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Gadolinium-based contrast agents are widely used in clinical magnetic resonance imaging (MRI) due to their strong paramagnetic properties and ability to enhance image contrast. Despite their diagnostic value, concerns remain regarding gadolinium toxicity and long-term tissue retention, particularly for less stable linear chelates. In this study, we report preliminary results on a newly synthesized gadolinium-based compound (L-Gd), in which the Gd3+ ion is coordinated to a specific ligand designed to improve biocompatibility. To evaluate the feasibility of L-Gd encapsulation within human RBCs (hRBCs) for drug delivery, its biocompatibility and cellular interactions were thoroughly investigated. RBCs represent an attractive biomimetic carrier system capable of limiting the direct exposure of tissues to paramagnetic agents while potentially improving circulation time and safety. In vitro assays demonstrated that L-Gd maintains high compatibility with hRBCs within specific concentration ranges, showing no significant hemolysis or morphological alterations. Furthermore, preliminary encapsulation studies indicate that L-Gd can be successfully associated with RBCs, supporting the potential of this approach for contrast agent delivery. These findings suggest that RBC-mediated transport of gadolinium complexes may represent a promising strategy to reduce toxicity and mitigate gadolinium retention. Further investigations will focus on optimizing encapsulation efficiency, relaxometric properties, and in vivo behavior of the L-Gd system.

Chlorophyll a derivatives were integrated in “all solid-state” dye sensitized solar cells (DSSCs) with a mesoporous TiO2 electrode and 2′,2′,7,7′-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifluorene as the hole-transport material. Despite modest power conversion efficiencies (PCEs) between 0.26% and 0.55% achieved for these chlorin dyes, a systematic investigation was carried out in order to elucidate their main limitations. To provide a comprehensive understanding of the parameters (structure, nature of the anchoring group, adsorption …) and their relationship with the PCEs, density functional theory (DFT) calculations, optical and photovoltaic studies and electron paramagnetic resonance analysis exploiting the 4-carboxy-TEMPO spin probe were combined. The recombination kinetics, the frontier molecular orbitals of these DSSCs and the adsorption efficiency onto the TiO2 surface were found to be the key parameters that govern their photovoltaic response.

Dendrimers exhibit unique interactions with cell membranes, arising from their nanometric size and high surface area. To a great extent, these interactions define their biological activity and can be reported in situ by spin-labelling techniques. Schiff-base carbosilane ruthenium (II) metallodendrimers are promising antitumor agents with a mechanism of action yet to explore. In order to study their in situ interactions with model cell membranes occurring at a molecular level, namely cetyltrimethylammonium bromide micelles (CTAB) and lecithin liposomes (LEC), electron paramagnetic resonance (EPR) was selected. Both a spin probe, 4-(N,N-dimethyl-N-dodecyl)ammonium-2,2,6,6-tetramethylpiperidine-1-oxyl bromide (CAT12), able to enter the model membranes, and a spin label, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) covalently attached at newly synthesized heterofunctional dendrimers, were used to provide complementary information on the dendrimer–membrane interactions. The computer-aided EPR analysis demonstrated a good agreement between the results obtained for the spin probe and spin label experiments. Both points of view suggested the partial insertion of the dendrimer surface groups into the surfactant aggregates, mainly CTAB micelles, and the occurrence of both polar and hydrophobic interactions, while dendrimer–LEC interactions involved more polar interactions between surface groups. We found out that subtle changes in the dendrimer structure greatly modified their interacting abilities and, subsequently, their anticancer activity.

Fibrous erionite is classified by the International Agency for Research on Cancer (IARC) as carcinogenic substance to humans (Group 1). In the areas where it is present in the bedrock, it may cause environmental exposure, and both professional and environmental exposures are possible when the bedrock is used for industrial applications (e.g., building materials). For health and environment protection, prevention is a priority action. In this framework, the recent guidelines of the Consensus Report of the Weinman International Conference on Mesothelioma suggest identifying locations where potentially hazardous mineral fibers (like erionite) are found in the environment, to prevent environmental exposure. The present study will show that one such potentially hazardous mineral fiber might be fibrous ferrierite. Here, the mineralogy, chemical-physical properties, and surface activity of a hydrothermal fibrous ferrierite from Monte Lake British Columbia (Canada) and a diagenetic fibrous ferrierite from Lovelock, Nevada (U.S.A.), were investigated using a combination of \"state of the art\" experimental methods including optical microscopy, electron microscopy and microprobe analysis, laser ablation-inductively coupled plasma-mass spectrometry (for the trace elements), vibrational spectroscopy, electron paramagnetic resonance, and synchrotron powder diffraction. The chemical-physical properties of these fibrous ferrierites (morphometric parameters, specific surface area, chemical composition with special attention to metals, mainly iron) that prompted adverse effects in vivo were compared to those of the positive carcinogenic standard fibrous erionite-Na from Jersey, Nevada (U.S.A.). The results of our study have demonstrated that, although there are differences in the crystal chemistry and genetic environment, ferrierite samples exhibit outstanding similarities with fibrous erionite samples: both fibrous erionite and fibrous ferrierite may occur in large amounts as microcrystalline fibrous-asbestiform phases in diagenetic rocks with fibers of breathable sizes. For both zeolites, iron is not structural but is associated with impurities lying at the surface of the fibers. Moreover, data useful to understand the surface activity of these fibrous ferrierites were collected. As far as hydrothermal sample is concerned, the EPR data indicate the presence of hydrophilic (SiO-, AlO-, SiOH) and hydrophobic (Si-O-Si) interacting surface groups able to bind the charged CAT1 probes at close sites and attract the probes in the water pools formed into the fiber aggregates. A high percentage of CAT1 probes weakly interacting with the surface due to competition with metal ions were observed for surface of the diagenetic sample. CAT8 probes were less adsorbed by its surface if compared to the diagenetic sample but the more charged surface provided a stronger binding strength for the diagenetic sample compared to the hydrothermal one. In summary, the results of this study indicate that fibrous ferrierite may represent a potential health hazard and, applying the precautionary principle, it should undergo a procedure of toxicity testing.

Amyloid peptide fibrillogenesis induced by Cu(II) ions is a key event in the pathogenesis of Alzheimer’s disease. Dendrimers have been found to be active in preventing fibril formation. Therefore, they hold promise for the treatment of Alzheimer’s disease. In this study, the fibrillation mechanism of amyloid peptide Aβ 1-40 was studied by adding Cu(II) in the absence and presence of 4 th generation poly(propyleneimine) glycodendrimer functionalized with sulfate groups, using dynamic light scattering (DLS), circular dichroism (CD), fluorescence, electron paramagnetic resonance (EPR) and molecular modeling (MD). The glycodendrimer was non-toxic to mHippoE-18 embryonic mouse hippocampal cells, selected as a nerve cell model, and decreased the toxicity of peptide aggregates formed after the addition of Cu(II). The binary systems of Cu(II)–glycodendrimer, Cu(II)–peptide, and glycodendrimer–peptide were first characterized. At the lowest Cu(II)/glycodendrimer molar ratios, Cu(II) was complexed by the internal-dendrimer nitrogen sites. After saturation of these sites, Cu(II) binding with sulfate groups occurred. Stable Cu(II)–peptide complexes formed within 5 min and were responsible for a transition from an α helix to a β-sheet conformation of Aβ 1-40. Glycodendrimer–peptide interactions provoked the stabilization of the α -helix, as demonstrated in the absence of Cu(II) by the Thioflavin T assay, and in the presence of Cu(II) by CD, EPR, and MD. Formation of fibrils is differentially modulated by glycodendrimer and Cu(II) concentrations for a fixed amount of Aβ 1-40. Therefore, this multidisciplinary study facilitated the recognition of optimal experimental conditions that allow the glycodendrimer to avoid the fibril formation induced by Cu(II).

The synthesis, EPR characterisation and biological evaluation of two new metallodendrimers, i.e. a poly(propyleneamine) dendrimer functionalized at the external surface with 4-bromo-1,8-naphthalimide and conjugated with Cu(II) and Zn(II), was performed with the aim to evaluate their antimicrobial and anticancer activity. The antimicrobial activity was investigated in meat-peptone broth against bacteria B. subtilis and P. aeruginosa , and the yeast C. lipolytica . The results showed that the compounds inhibited effectively the tested pathogens even after their deposition on a textile fabric. Anticancer activity was investigated against three human permanent cell lines from non-small cell lung cancer (A549), triple negative breast cancer (MDA-MB-231) and carcinoma of the uterine cervix (HeLa) in the c = 0.01–30 μM concentration range. The results suggest that these compounds are promising for application in biomedicine as anticancer drugs in the design of new effective preparations. The antimicrobial and anticancer activity may be related to the peculiar structural and dynamical properties revealed for the Cu(II) complexes, by a computer aided analysis of the electron paramagnetic resonance (EPR) spectra. This analysis indicated the formation, at the lowest Cu(II) concentrations, of a flexible rhombic Cu-N4 coordination with the internal amino groups of the dendrimer, which transformed into a Cu2-N4 coordination already at 0.25 equiv. of Cu(II).

Nowadays, fibrous minerals pose as significant health hazards to humans, and exposure to these fibers can lead to the development of severe pulmonary diseases. This work investigated the morphology, crystal structure, chemistry, and surface activity of fibrous ferrierite recently found in northern Italy through an integrated approach using scanning electron microscopy–energy dispersive spectroscopy, electron microprobe, inductively coupled plasma atomic emission spectrometry, X-ray powder diffraction, and electron paramagnetic resonance. Our results show that a notable amount of ferrierite fibers are breathable (average length ~22 µm, average diameter 0.9 µm, diameter-length ratio >> 1:3) and able to reach the alveolar space (average Dae value 2.5 μm). The prevailing extra-framework cations are in the Mg > (Ca ≈ K) relationship, R is from 0.81 to 0.83, and the Si/Al ratio is high (4.2–4.8). The bond distances suggest the occurrence of some degree of Si,Al ordering, with Al showing a site-specific occupation preference T1 > T2 > T3 > T4. Ferrierite fibers show high amounts of adsorbed EPR probes, suggesting a high ability to adsorb and interact with related chemicals. According to these results, fibrous ferrierite can be considered a potential health hazard, and a precautionary approach should be applied when this material is handled. Future in vitro and in vivo tests are necessary to provide further experimental confirmation of the outcome of this work.

Amyloid peptide fibrillogenesis induced by Cu（II） ions is a key event in the pathogenesis of Alzheimer＇s disease. Dendrimers have been found to be active in preventing fibril formation. Therefore, they hold promise for the treatment of Alzheimer＇s disease. In this study, the fibrillation mechanism of amyloid peptide Aβ 1-40 was studied by adding Cu（II） in the absence and presence of 4th generation poly（propyleneimine） glycodendrimer functionalized with sulfate groups, using dynamic light scattering （DLS）, circular dichroism （CD）, fluorescence, electron paramagnetic resonance （EPR） and molecular modeling （MD）. The glycodendrimer was non-toxic to mHippoE-18 embryonic mouse hippocampal cells, selected as a nerve cell model and decreased the toxicity of peptide aggregates formed after the addition of Cu（II）. The binary systems of Cu（II）-glycodendrimer, Cu（II）-peptide, and glycodendrimer-peptide were first characterized. At the lowest Cu（II）/glycodendrimer molar ratios, Cu（II） was complexed by the internal-dendrimer nitrogen sites. After saturation of these sites, Cu（II） binding with sulfate groups occurred. Stable Cu（II）-peptide complexes formed within 5 min and were responsible for a transition from an α helix to a β-sheet conformation of Aβ 1-40. Glycodendrimer-peptide interactions provoked the stabilization of the a-helix, as demonstrated in the absence of Cu（II） by the Thioflavin T assay, and in the presence of Cu（II） by CD, EPR, and MD. Formation of fibrils is differentially modulated by glycodendrimer and Cu（II） concentrations for a fixed amount of Aβ 1-40. Therefore, this multidisciplinary study facilitated the recognition of optimal experimental conditions that allow the glycodendrimer to avoid the fibril formation induced by Cu（II）.

The presence, in nature, of asbestos similar particles, highly toxic and potentially cancerogenic for human healthy is well known (1). Inhalation of the fibrous form of erionite, has been shown to cause effects compared to those observed with mineral fibers classified as ‘‘asbestos,’’ including malignant mesothelioma, a disease typically associated with occupational and environmental exposures to asbestos (2). In this work various zeolite materials have been considered because of their suspected carcinogenic activity and, the possible interactions occurring between asbestiform fibers and U937 cell, a human hemopoietic cell line, have been evaluated. Chemical and morpho-functional analyses have been carried out, both to characterize fiber structure and cell response. Cells showed the ability to internalize the minerals, as observed after TEM analyses. With zeolite exposure time increasing, a diffuse cell damage with features of apoptotic and necrotic death can be evidenced (3). These findings suggest that the fibrous form of scolecite or offretite too can be considered potentially toxic for cell culture in vitro.