with the ordered Si,AI pattern suggested by an Si/Al ratio equal to 1 shown by afghanite and other members of the cancrinite-group. The Si-O and Al-O bond distances, 1.61(2) Angstrom and 1.72(2) Angstrom respectively, found in the structure refinement, are in accordance with an ordered Si,AI distribution which is allowed by the P31c space group, a maximal non isomorphic subgroup of P6(3)mc. Afghanite contains six 11-hedra (cancrinite) cages and two 23-hedra (liottite) cages. Four cancrinite cages are stacked along [0 0 z]. They contain a regular....Ca-Cl-Ca-Cl.... chain similar to that observed in davyne and related phases: in particular Ca is located near the center of the bases whereas Cl is near the center of the cage. A liottite cage with a base-sharing cancrinite cage is stacked along [2/3 1/3 z] and [1/3 2/3 z]. The liottite cage hosts a maximum of three sulphate groups which alternate regularly with cation-containing planes. The cancrinite cage, that shares the bases with the liottite cages, presents a disordered distribution of Cl and F reading to two possible configurations similar to those observed in liottite

The Use of Energy Dispersive X-ray Diffraction (EDXD) for the Investigation of the Structural and Compositional Features of Old and Modern Papers

Abstract This work reports the first application of the Energy Dispersive X-ray Diffraction (EDXD) for the investigation of the structural and compositional features of old and modern papers. Based on the differences observed among various types of paper and building an appropriate database we expect to be able to rapidly identify the provenance of the paper itself using a fast non-destructive technique. This result is quite interesting in the field of art conservation and archaeometry

Closing the knowledge gap on the composition of the asbestos bodies

Asbestos bodies (AB) form in the lungs as a result of a biomineralization process initiated by the alveolar macrophages in the attempt to remove asbestos. During this process, organic and inorganic material deposit on the foreign fibers forming a Fe-rich coating. The AB start to form in months, thus quickly becoming the actual interface between asbestos and the lung tissue. Therefore, revealing their composition, and, in particular, the chemical form of Fe, which is the major component of the AB, is essential to assess their possible role in the pathogenesis of asbestos-related diseases. In this work we report the result of the first x-ray diffraction measurements performed on single AB embedded in the lung tissue samples of former asbestos plant workers. The combination with x-ray absorption spectroscopy data allowed to unambiguously reveal that Fe is present in the AB in the form of two Fe-oxy(hydroxides): ferrihydrite and goethite. The presence of goethite, which can be explained in terms of the transformation of ferrihydrite (a metastable phase) due to the acidic conditions induced by the alveolar macrophages in their attempt to phagocytose the fibers, has toxicological implications that are discussed in the paper

Surface and bulk modifications of amphibole asbestos in mimicked gamble's solution at acidic PH

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

Surface and Bulk Modifications of Fibrous Erionite in Mimicked Gamble's Solution at Acidic pH

This study aimed at investigating both the surface and bulk modifications occurring on fibrous erionite during leaching in a mimicked Gamble's solution (MGS) at pH of 4.5 and T = 37 degrees C, up to one month of incubation. Samples were characterized by a multi-analytical approach: field-emission scanning electron microscopy (FE-SEM) was employed to investigate the morphological changes of both pristine and reacted fibres, inductively coupled plasma optical emission spectrometry (ICP-OES) was used to measure the concentration of the released cations; X-ray photoelectron spectroscopy (XPS) was exploited for highlighting possible modifications of surface chemistry; X-ray powder diffraction (XRPD) and high-resolution transmission electron microscopy (HR-TEM) were applied aiming to get information on the structural state of the fibres following the incubation. ICP results integrated with those obtained by both bulk- and surface-chemical characterization highlighted that erionite binds Na especially in the first 24 h of sample incubation in the MGS, following ion exchange with the extra framework cations, in particular Ca. Moreover, our new results show that the Na binding process caused structural modifications with the migration of Na toward the Ca2 site and redistribution of the cations within the erionite cage. TEM investigation pointed out that the interaction between erionite and MGS results in the formation of a new surface amorphous layer with an irregular lobate pattern on an earlier surface weathered layer. However, the silicate framework is not weakened by incubation in the MGS at acidic pH. In addition, on the basis of the Si release normalized to the mineral surface area, fibrous erionite resulted significantly more biodurable than amphibole asbestos. Notably, considering the primary role played by biodurability in inducing pathogenicity, this result certainly supports in vivo observations showing that erionite is much more tumorigenic than asbestos. Moreover, the ions released by erionite when immersed in MGS may trigger biological effects, such as those on lipid packing and membrane permeability. On this basis, we expect a regulatory definition that would provide protection from this carcinogenic fibre

Dissolution Reaction and Surface Modification of UICC Amosite in Mimicked Gamble’s Solution: A Step towards Filling the Gap between Asbestos Toxicity and Its Crystal Chemical Features

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 degrees 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