Mass spectrometry of beta-ketoesters. Some evidence of their tautomerism

Mass spectrometric evidence of tautomerism is reported for beta-ketoesters. The analysis of the corresponding mass spectra has allowed specific assignment of fragment ions to tautomers. The predictive value of this methodology is supported by the influence of substitution pattern of these compounds on these equilibria. Experimental data are strongly supported by Austin Model 1 semiempirical calculations indicating that mass spectrometry could be resourced as a tool for the investigation of tautomerism of neutral species in the gas phase.     

Solvation structure and transport of acidic protons in ionic liquids: a first-principles simulation study

Ab initio simulations of a single molecule of HCl in liquid dimethyl imidazolium chloride [dmim][Cl] show that the acidic proton exists as a symmetric, linear ClHCl(-) species. Details of the solvation structure around this molecule are given. The proton-transfer process was investigated by applying a force along the antisymmetric stretch coordinate until the molecule broke. Changes in the free energy and local solvation structure during this process were investigated. In the reaction mechanism identified, a free chloride approaches the proton from the side. As the original ClHCl(-) distorts and the incoming chloride forms a new bond to the proton, one of the original chlorine atoms is expelled and a new linear molecule is formed.     

Atomistic nature of transient and steady-state responses

We find experimentally that a system comprised of nanosized features no longer shows fixed steady characteristics as in solid-state devices, and instead, because of the chemistry of the nanostructure, the thermal motion of the atoms, and the external fields, the nanosized system shows intermittent behavior, that is, transient behavior. This transient response for nanosized systems might misguide conclusions regarding observed negative differential resistance (NDR) which is due to the collective nuclei rearrangements to more stable conformations under the presence of an applied field yielding, in many cases, resonances between conformations that can sustain during the steady-state period. This NDR yields peculiar behavior that needs to be considered to design molecular and nanoelectronic devices. In addition, the commonly sharp contrast between transient and steady responses blurs at the nanoscale. In nanosize systems, the time constants or transient response times depend on the velocity of the rearrangements of the atoms in the system or molecule.     

An exact and heuristic approach for the <Emphasis Type="Italic">d</Emphasis>-minimum branch vertices problem

Given a connected graph \(G=(V,E)\), the d-Minimum Branch Vertices (d-MBV) problem consists in finding a spanning tree of G with the minimum number of vertices with degree strictly greater than d. We developed a Miller–Tucker–Zemlin based formulation with valid inequalities for this problem. The results obtained for different values of d show the effectiveness of the proposed method, which has solved several instances faster than previous methods. Also, an heuristic is proposed for this problem, that was tested on several instances of the Minimum Branch Vertices problem, which is the d-MBV problem, when \(d = 2\).     

The Role of Essential Oils and Their Main Compounds in the Management of Cardiovascular Disease Risk Factors

Cardiovascular diseases (CVDs) are a global health burden that greatly impact patient quality of life and account for a huge number of deaths worldwide. Despite current therapies, several side effects have been reported that compromise patient adherence; thus, affecting therapeutic benefits. In this context, plant metabolites, namely volatile extracts and compounds, have emerged as promising therapeutic agents. Indeed, these compounds, in addition to having beneficial bioactivities, are generally more amenable and present less side effects, allowing better patient tolerance. The present review is an updated compilation of the studies carried out in the last 20 years on the beneficial potential of essential oils, and their compounds, against major risk factors of CVDs. Overall, these metabolites show beneficial potential through a direct effect on these risk factors, namely hypertension, dyslipidemia and diabetes, or by acting on related targets, or exerting general cellular protection. In general, monoterpenic compounds are the most studied regarding hypotensive and anti-dyslipidemic/antidiabetic properties, whereas phenylpropanoids are very effective at avoiding platelet aggregation. Despite the number of studies performed, clinical trials are sparse and several aspects related to essential oil’s features, namely volatility and chemical variability, need to be considered in order to guarantee their efficacy in a clinical setting.