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The current article reports the investigation of three new Ni(II) complexes with ONS-donor dithiocarbazate ligands: [Ni(L1)PPh3] (1), [Ni(L2)PPh3] (2), and [Ni(L2)Py] (3). Single-crystal X-ray analyses revealed mononuclear complexes with a distorted square planar geometry and the metal centers coordinated with a doubly deprotonated dithiocarbazate ligand and coligand pyridine or triphenylphosphine. The non-covalent interactions were investigated by the Hirshfeld surface and the results revealed that the strongest interactions were π⋅⋅⋅π stacking interactions and non-classical hydrogen bonds C–H···H and C–H···N. Physicochemical and spectroscopic methods indicate the same structures in the solid state and solution. The toxicity effects of the free ligands and Ni(II) complexes were tested on the human breast cancer cell line MCF-7 and non-malignant breast epithelial cell line MCF-10A. The half-maximal inhibitory concentration (IC50) values, indicating that the compounds were potent in inhibiting cell growth, were obtained for both cell lines at three distinct time points. While inhibitory effects were evident in both malignant and non-malignant cells, all three complexes demonstrated lower IC50 values for malignant breast cell lines than their non-malignant counterparts, suggesting a stronger impact on cancerous cell lines. Furthermore, molecular docking studies were performed showing the complex (2) as a promising candidate for further therapeutic exploration.

The present work reports the influence of the presence of different ions (Cl−, Br−, NO3−, or SO42−) on the formation and proprieties of Cu(II) complexes with pyridoxal-benzoylhydrazone (PLBHZ). Four new complexes were successfully synthesized, [CuCl2(PLBHZ)] (1), [CuBr2(PLBHZ)] (2), [CuCl(PLBHZ)H2O]⋅NO3⋅H2O (3), and [CuSO4(PLBHZ)H2O]⋅3H2O (4), and characterized by spectroscopic and physicochemical methods. A single-crystal X-ray study reveals the Schiff base coordinated to the metal center tridentate by the ONS-donor system, resulting in distorted square pyramidal coordination geometries. Noncovalent interactions were investigated by 3D Hirshfeld surface analysis by the dnorm function, 2D fingerprint plots, and full interaction maps. The ion exchange is important in forming three-dimensional networks with π⋅⋅⋅π stacking interactions and intermolecular hydrogen bonds. The in vitro biological activity of the free ligand and metal complexes was evaluated against Gram-positive and Gram-negative bacterial strains and the free pyridoxal-hydrazone ligand showed higher activity than their Cu(II) complexes. Molecular docking was used to predict the inhibitory activity of the ligand and complexes against Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli bacteria.

In the search for new metal complexes with antitumor potential, two dithiocarbazate ligands derived from 1,1,1-trifluoro-2,4-pentanedione (H2L1) and (H2L2) and four Ni(II) complexes, [Ni(L1)PPh3] (1), [Ni(L1)Py] (2), [Ni(L2)PPh3] (3), and [Ni(L2)Py] (4), were successfully synthesized and investigated by physical-chemistry and spectroscopic methods. The crystal structure of the H2L1 and the Ni(II) complexes has been elucidated by single-crystal X-ray diffraction. The obtained structure from H2L1 confirms the cyclization reaction and formation of the pyrazoline derivative. The results showed square planar geometry to the metal centers, in which dithiocarbazates coordinated by the ONS donor system and a triphenylphosphine or pyridine molecule complete the coordination sphere. Hirshfeld surface analysis by dnorm function was investigated and showed π–π stacking interactions upon the molecular packing of H2L1 and non-classical hydrogen bonds for all compounds. Fingerprint plots showed the main interactions attributed to H⋅H C⋅H, O⋅H, Br⋅H, and F⋅H, with contacts contributing between 1.9% and 38.2%. The mass spectrometry data indicated the presence of molecular ions [M + H]+ and characteristic fragmentations of the compounds, which indicated the same behavior of the compounds in solution and solid state. Molecular docking simulations were studied to evaluate the properties and interactions of the free dithiocarbazates and their Ni(II) complexes with selected proteins and DNA. These results were supported by in vitro cytotoxicity assays against four cancer cell lines, showing that the synthesized metal complexes display promising biological activity.

Coalitional presidentialism is a power-sharing strategy deployed in multiparty presidentialist democracies that entails the distribution of cabinet positions to coalition partners to facilitate governability. This model of governance is increasingly common worldwide, gaining growing scholarly interest. The consequences of coalitional presidentialism for women’s cabinet representation, however, have received scant attention. In this article, we provide a gendered analysis of the Brazilian experience with coalitional presidentialism. Through the quantitative analysis of an original dataset of all ministerial appointments ( N = 597) under eight Brazilian presidents (1985–2019) and a descriptive assessment of the coalitional dynamics during that period, we evaluate the Brazilian experience with coalitional presidentialism through the lens of Feminist Institutionalism. We show that coalitional presidentialism restricts women's access to cabinet seats, with the demands of multiparty coalition formation and management often overriding presidential considerations about descriptive representation, and coalition parties rarely advancing women to fill portfolios allocated to them by the president.

The current research describes the synthesis and characterization of 2-acetylpyridine N(4)-cyclohexyl-thiosemicarbazone ligand (HL) and their two metal complexes, [Au(L)Cl][AuCl2] (1) and [Pd(L)Cl]·DMF (2). The molecular structures of the compounds were determined by physicochemical and spectroscopic methods. Single crystal X-ray diffraction was employed in the structural elucidation of the new complexes. The complexes showed a square planar geometry to the metal center Au(III) and Pd(II), coordinated with a thiosemicarbazone molecule by the NNS-donor system and a chloride ion. Complex (1) also shows the [AuCl2]− counter-ion in the asymmetric unit, and complex (2) has one DMF solvent molecule. These molecules play a key role in the formation of supramolecular structures due to different interactions. Noncovalent interactions were investigated through the 3D Hirshfeld surface by the dnorm function and the 2D fingerprint plots. The biological activity of the compounds was evaluated in vitro against the human glioma U251 cells. The cytotoxicity results revealed great antitumor activity in complex (1) compared with complex (2) and the free ligand. Molecular docking simulations were used to predict interactions and properties with selected proteins and DNA of the synthesized compounds.

What happens when a traditional source of political capital becomes a health hazard? Stigmatized electoral practices, such as vote buying, are a double-edged sword: While these strategies may signal candidates’ electoral strength, they may also entail reputational costs. In normal times, street campaigns are a non-stigmatized electoral practice. During the Covid-19 pandemic, however, they imposed health risks. Employing data from a national survey experiment conducted in Brazil prior to the 2020 municipal elections ( N = 2025), we extend research on the employment of stigmatized campaigns and the gendered dynamics of electoral viability. We find that voters evaluate candidates who engage in face-to-face activities as less electorally viable and report lower intent to support them. These dynamics do not impact all candidates equally: Voters more harshly punish women candidates who conduct street campaigns than men, leading women to lose the advantage they have over men when both employ non-stigmatized campaign practices.

Cannabidiol (CBD) is a non-intoxicating compound extracted from Cannabis sativa, showing antidepressant-like effects in different rodent models. However, inconsistent results have been described depending on the species and the strain used to assess depressive-like behavior. Moreover, only a few studies investigated the effect of CBD in female rodents. Therefore, we aimed to (i) investigate the effects of CBD in two different strains of mice (Swiss and C57BL/6) and a rat model of depression based on selective breeding (Flinders Sensitive and Resistant Lines, FSL and FRL) subjected to tests predictive of antidepressant-like effects and (ii) investigate the influence of sex in the effects of CBD in both mice and rats. CBD induced an antidepressant-like effect in male Swiss but not in female Swiss or C57BL/6 mice in the tail suspension test (TST). In male FSL rats, CBD produced an antidepressant-like effect 1 h post injection. However, in female FSL, CBD induced a bimodal effect, increasing the immobility time at 1 h and decreasing it at 2 h. In conclusion, strain, sex, and administration time affect CBD’s behavioral response to rodents exposed to tests predictive of antidepressant effects.

We examine the distribution and consequences of postmaterialist value orientations among national legislators in Brazil. Using data collected in the Brazilian Legislative Survey in 2013, we undertake the first systematic study of postmaterialism within the National Congress and the party system and map the materialist/postmaterialist scale onto other salient divisions within the political class. We present five main findings. First, political elites evince vastly higher commitment to postmaterialism than the mass public. Second, Brazilian political elites drawn from constituencies with higher human development are more postmaterialist than their counterparts in other constituencies. Third, within the political class, the materialist/post¬materialist cleavage overlaps in important ways with the left–right cleavage. Fourth, although postmaterialism successfully predicts elite attitudes on a number of “new politics†issues that are unrelated to the construction of the postmaterialist scale itself, postmaterialism is a poor predictor of voting behavior on the Congressional floor. Fifth, as others before us, we find institutional factors to be better predictors of legislative voting behavior in the Brazilian context.

The title complex, [AuCl(C18H16N5S)]Cl·1.5H2O, may be considered as a gold(I) compound with the corresponding metal site coordinated by a thiosemicarbazone ligand through the S atom. The ligand adopts an E conformation and the gold(I) atom displays the expected linear geometry with a Cl atom also bonded to the metal ion [Cl—Au—S = 174.23 (5)°]. One of the pyridyl rings is protonated, giving the gold complex an overall positive charge. Two solvent water molecules, one of which is located on a twofold rotation axis, and a non-coordinating chloride ion complete the structural assembly. The molecular structure is stabilized by intramolecular and intermolecular N—H...Cl, N—H...N, O—H...Cl and O—H...O hydrogen bonding.

The title compound, C16H14Cl2O2, is a chiral mitotane derivative that contains a dioxolane ring and crystallizes from methanol as a racemic mixture. It was obtained in high yield from mitotane and ethyleneglycol in alkaline medium, followed by neutralization with sulfuric acid and extraction with ethyl acetate. The molecular structure is stabilized by an intramolecular C— H... O hydrogen bond. The dihedral angle between the aromatic rings is 80.1 (2)°. The dioxolane ring adopts a puckered envelope conformation with an O atom as the flap.

In the structure of the title chalcone, C17H14O2, derived from cinnamaldehyde, the olefine group has a trans configuration. The molecular conformation is stabilized by an intramolecular O—H...O hydrogen-bond interaction with graph-set motif S(6).

New democracies inherit a variety of institutions from prior authoritarian regimes, including political parties, militaries and entrenched oligarchies. While these authoritarian legacies have generally been well-researched, one set of institutions has received relatively little attention: state-backed trade unions that lose official sponsorship after democratizing transitions. In most new democracies and competitive authoritarian regimes, these "legacy unions" have remained the dominant workers' organizations despite few internal reforms. Previous research on the causes and consequences of legacy union dominance has rested on case studies of post-transition countries and small-N comparisons. In this article, we offer a global perspective on the fates of legacy unions by introducing new data about the relative importance of legacy unions in post-Third Wave democracies. We show that most legacy unions survive democratic transitions and remain dominant in new democracies, although with significant regional variation. Our data and analyses suggest that these trade unions are authoritarian legacies which continue to influence labour politics in new democracies. Dominant legacy unions are associated with lower labour movement fragmentation and better-protected labour rights in new democracies. [ABSTRACT FROM AUTHOR]