Compost application enhances soil structure, fertility, and microbial activity, reducing the need for chemical inputs and supporting agroecosystem resilience, while mycorrhizal symbiosis improves nutrient and water uptake efficiency, thereby increasing crop tolerance to abiotic stresses. Moreover, both compost and mycorrhizae contribute to soil carbon sequestration, offering an environmental-friendly solution to mitigate greenhouse gas emissions while maintaining long-term soil productivity and health. The use of municipal solid waste (MSW)-derived compost in agriculture supports a circular economy by recycling organic waste into valuable soil amendments, aligning with zero-waste principles and reducing pressure on landfills. In this work, we treated grapevine plants with MSW-compost, arbuscular mycorrhizal fungi (AMF) or the combination of both, in a pot experiment with agricultural soil as growth substrate. Root mycorrhization was evaluated by staining and microscopy, while effects on the aerial parts of the plant were evaluated by measurement of the reflectance spectra of leaves. Results showed that MSW-compost increased the root mycorrhization by native AMF (i.e. in non-AMF inoculated plants), leading to mycorrhization levels comparable to those obtained with the addition of commercial inoculum. At the same time, MSW-compost amended plants showed a delayed leaf senescence. The integration of compost and arbuscular mycorrhizal fungi (AMF) represents a promising strategy to both improve adaptation of agriculture to climate change and reduce our dependence on synthetic fertilizers, fostering virtuous practices in sustainable agricultural systems.

Bone represents one of the most common sites for metastasis originating from solid tumors, especially breast and prostate cancers, causing severe complications like pain, fractures, and impaired quality of life. Hydroxyapatite (HA) nanoparticles (NPs) have been considered as good candidates for bone-targeted drug delivery due to their biocompatibility and osteoconductivity. In this study, we developed selenium-doped hydroxyapatite (HASe) NPs with reduced selenium content (up to 2.40 wt%) with the aim of overcoming the toxicity issues associated with previously reported higher Se doping levels. The HA-based NPs were thoroughly characterized to evaluate their morphological, colloidal, and compositional features, supporting the effective incorporation of selenium (Se) within the HA structure. In vitro cytotoxicity assays on MCF7wt breast cancer cells demonstrated a clear Se dose-dependent reduction in viability. To improve the anticancer potential, HA and selected HASe NPs were further functionalized with two HA-binding anti-tumor platinum-bisphosphonate (PtBP) complexes. The resulting PtBP-HASe NPs exhibited stronger cytotoxicity than PtBP-HA, despite their lower platinum content, highlighting an additional effect due to the presence of Se. Notably, PtBP-HASe NPs maintained a cytotoxic profile comparable to more highly doped HASe formulations, while reducing their Se content, potentially improving safety. Mechanistic investigations confirmed that reactive oxygen species (ROS) contribute to the antiproliferative activity of both the platinum complexes and the functionalized NPs, providing insight into the redox-mediated cytotoxicity of these nanomaterials. These findings suggest that PtBP-HASe NPs represent a promising dual-action biomaterial for bone-targeted cancer therapy, combining anticancer efficacy with enhanced biocompatibility potential.

The Endoplasmic Reticulum Quality Control (ERQC) machinery is highly conserved among eukaryotes and assists the newly synthetized proteins in the folding process. Previous works have reported the involvement of ERQC in plant immunity and biotic stress response. However, the interaction between ERQC pathway and heavy metals exposure has been poorly investigated in plants. In the present study, we showed that the Arabidopsis thaliana rsw3 mutant, characterised by a reduced activity of the ER Glucosidase II enzyme, exhibits an increased tolerance to cadmium (Cd) stress. Under standard conditions, rsw3 seedlings exhibit shorter primary roots compared to Wild-type (Wt) plantlets, because of a constitutive ER stress and a consequent upregulation of both ERQC and Unfolded Protein Response (UPR) stress markers in root or shoot tissues. Interestingly, differently from Wt seedlings, these markers remain unchanged in rsw3 under Cd stress. Biochemical data here provided linked the enhanced Cd tolerance of rsw3 to the brassinosteroid receptor 1, BRI1, as the partial impairment of GII activity positively affects the accumulation of the active form of BRI1 receptor on the plasma membrane under Cd stress.

Deep eutectic solvents (DESs) are environmentally friendly solvents formed by combining hydrogen bond donors and acceptors, resulting in a eutectic mixture with a lower melting point than the individual components. While there is extensive research on the electrochemical synthesis of platinum nanoparticles in DESs, to the best of our knowledge, there are no studies on the chemical reactivity of platinum(II) complexes in these systems. This study investigates the simple model reaction between K2PtCl4 and ethylenediamine (en), exploring the behaviour in DES environment, to optimize the synthesis of simple cisplatin-like platinum compounds with the potential objective of improving the traditional methods, decreasing the number of steps required for obtaining target compounds and reducing chemical waste. The reactions were performed in two hydrophilic DESs: choline chloride:glycerol 1:2 (glyceline, GL) and choline chloride:ethylene glycol 1:2 (ethaline, EG). The experiments, conducted in a 70% (v/v) DES and 30% 1:1 H2O/D2O mixture to allow for direct NMR analysis, revealed that en quickly formed [PtCl2(en)], which further reacted to produce [Pt(en)2]Cl2. Reaction products were characterised by 1D (1H and 195Pt{1H}) and 2D ([1H,13C]-HSQC and [1H,15N]-HSQC) NMR experiments. The discolouration of solutions, due to the consumption of K2PtCl4, and the precipitation of the purple Magnus salt [Pt(en)2][PtCl4] occurred over time. The main observed difference between the two solvent mixtures was the slower reactivity in glyceline, due to the much higher viscosity of the solution. Diffusion-ordered spectroscopy (DOSY) indicated lower water mobility in DES mixtures than pure water, with the reaction products closely associated with DES molecules.

The contribution of non-indigenous species to the transfer of contaminants in invaded food webs represents an active research area. Here we measured trace metals and CN stable isotopes in five populations of the invasive Atlantic blue crab Callinectes sapidus and in baseline bivalve species from Spain, Italy and Greece. They were used to estimate trophic transfer effects and the trophic position and isotopic niche of C. sapidus. Maximum trophic transfer effects occurred where the crab showed the largest isotopic niches and highest trophic positions; furthermore, the consistency of trace metal profiles between bivalves and crabs co-varied with the trophic position of the latters. Omnivory may influence the success of an invasive species, but also limit its effectiveness for biomonitoring. However, our results indicated that stable isotopes analysis provides a clarifying background where to cast patterns of contamination of the blue crab as well as of other omnivorous biomonitor species.

It is generally accepted that adjacent guanine residues in DNA are the primary target for platinum antitumor drugs and that differences in the conformations of the Pt-DNA adducts can play a role in their antitumor activity. In this study, we investigated the effect of the carrier ligand cis-1,3-diaminocyclohexane (cis-1,3-DACH) upon formation, stability, and stereochemistry of the (cis-1,3-DACH)PtG2 and (cis-1,3-DACH)Pt(d(GpG)) adducts (G = 9-EthlyGuanine, guanosine, 5′- and 3′-guanosine monophosphate; d(GpG) = deoxyguanosil(3′-5′)deoxyguanosine). A peculiar feature of the cis-1,3-DACH carrier ligand is the steric bulk of the diamine, which is asymmetric with respect to the Pt-coordination plane. The (cis-1,3-DACH)Pt(5′GMP)2 and (cis-1,3-DACH)Pt(3′GMP)2 adducts show preference for the ΛHT and ∆HT conformations, respectively (HT stands for Head-to-Tail). Moreover, the increased intensity of the circular dichroism signals in the cis-1,3-DACH derivatives with respect to the analogous cis-(NH3)2 species could be a consequence of the greater bite angle of the cis-1,3-DACH carrier ligand with respect to cis-(NH3)2. Finally, the (cis-1,3-DACH)Pt(d(GpG)) adduct is present in two isomeric forms, each one giving a pair of H8 resonances linked by a NOE cross peak. The two isomers were formed in comparable amounts and had a dominance of the HH conformer but with some contribution of the ΔHT conformer which is related to the HH conformer by having the 3′-G base flipped with respect to the 5′-G residue.

A new 2-amino imidazole derivative, 5-(4-chlorophenyl)-N,1-di-o-tolyl-1H-imidazole-2-amine (3), has been synthesized using a green approach. The reaction was conducted in a ChCl (cholinium chloride)/urea eutectic mixture, which is a nature-inspired and environmentally friendly reaction medium. The proposed reaction mechanism involves the preliminary regioselective alkylation of the Nsp2 of guanidine (2), followed by an intramolecular condensation between the carbonyl moiety and the secondary N′sp3. Finally, a tautomerization/aromatization step furnished the final product (3). Notably, 2-amino imidazole (3) could be isolated in high yield (91%), just by filtration from the DES/water mixture and subsequent crystallization; the remaining ChCl/urea could be recycled, after water removal, for four consecutive reactions without any significant drop in the (3) yield. The product has been fully characterized by 1H, 13C, 2D 1H-13C HSQC, and 2D 1H-13C HMBC NMR; FT-IR spectroscopy; and EI-MS spectrometry.

Pomegranate (Punica granatum L.) fruits are a historical agricultural product of the Mediterranean basin that became increasingly popular in the latest years for being rich in antioxidants and other micronutrients, and are extensively commercialized as fruits, juice, jams and, in some Eastern countries, as a fermented alcoholic beverage. In this work, four different pomegranate wines specifically designed using combinations of two cultivars (Jolly Red and Smith) and two yeast starters with markedly different characteristics (Saccharomyces cerevisiae Clos and Saccharomyces cerevisiae ex-bayanus EC1118) were analyzed. The chemical characterization of the wines together with the originating unfermented juices was performed by 1H NMR spectroscopy metabolomic analysis. The full spectra were used for unsupervised and supervised statistical multivariate analysis (MVA), namely Principal Component Analysis (PCA), Orthogonal Partial Least Squares Discriminant Analysis (OPLS-DA), and sparse PCA (SPCA). The MVA of the wines showed a clear discrimination between the cultivars, and a smaller, yet significant, discrimination between the yeasts used. In particular, a higher content of citrate and gallate was observed for the Smith cv. and, on the contrary, a statistically significant higher content of fructose, malate, glycerol, 2,3 butanediol, trigonelline, aromatic amino acids and 4-hydrophenylacetate was observed in Jolly Red pomegranate wines samples. Significant interaction among the pomegranate cultivar and the fermenting yeast was also observed. Sensorial analysis was performed by a panel of testing experts. MVA of tasting data showed that the cultivar significantly affected the organoleptic parameters considered, while the yeast had a minor impact. Correlation analysis between NMR-detected metabolites and organoleptic descriptors identified several potential sensorially-active molecules as those significantly impacting the characteristics of the pomegranate wines.

The Pd-catalyzed amino- and alkoxycarbonylation of aryl iodides has been exploited, for the first time, in a bioinspired Deep Eutectic Solvent and under gas-free conditions, by using Mo(CO)(6) as the CO source. The method allows for the preparation of carboxylic amides and esters in high yields (up to 99 %), short reaction time (2 h) and under mild reaction conditions (80 degrees C), with a low catalyst loading (2.5 mol %). Noteworthy, in the case of N-hexylbenzamide, it has been demonstrated that both the catalyst and DES can be used for four consecutive runs, with a moderate decrease of catalytic efficiency. The methodology has been also applied to the preparation of an Active Pharmaceutical Ingredient used for the treatment of human scabies and lice.

A new 2-amino imidazole derivative, 5-(4-chlorophenyl)-N,1-di-o-tolyl-1H-imidazole-2-amine (3), has been synthesized using a green approach. The reaction was conducted in a ChCl (cholinium chloride)/urea eutectic mixture, which is a nature-inspired and environmentally friendly reaction medium. The proposed reaction mechanism involves the preliminary regioselective alkylation of the Nsp2 of guanidine (2), followed by an intramolecular condensation between the carbonyl moiety and the secondary N′sp3. Finally, a tautomerization/aromatization step furnished the final product (3). Notably, 2-amino imidazole (3) could be isolated in high yield (91%), just by filtration from the DES/water mixture and subsequent crystallization; the remaining ChCl/urea could be recycled, after water removal, for four consecutive reactions without any significant drop in the (3) yield. The product has been fully characterized by 1H, 13C, 2D 1H-13C HSQC, and 2D 1H-13C HMBC NMR; FT-IR spectroscopy; and EI-MS spectrometry.

Arsenic (As) is a well-known toxic metalloid, but environmental risks due to excessive As content in soils or sediments depend on the chemical forms present and their relative mobility. Long-term exposure to arsenic may cause several diseases. In order to assess the possible risks in the heavily impacted Consorzio per lo Sviluppo Industriale e di Servizi Reali alle Imprese (Consortium for Industrial Development and Effective Services for Business, S.I.S.R.I.) industrial area of Brindisi (Apulia, southern Italy), 38 soil samples were collected in the area, from 18 sampling points previously determined as outliers. Total As determination, speciation analysis, and a cession test with acetic acid were performed. Speciation analysis was performed by HPLC coupled to hydride generation-atomic absorption spectroscopy (HG-AAS). Total As determination obtained by mineralization showed a concentration range between 51.8 and 169.6 mg kg−1, which is higher than the limit of 50 mg kg−1 established by D.M. (Ministerial Decree) 471/99 for industrial areas. The highest concentrations of extracted As were obtained in the top-soil layers. As(III) and As(V) were detected in all the samples, while the concentrations of the organic species monomethyl arsonic acid (MMAA) and dimethyl arsenic acid (DMAA) were always under the detection limit. The samples releasing the highest As quantities in the acetic acid cession test were in every circumstance collected from the superficial soil levels. The different amounts of As determined in the sampling sites could depend on the distance from the specific sources of pollution, even if it is very difficult to identify them in a very complex industrial zone such as the S.I.S.R.I. area of Brindisi. In this study, As occurs mainly as relatively immobile or slowly exchangeable forms: for this reason, it is more abundant in the top-soil and is little affected by the action of rainwater, which transports only reduced quantities of As into the deeper layers.

We report about the response of Arabidopsis thaliana to chronic and temporary Cd2+ stress, and the Cd2+ induced activation of ER stress and unfolded protein response (UPR). Cd2+-induced UPR proceeds mainly through the bZIP60 arm, which in turn activates relevant ER stress marker genes such as BiP3, CNX, PDI5 and ERdj3B in a concentration- (chronic stress) or time- (temporary stress) dependent manner. A more severe Cd-stress triggers programmed cell death (PCD) through the activation of the NAC089 transcription factor. Toxic effects of Cd2+ exposure are reduced in the Atbzip28/bzip60 double mutant in terms of primary root length and fresh shoot weight, likely due to reduced UPR and PCD activation. We also hypothesised that the enhanced Cd2+ tolerance of the Atbzip28/bzip60 double mutant is due to an increase in brassinosteroids signaling, since the amount of the brassinosteroid insensitive1 receptor (BRI1) protein decreases under Cd2+ stress only in Wt plants. These data highlight the complexity of the UPR pathway, since the ER stress response is strictly related to the type of the treatment applied and the multifaceted connections of ER signaling. The reduced sensing of Cd2+ stress in plants with UPR defects can be used as a novel strategy for phytoremediation.

Despite many advantages, digital impressions, when compared to the conventional one, produce contrasting results and their complete substitution is still under debate. This comparative study aims to test a way to perform a clinical evaluation of digital impression Accuracy and Trueness with a gypsum check. After calculating the Trueness, Precision, and Accuracy of the digital impressions, a gypsum check was fabricated and screwed on implant abutments. The impression was not considered reliable if the gypsum check fractured during the insertion. The gypsum check test was correlated to a cut-off of 100 µm Trueness. Mean Trueness was 151.19 ± 37.23 µm of the first optical impression and 125.47 ± 41.90 µm of the second optical impression. The Precision mean was 39.76 ± 10.89 µm. The mean Accuracy percentage was 98.69 ± 0.29%. The gypsum checks fractured 10 times on 42 tests, and in any case, the Trueness value was above the 100 µm cut off, with a p = 0.001. A gypsum check screwed onto an implant abutment could be considered a way to perform clinical measurement of Trueness, allowing the clinician to understand if the Trueness value is higher or lower than 100 µm and reflecting the reliability of digital impressions.

A new 2-amino imidazole derivative, 5-(4-chlorophenyl)-N,1-di-o-tolyl-1H-imidazole-2-amine (3), has been synthesized using a green approach. The reaction was conducted in a ChCl (cholinium chloride)/urea eutectic mixture, which is a nature-inspired and environmentally friendly reaction medium. The proposed reaction mechanism involves the preliminary regioselective alkylation of the Nsp2 of guanidine (2), followed by an intramolecular condensation between the carbonyl moiety and the secondary N′sp3. Finally, a tautomerization/aromatization step furnished the final product (3). Notably, 2-amino imidazole (3) could be isolated in high yield (91%), just by filtration from the DES/water mixture and subsequent crystallization; the remaining ChCl/urea could be recycled, after water removal, for four consecutive reactions without any significant drop in the (3) yield. The product has been fully characterized by 1H, 13C, 2D 1H-13C HSQC, and 2D 1H-13C HMBC NMR; FT-IR spectroscopy; and EI-MS spectrometry.

In the original publication [...].

Dittrichia viscosa uptake and translocation of the metalloid As is not fully understood and some data are contradictory, but its adaptability to this pollutant is known and is dependent on its genetic variability. D. viscosa is not a hyperaccumulator plant, but it can grow in high-drought conditions while still producing large biomass, even tolerating significant concentrations of As3+ and As5+. In spite of these remarkable characteristics, adaptive modification of performances is not predictable in wild populations. In previous work, we established experimental clonal populations to perform a functional study on the aquaporin NIP1.1. Here, we propose a strategy to select a clonal population of D. viscosa with a defined phenotype related to As tolerance and to reduced NIP1.1 expression levels for phytoremediation applications. From the previous work, we selected four independent clones, two of them belonging to the weak population (W8 and W9) and the other two belonging to the strong population (S1 and S3). The weak and strong populations differ for a different expression ratio root/shoot of DvNip1;1 that brings a different tolerance to As presence. The stress response of the populations, revealed by the CAT enzymatic test, was statistically correlated to the clones, but not to As uptake. Performance of the selected plants on a second unrelated metallic pollutant, Cd, was evaluated, showing that Cd uptake is also independent from the tolerant phenotype. In vitro culture methods using solid media and temporary immersion bioreactors were compared to propose an optimized combined protocol. The procedure yielded propagation of genetically stable tolerant clonal lines with good uptake of As and Cd. The plants, mass-produced with the developed in vitro protocol, were able to maintain their acquired abilities and are potentially able be later applied in phytoremediation or contaminated areas' re-naturalization.

Aims Climate change imposes adaptation of viticulture in risk areas, such as the Mediterranean. Mycorrhization is a valid tool to reduce the impact of the expected temperature/drought increase. Aim of this work was to test the effects of mycorrhization on grapevine vegetative growth, element composition of soil/leaves, and microbiota of bulk soil/rhizosphere/endorhiza, in the field, under exacerbated summer stress conditions obtained by planting the rootstocks in June. Methods 118 rooted cuttings of 1103-Paulsen ( Vitis berlandieri × Vitis rupestris ) were planted in Salento (Apulia, Southern Italy); about half of them were mycorrhized. Leaf Area Index, shoot growth and survival rate were monitored across two growing seasons. Leaf/shoot weight, chemical analysis of 25 elements, and 16S rRNA gene metabarcoding of bulk soil/rhizosphere/endorhiza were performed on subsamples. Results Mycorrhized plants showed significantly higher survival rate and growth, and accumulated significantly higher amounts of 18 elements. 27 endorhizal OTUs (representing ~20% of total sequences) were differently distributed (20 OTUs more abundant in mycorrhized plants); in the rhizosphere, instead, 12 OTUs (~2.5% of total sequences) were differently distributed. A few Actinobacterial OTUs were enriched by mycorrhization in the root endosphere; the same OTUs were the most correlated with the chemical elements, suggesting a role in element dynamics. These OTUs were not hub taxa of the co-occurrence network. Conclusions This work shed light onto the interactions between mycorrhiza and microbiome, in the context of plant element dynamics, which is useful to identify potential target candidates for biotechnological applications, thus moving towards a more sustainable, ecosystem-based viticulture.

Pomegranate peel extract is rich of interesting bioactive chemicals, principally phenolic compounds, which have shown antimicrobial, anticancer, and antioxidative properties. The aim of this work was to improve extract' bioactivity through the adsorption on calcium carbonate nanocrystals. Nanocrystals revealed as efficient tools for extract adsorption reaching 50% of loading efficiency. Controlled release of the contained metabolites under acidic pH has been found, as it was confirmed by quantitative assay and qualitative study through NMR analysis. Specific functionality of inorganic nanocarriers could be also tuned by biopolymeric coating. The resulting coated nanoformulations showed a great antimicrobial activity against B. cinerea fungus preventing strawberries disease better than a commercial fungicide. Furthermore, nanoformulations demonstrated a good antiproliferative activity in neuroblastoma and breast cancer cells carrying out a higher cytotoxic effect respect to free extract, confirming a crucial role of nanocarriers. Finally, pomegranate peel extract showed a very high radical scavenging ability, equal to ascorbic acid. Antioxidant activity, measured also in intracellular environment, highlighted a protective action of extract-adsorbed nanocrystals twice than free extract, providing a possible application for new nutraceutical formulations.

New compounds structurally derived from oxaliplatin exhibit high potency in malignant pancreatic adenocarcinoma cells. Their mechanism of antiproliferative action in pancreatic cancer cells involves inhibition of de novo lipid synthesis.

In order to evaluate the local environmental risk deriving from coal transport and burning, 30 soil samples were collected along the coal conveyor belt and around the coal-burning power plant Federico II of Brindisi (Apulia, southern Italy). Since soil pollution of metals and metalloids is measured not only by their total concentration but also by evaluating their mobility and availability, arsenic sequential extraction, leaching test and speciation analysis were performed. The analytical results showed that the most abundant As amount was contained in the final residue of the sequential extraction procedure, the so-called occluded As, embedded in rock formations such as sulphides. Moreover speciation chemical analysis showed that As(V) was by far the most abundant species, whereas As(III), which represents the most soluble and available species, was only a very small fraction. No arsenic organic species were detected in the soil samples.