Heterotopic mechanically interlocked molecules contain different binding sites within their structure, allowing them to recognize specific ion pairs (cations and anions) with a high affinity. The employment of heteroditopic receptors offers advantages over monotopic analogues, in general, being composed of both cation and anion binding sites. The present study elucidates the electronic structure-based recognition of anions and cations of a heteroditopic [2]catenane, IO. Spherical cations and anions have been employed. The structure of IO was modified by replacing its original oxygen atoms of the crown-ether moiety by sulfur atoms and σ-hole donor iodines by -Te-CH3 groups leading to the modified [2]catenanes IS and TeO, respectively. Energy decomposition analysis (EDA) and natural orbital for chemical valence reveals that the cations exhibit the strongest interaction with the binding pockets of all structures, with Cu+, Li+, and Ni2+ presenting the most stabilizing values, ΔEIOtot = -198.2, -175.1, and -653.4 kcal·mol-1, and ΔEIStot= -226.4, -154.0, -702.5 kcal·mol-1, respectively. In contrast, anion recognition presented to be significantly lower, being purely dependent on the strength of the σ-hole donors and the size of the applied anion, with Cl- exhibiting the most stable interaction, where ΔEIOtot = -109.9 kcal·mol-1. It was also found that the anion recognition for this particular molecule does not affect the cation recognition, significantly. The EDA results confirm that changing from a harder (O) to a softer (S) interactive environment will have considerable impact on cation recognition, thereby demonstrating the pivotal role, following the size match rule.
Breast cancer (BC) is one of the most challenging types of cancer in women. Triple-negative breast cancer (TNBC) is an aggressive and rapidly progressive subtype that lacks targeted therapies, relying primarily on chemotherapy. Given the limited treatment options for TNBC, novel therapeutic strategies are needed to address this disease. In this context, here we report the synthesis and characterization of four ruthenium(II) complexes containing naphthoquinone derivatives as ligands: [Ru(NQ1)(bipy)(dppen)]PF6 (Ru1), [Ru(NQ2)(bipy)(dppen)]PF6 (Ru2), [Ru(NQ1)(bipy)(DPEphos)]PF6 (Ru3), and [Ru(NQ2)(bipy)(DPEphos)]PF6 (Ru4), where bipy = 2,2'-bipyridine, dppen = 1,2-bis(diphenylphosphino)ethylene, DPEphos = bis[(2-diphenylphosphino)phenyl]ether, and NQ1 and NQ2 = deprotonated lawsone and lapachol, respectively. Mass spectrometry and elemental analyses were used to confirm the purity of the complexes. In vitro assays showed that Ru1-Ru4 were cytotoxic against MDA-MB-231 and MCF-7 (breast cancer cell lines) and A549 (lung cell line). The compounds exhibited lower IC50 values than cisplatin, used as a control. Ru4 was the most promising compound, with the highest selectivity index for the triple-negative breast cancer cell line (SI = 25.5). Furthermore, this complex inhibited colony formation, induced apoptosis, and affected the cell cycle in these cancer cells. Western blot analysis showed increased cleaved caspase-3 expression, corroborating the apoptotic mechanism observed by flow cytometry. Furthermore, cell uptake studies showed that ruthenium was found at the intracellular level after treatment with the MDA-MB-231 cell line. DNA-binding studies revealed an interaction between Ru1-Ru4 and Ct-DNA via the minor groove pocket, as confirmed by molecular docking. Overall, our results suggest [Ru(NQ2)(bipy)(DPEphos)]PF6 (Ru4) to be a promising cytotoxic agent against breast cancer.
The misunderstanding of adolescence has had a direct impact on the creation of public policies that directly serve this population. The aim of this study was to understand how socio-education takes place between the guarantee of rights and the social vulnerabilities that exist in the territory. This section of the research involves the development of six focus groups with twelve adolescent participants, as well as a semi-structured interview with family members. The content was analyzed using pre-established categories and subcategories obtained after data collection. It was pointed out that offending should be seen as a multifactorial cause, motivated mainly by social disenfranchisement and the absence of a clear and effective system for guaranteeing rights, which includes all public policies.
Este relato de experiência analisa o Grupo de Estudos Experiências e Vivências Sexuais e de Gênero, criado em 2025 na Saúde Mental Camarada, como dispositivo psicodramático decolonial, transfuncional e virtual. A materialidade analítica compreende escolhas metodológicas, estratégias de intervenção, manejos e processamento reflexivo da codireção, sem análise de dados individuais. Oito encontros são discutidos como cenas analisadoras da articulação entre a formação política, o gênero, a sexualidade e a saúde mental. A experiência permite examinar possibilidades e limites dos métodos de ação em ambiente virtual, mobilizar a noção de vínculos insurgentes e formular a ideia de revoluções mínimas como operadores interpretativos. Concluiu-se que grupos formativos podem favorecer a desprivatização do sofrimento sem se converterem em psicoterapia.
