Insights into Triazolylidene Ligands Behaviour at a Di-Iron Site Related to [FeFe]-Hydrogenases

The behaviour of triazolylidene ligands coordinated at a {Fe₂(CO)₅(µ-dithiolate)} core related to the active site of [FeFe]-hydrogenases have been considered to determine whether such carbenes may act as redox electron-reservoirs, with innocent or non-innocent properties. A novel complex featuring a mesoionic carbene (MIC) [Fe₂(CO)₅(Pmpt)(µ-pdt)] (1; Pmpt = 1-phenyl-3-methyl-4-phenyl-1,2,3-triazol-5-ylidene; pdt = propanedithiolate) was synthesized and characterized by IR, ¹H, ¹³C{¹H} NMR spectroscopies, elemental analyses, X-ray diffraction, and cyclic voltammetry. Comparison with the spectroscopic characteristics of its analogue [Fe₂(CO)₅(Pmbt)(µ-pdt)] (2; Pmbt = 1-phenyl-3-methyl-4-butyl-1,2,3-triazol-5-ylidene) showed the effect of the replacement of a n-butyl by a phenyl group in the 1,2,3-triazole heterocycle. A DFT study was performed to rationalize the electronic behaviour of 1, 2 upon the transfer of two electrons and showed that such carbenes do not behave as redox ligands. With highly perfluorinated carbenes, electronic communication between the di-iron site and the triazole cycle is still limited, suggesting low redox properties of MIC ligands used in this study. Finally, although the catalytic performances of 2 towards proton reduction are weak, the protonation process after a two-electron reduction of 2 was examined by DFT and revealed that the protonation process is favoured by S-protonation but the stabilized diprotonated intermediate featuring a {Fe-H⋯H-S} interaction does not facilitate the release of H₂ and may explain low efficiency towards HER (Hydrogen Evolution Reaction).     

Intermolecular Forces Driving Hexamethylenetetramine Co-Crystal Formation,a DFT and XRD Analysis

Interest in co-crystals formation has been constantly growing since their discovery, almost a century ago. Such success is due to the ability to tune the physical-chemical properties of the components in solid state by avoiding a change in their molecular structure. The properties influenced by the co-crystals formation range from an improvement of mechanical features and chemical stability to different solubility. In the scientific research area, the pharmacological field is undoubtedly one of those in which an expansion of the co-crystal knowledge can offer wide benefits. In this work, we described the crystalline structure of hexamethylenetetramine co-crystallized with the isophthalic acid, and we compared it with another co-crystal, showing the same components but different stoichiometry. To give a wider overview on the nature of the interactions behind the observed crystal packing and to rationalize the reasons of its formation, a computational analysis on such structures was carried out.     

Towed wheel shimmy suppression through a nonlinear tuned vibration absorber

The implementation of the nonlinear tuned vibration absorber (NLTVA) for the suppression of shimmy vibration in towed wheels is addressed in this study. We adopt a modified straight tangent tyre model of a single-degree-of-freedom towed wheel system with an attached NLTVA. Stability analysis illustrated that the NLTVA can significantly improve the stability of the equilibrium of the wheel. Bifurcation analysis highlighted the existence of large bistable regions, which undermines the system’s safety. However, numerical continuation analysis, coupled with a dynamical integrity investigation, revealed that the addition of an intentional softening nonlinearity in the absorber restoring force characteristic enables the complete suppression of the bistable regions, also reducing the amplitude of shimmy oscillations in the unstable region. Quasiperiodic motions were also identified; however, their practical relevance seems marginal.

     

Novel Tyrosine Kinase Inhibitors to Target Chronic Myeloid Leukemia

This paper reports on a novel series of tyrosine kinase inhibitors (TKIs) potentially useful for the treatment of chronic myeloid leukemia (CML). The newly designed and synthesized compounds are structurally related to nilotinib (NIL), a second-generation oral TKI, and to a series of imatinib (IM)-based TKIs, previously reported by our research group, these latter characterized by a hybrid structure between TKIs and heme oxygenase-1 (HO-1) inhibitors. The enzyme HO-1 was selected as an additional target since it is overexpressed in many cases of drug resistance, including CML. The new derivatives 1a–j correctly tackle the chimeric protein BCR-ABL. Therefore, the inhibition of TK was comparable to or higher than NIL and IM for many novel compounds, while most of the new analogs showed only moderate potency against HO-1. Molecular docking studies revealed insights into the binding mode with BCR-ABL and HO-1, providing a structural explanation for the differential activity. Cytotoxicity on K562 CML cells, both NIL-sensitive and -resistant, was evaluated. Notably, some new compounds strongly reduced the viability of K562 sensitive cells.     

Red Orange and Bitter Orange IntegroPectin: Structure and Main Functional Compounds

DRIFT, HPLC-MS, and SPME-GC/MS analyses were used to unveil the structure and the main functional compounds of red (blood) orange (Citrus sinensis) and bitter orange (Citrus aurantium). The IntegroPectin samples show evidence that these new citrus pectins are comprised of pectin rich in RG-I hairy regions functionalized with citrus biophenols, chiefly flavonoids and volatile molecules, mostly terpenes. Remarkably, IntegroPectin from the peel of fresh bitter oranges is the first high methoxyl citrus pectin extracted via hydrodynamic cavitation, whereas the red orange IntegroPectin is a low methoxyl pectin. C. aurantium IntegroPectin has a uniquely high concentration of adsorbed flavonoids, especially the flavanone glycosides hesperidin, naringin, and eriocitrin.     

Natural Cryoprotective and Cytoprotective Agents in Cryopreservation: A Focus on Melatonin

Cryoprotective and cytoprotective agents (Cytoprotective Agents) are fundamental components of the cryopreservation process. This review presents the essentials of the cryopreservation process by examining its drawbacks and the role of cytoprotective agents in protecting cell physiology. Natural cryoprotective and cytoprotective agents, such as antifreeze proteins, sugars and natural deep eutectic systems, have been compared with synthetic ones, addressing their mechanisms of action and efficacy of protection. The final part of this article focuses melatonin, a hormonal substance with antioxidant properties, and its emerging role as a cytoprotective agent for somatic cells and gametes, including ovarian tissue, spermatozoa and spermatogonial stem cells.     

Four Methods to Distinguish between Fractal Dimensions in Time Series through Recurrence Quantification Analysis

Fractal properties in time series of human behavior and physiology are quite ubiquitous, and several methods to capture such properties have been proposed in the past decades. Fractal properties are marked by similarities in statistical characteristics over time and space, and it has been suggested that such properties can be well-captured through recurrence quantification analysis. However, no methods to capture fractal fluctuations by means of recurrence-based methods have been developed yet. The present paper takes this suggestion as a point of departure to propose and test several approaches to quantifying fractal fluctuations in synthetic and empirical time-series data using recurrence-based analysis. We show that such measures can be extracted based on recurrence plots, and contrast the different approaches in terms of their accuracy and range of applicability.     

Emerging Direct Targeting β-Catenin Agents

Aberrant accumulation of β-catenin in the cell nucleus as a result of deregulation of the Wnt/β-catenin pathway is found in various types of cancer. Direct β-catenin targeting agents are being researched despite obstacles; however, specific β-catenin drugs for clinical treatments have not been approved so far. We focused on direct β-catenin targeting of potential therapeutic value as anticancer agents. This review provides recent advances on small molecule β-catenin agents. Structure-activity relationships and biological activities of reported inhibitors are discussed. This work provides useful knowledge in the discovery of β-catenin agents.