Experimental and Theoretical Study of the Stability of the Complex Fisetin–Cu(II) and A Comparative Study of Free Ligand and Complex Interaction with Molecular Singlet Oxygen

In this work, the flavonol fisetin was selected in order to study its reactivity against Cu(II), a metal ion of interest in biological media and industry. The stoichiometry and apparent formation constant of the complex in ethanolic medium at 25°C were evaluated using spectrophotometric techniques. The resulting stoichiometry was a 1:1 ligand:metal complex, and a log K = 5.17 ± 0.12 was determined. Since two possible chelation sites can be proposed for the complex formation, quantum chemistry calculations were performed on these structures. Calculations suggest that the hydroxyl-keto site is more stable for the complex formation than the catechol site. Flavonoids could exert protection against oxidative damage caused by reactive oxygen species, and this biological activity could be affected by chelation with metal ions. This led us to perform a study on the interaction of both, free flavonoid and complex, with reactive oxygen species. Our results showed both compounds quench molecular singlet oxygen photogenerated with visible light, mainly in a physical fashion. In order to analyze a possible protective effect of flavonoid and its complex against oxidative damage in biological environments, the amino acid tryptophan was selected as a model oxidation system. Free flavonoid does not have a marked protective effect, whereas its complex showed a relevant protective effect.     

A fix-and-optimize matheuristic for university timetabling

University course timetabling covers the task of assigning rooms and time periods to courses while ensuring a minimum violation of soft constraints that define the quality of the timetable. These soft constraints can have attributes that make it difficult for mixed-integer programming solvers to find good solutions fast enough to be used in a practical setting. Therefore, metaheuristics have dominated this area despite the fact that mixed-integer programming solvers have improved tremendously over the last decade. This paper presents a matheuristic where the MIP-solver is guided to find good feasible solutions faster. This makes the matheuristic applicable in practical settings, where mixed-integer programming solvers do not perform well. To the best of our knowledge this is the first matheuristic presented for the University Course Timetabling problem. The matheuristic works as a large neighborhood search where the MIP solver is used to explore a part of the solution space in each iteration. The matheuristic uses problem specific knowledge to fix a number of variables and create smaller problems for the solver to work on, and thereby iteratively improves the solution. Thus we are able to solve very large instances and retrieve good solutions within reasonable time limits. The presented framework is easily extendable due to the flexibility of modeling with MIPs; new constraints and objectives can be added without the need to alter the algorithm itself. At the same time, the matheuristic will benefit from future improvements of MIP solvers. The matheuristic is benchmarked on instances from the literature and the 2nd International Timetabling Competition (ITC2007). Our algorithm gives better solutions than running a state-of-the-art MIP solver directly on the model, especially on larger and more constrained instances. Compared to the winner of ITC2007, the matheuristic performs better. However, the most recent state-of-the-art metaheuristics outperform the matheuristic.     

Changing alpha with time: implications for fifth-force-type experiments and quintessence

If the recent observations suggesting a time variation of the fine structure constant are correct, they imply the existence of an ultralight scalar particle. This particle inevitably couples to nucleons through the alpha dependence of their masses and thus mediates an isotope-dependent long-range force. The strength of the coupling is within a couple of orders of magnitude of the existing experimental bounds for such forces. The new force can be potentially measured in precision experimental tests of the equivalence principle. Because of a coincidence of the required time scales, the scalar field can at the same time play the role of a quintessence field.     

Optical fiber nanometer-scale Fabry-Perot interferometer formed by the ionic self-assembly monolayer process

The ionic self-assembly monolayer process is a novel technique that has already been used to deposit ultrathin films on glass, polymer, and silicon substrates of different sizes and shapes. This technique is presented as a new tool with which to apply coatings on optical fibers. A nanometer-scale interferometric cavity was built up at the end of an optical fiber with discrete thickness increments of 4.75 nm for a total thickness of 1 mum . Theoretical and experimental aspects of the nanometer-scale Fabry-Perot cavity are described, and both theoretical and experimental results show good agreement.     

Multivariate moment based extreme value index estimators

Modeling extreme events is of paramount importance in various areas of science—biostatistics, climatology, finance, geology, and telecommunications, to name a few. Most of these application areas involve multivariate data. Estimation of the extreme value index plays a crucial role in modeling rare events. There is an affine invariant multivariate generalization of the well known Hill estimator—the separating Hill estimator. However, the Hill estimator is only suitable for heavy tailed distributions. As in the case of the separating multivariate Hill estimator, we consider estimation of the extreme value index under the assumptions of multivariate ellipticity and independent identically distributed observations. We provide affine invariant multivariate generalizations of the moment estimator and the mixed moment estimator. These estimators are suitable for both light and heavy tailed distributions. Asymptotic properties of the new extreme value index estimators are derived under multivariate elliptical distribution with known location and scatter. The effect of replacing true location and scatter by estimates is examined in a thorough simulation study. We also consider two data examples: one financial application and one meteorological application.     

Potential of the Compounds from Bixa orellana Purified Annatto Oil and Its Granules (Chronic®) against Dyslipidemia and Inflammatory Diseases: In Silico Studies with Geranylgeraniol and Tocotrienols

Some significant compounds present in annatto are geranylgeraniol and tocotrienols. These compounds have beneficial effects against hyperlipidemia and chronic diseases, where oxidative stress and inflammation are present, but the exact mechanism of action of such activities is still a subject of research. This study aimed to evaluate possible mechanisms of action that could be underlying the activities of these molecules. For this, in silico approaches such as ligand topology (PASS and SEA servers) and molecular docking with the software GOLD were used. Additionally, we screened some pharmacokinetic and toxicological parameters using the servers PreADMET, SwissADME, and ProTox-II. The results corroborate the antidyslipidemia and anti-inflammatory activities of geranylgeraniol and tocotrienols. Notably, some new mechanisms of action were predicted to be potentially underlying the activities of these compounds, including inhibition of squalene monooxygenase, lanosterol synthase, and phospholipase A₂. These results give new insight into new mechanisms of action involved in these molecules from annatto and Chronic^®.     

Physicochemical Characterization and Simulation of the Solid–Liquid Equilibrium Phase Diagram of Terpene-Based Eutectic Solvent Systems

The characterization of terpene-based eutectic solvent systems is performed to describe their solid–liquid phase transitions. Physical properties are measured experimentally and compared to computed correlations for deep eutectic solvents (DES) and the percentage relative error e_r for the density, surface tension, and refractive index is obtained. The thermodynamic parameters, including the degradation, glass transition and crystallization temperatures, are measured using DSC and TGA. Based on these data, the solid–liquid equilibrium phase diagrams are calculated for the ideal case and predictions are made using the semi-predictive UNIFAC and the predictive COSMO RS models, the latter with two different parametrization levels. For each system, the ideal, experimental, and predicted eutectic points are obtained. The deviation from ideality is observed experimentally and using the thermodynamic models for Thymol:Borneol and Thymol:Camphor. In contrast, a negative deviation is observed only experimentally for Menthol:Borneol and Menthol:Camphor. Moreover, the chemical interactions are analyzed using FTIR and ¹H-NMR to study the intermolecular hydrogen bonding in the systems.     

Synthesis and Characterisation of Luminescent [CrIII2L(μ-carboxylato)]3+ Complexes with High-Spin S=3 Ground States (L=N6S2 donor ligand)

The synthesis, structure, magnetic, and photophysical properties of two dinuclear, luminescent, mixed-ligand [Cr^III₂L(O₂CR)]³⁺ complexes (R=CH₃ ( 1 ), Ph ( 2 )) of a 24-membered binucleating hexa-aza-dithiophenolate macrocycle (L)²⁻ are presented. X-ray crystallographic analysis reveals an edge-sharing bioctahedral N₃Cr(μ-SR)₂(μ_1,3-O₂CR)CrN₃ core structure with μ_1,3-bridging carboxylate groups. A ferromagnetic superexchange interaction between the electron spins of the Cr³⁺ ions leads to a high-spin (S=3) ground state. The coupling constants (J=+24.2(1) cm⁻¹ ( 1 ), +34.8(4) cm⁻¹ ( 2 ), H=−2JS₁S₂) are significantly larger than in related bis-μ-alkoxido-μ-carboxylato structures. DFT calculations performed on both complexes reproduce both the sign and strength of the exchange interactions found experimentally. Frozen methanol-dichloromethane 1 : 1 solutions of 1 and 2 luminesce at 750 nm when excited into the ⁴LMCT state on the ⁴A₂ → ²T₁ (ν₂) bands (λ_exc=405 nm). The absolute quantum yields (Φ_L) for 1 and 2 were found to be strongly temperature dependent. At 77 K in frozen MeOH/CH₂Cl₂ glasses, Φ_L=0.44±0.02 (for 1 ), Φ_L=0.45±0.02 (for 2 ).     

On lubrication models for vertical rivulet flows

Meccanica - Rivulet flows are ubiquitous both in nature and industrial applications. Because of the typical length scales involved, most analyses of these flows rely on the so-called lubrication...