Novel tetraplatinated metalloporphyrin-based photosensitizers (PSs) are reported, which show excellent phototoxic indexes (PIs) up to 5800 against HeLa cells, which is, to the best of our knowledge, the highest value reported for any porphyrin so far. Furthermore, ⁶⁷Zn isotope labelling allowed the determination of the ratio of zinc to platinum inside the cells using ICP-MS.

The abandonment of farmland in Europe is a significant issue due to its environmental, socio-economic, and landscape consequences. This tendency mainly impacts marginal and inner areas, located far from large urban districts, because of biophysical and/or socio-economic factors. Although European and national regulations try to turn the fragility of these territories into an opportunity for sustainable development, many of these areas, especially in southern Europe, continue to suffer socio-economic disparities. For this reason, it is necessary to consider regional and district-wide initiatives that can economically revitalize marginal areas while safeguarding their natural capital. Alternative cropping systems, capable of optimizing the quality of some food crops, can play an essential role in the economic development of populations living in marginal areas. These areas, represented by inland zones often abandoned due to the difficulty of applying mechanized agriculture, can represent an opportunity to rediscover sustainable and profitable practices. Among the high-value crops, saffron (Crocus sativus L.), “red gold” and “king of spices”, stands out for its potential. Indeed, thanks to the use of tuff tubs, a more eco-sustainable choice compared to the plastic pots already mentioned in the literature, it is possible to improve the quality of this spice. Furthermore, Crocus sativus L. not only lends itself to multiple uses but also represents a valid opportunity to supplement agricultural income. This is made possible by its high profitability and beneficial properties for human health, offering a way to diversify agricultural production with positive economic and social impacts. It is known that the saffron market in Italy suffers from competition from developing countries (Iran, Morocco, India) capable of producing saffron at lower costs than European countries, thanks to the lower cost of labor. Therefore, this study seeks to identify marginal areas that can be recovered and valorized through an eco-sustainable cultivation system with the potential to enhance the quality of this spice, making it unique and resilient to competition. Specifically, this paper is organized on a dual scale of investigation: (a) at the local level to demonstrate the economic-ecological feasibility of saffron cultivation through the adoption of an alternative farming technique on an experimental site located in Tricarico (Basilicata—Southern Italy, 40°37′ N, 16°09′ E; 472 m. a.s.l.) that, although fertile, is not suitable for mechanized cropping systems; (b) at the regional level through a spatially explicit land suitability analysis to indicate the possible location where to export saffron cultivation. The final map, obtained by combining geo-environmental variables, can be considered a precious tool to support policymakers and farmers to foster a broad agricultural strategy founded on new crop management systems. The adoption of this alternative agroecological system could optimize the use of land resources in the perspective of increasing crop productivity and profitability in marginal agricultural areas.

The hydrophobic effect is the main factor that drives the folding of polypeptide chains. In this study, we have examined the influence of the hydrophobic effect in the context of the main mechanical forces approach, mainly in relation to the establishment of specific interplays, such as hydrophobic and CH–π cloud interactions. By adopting three oligopeptides as model systems to assess folding features, we demonstrate herein that these finely tuned interactions dominate over electrostatic interactions, including H-bonds and electrostatic attractions/repulsions. The folding mechanism analysed here demonstrates cooperation at the single-residue level, for which we propose the terminology of “single residues cooperative folding”. Overall, hydrophobic and CH–π cloud interactions produce the main output of the hydrophobic effect and govern the folding mechanism, as demonstrated in this study with small polypeptide chains, which in turn represent the main secondary structures in proteins.

The folding of peptides and proteins is rigidly reliant on the ‘chemical information’ carried by the specific amino acid sequence. In this study, three polypeptides (PDBs: 2jof, 1res and 1prv) were investigated as model systems to assess their folded features, thereby enabling further understanding of mechanisms that play a role in regulating the folding process more widely. A novel physico‐chemical approach of analysis is proposed herein, focusing on chemical interactions and their related mechanical forces that we trust are determinant to drive the folding. Through this methodology, we have predicted the conformations adopted by the three polypeptides and compared the outcomes to those experimentally determined, achieving a substantial structural agreement. Molecular dynamic simulations have been carried out to further support our calculations and structural results. Within the three models, we demonstrate that the interaction of each amino acid residue with its neighbour residues is a crucial determinant for the formation of the 3D stable native structures. This article provides initial evidence that the folding occurs by means of mechanical forces developed upon establishing chemical interactions amongst residues, which, in turn, are peculiar to each specific amino acid present in each position of the peptide chain.

The genetic material in living systems is mainly stored in DNA molecules, which in turn play a dominant biological role in relation to the coding and transfer of genetic information, the biosynthesis of proteins and RNA and the packaging and regulation of DNA expression and accessibility. These features, strictly dictated by the three-dimensional structure of DNA, are governed by non-covalent chemical interactions that drive the folding process of these biological macromolecules. The Main Mechanical Forces (MMFs) approach is a recently formulated calculation method, based on the accurate prediction of structural features of biomolecules through an in-depth assessment of the interplay between specific non-covalent chemical interactions and related mechanical forces developed during the folding process. By adopting the MMFs method in the context of nucleic acids, we report here the results obtained in terms of predicting three-dimensional DNA oligomer tertiary structures. To this end, we have developed tailored nucleic acid-specific equations, enabling to predict the torsion angles (with a relevant level of agreement with experimental values) of the phosphate-sugar backbone of the three model molecules A-, B- and Z- DNA used in this study. To increase the validity of this methodology, we have conducted RMSD measurements, indicating that there is a weak but rather acceptable match between the calculated vs. predicted A-DNA structure, whereas the prediction of the BII-DNA and Z-DNA tertiary structures was fully correct.