Can simple enones be useful partners for the catalytic stereoselective alkylation of indoles?

A new catalytic system for the first example of enantioselective Friedel-Crafts-type (FC) addition of indoles to simple enones is described. The use of an equimolar amount of chiral [Al(salen)Cl] and 2,6-lutidine (10 mol %) was found to be effective in promoting the conjugate addition of indoles to (E)-arylcrotyl ketones, furnishing the corresponding beta-indolyl ketones in excellent yield and high enantioselectivity (ee up to 89%). The role of the base was investigated through spectroscopic as well as computational analyses, which suggested that in situ formation of a new chiral (base.[Al(salen)]) complex was operating under our reaction conditions. In particular, a stable cationic [Al(salen)] hexacoordinate trans complex with the additive base and the enone is suggested as being responsible for the stereocontrolled reaction. Finally, detailed monitoring of the reaction course was carried out showing that a conventional FC pathway induced by [Al(salen)Cl] acting as a Lewis acid is operating.     

A dysprosium single molecule magnet outperforming current pseudocontact shift agents

A common criterion for designing performant single molecule magnets and pseudocontact shift tags is a large magnetic anisotropy. In this article we present a dysprosium complex chemically designed to exhibit strong easy-axis type magnetic anisotropy that is preserved in dichloromethane solution at room temperature. Our detailed theoretical and experimental studies on the magnetic properties allowed explaining several features typical of highly performant SMMs. Moreover, the NMR characterization shows remarkably large chemical shifts, outperforming the current state-of-the art PCS tags.

A robust dysprosium(iii) single molecule magnet with large uniaxial magnetic anisotropy induces pseudocontact shifts at almost doubled distance compared to standard shift agents.     

Insights on the Modulation of SIRT5 Activity: A Challenging Balance

SIRT5 is a member of the Sirtuin family, a class of deacetylating enzymes consisting of seven isoforms, involved in the regulation of several processes, including gene expression, metabolism, stress response, and aging. Considering that the anomalous activity of SIRT5 is linked to many pathological conditions, we present herein an overview of the most interesting modulators, with the aim of contributing to further development in this field.     

Metabolic Profile of Agropyron repens (L.) P. Beauv. Rhizome Herbal Tea by HPLC-PDA-ESI-MS/MS Analysis

Agropyron repens (L.) P. Beauv. (couch grass) is a world-wide infesting rhizomatous plant with pharmacological applications. Chemical research is focused on its allelopathic and anti-inflammatory components, which are mainly present in the essential oil. Conversely, the aqueous extracts have been sparingly investigated, although the herbal tea is by far the most used formulation. To fill the gap, the metabolic profile of Agropyron repens rhizome herbal tea was investigated by electrospray ionization (ESI) tandem–mass spectrometry (MS/MS); the phenolic profile was investigated by HPLC-PDA-ESI-MS/MS. ESI-MS fingerprinting was provided, evidencing diagnostic ions for saccharides, organic acids and amino acids. The HPLC-PDA-ESI-MS/MS analysis evidenced at least 20 characteristic phenolic compounds, the most representative being caffeoyl and feruloyl quinic esters, followed by coumaric, caffeic and ferulic acids, and hesperidin among flavonoids. In addition, the essential amino acid tryptophan was identified for the first time. The results suggest new perspectives of applications for Agropyron repens rhizome.     

A corresponding states principle-based equation for the surface tension of Alkenes

This study presents a new formula for the surface tension prediction of alkenes. As a first step, an analysis of the available data of the experimental surface tension data for alkenes was performed. The experimental data were collected, after a careful literature survey, for the following pure fluids: propene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, and 1-pentadecene. Then, the experimental data were regressed with the most reliable semi-empirical correlating methods based on the corresponding state theory existing in the literature. As a final step, an analysis of the available data of the experimental surface tension data for alkenes was performed starting from the two recently proposed equations for the prediction of the surface tension of refrigerants based on the corresponding states principle. To minimize the deviation between the predicted data and the experimental data and to find the optimal equation coefficients for experimental data regression, a (μ + λ)-evolution strategy was adopted. The analysis showed that the equation that gave the best results for the prediction of the surface tension of alkenes was the one with a very limited number of parameters. The finally proposed equation is very simple and gives a noticeable improvement with respect to the existing equations. It is based on the corresponding state principle, containing the acentric factor, the critical temperature, and pressure.     

Local branching

The availability of effective exact or heuristic solution methods for general Mixed-Integer Programs (MIPs) is of paramount importance for practical applications. In the present paper we investigate the use of a generic MIP solver as a black-box ``tactical' tool to explore effectively suitable solution subspaces defined and controlled at a ``strategic' level by a simple external branching framework. The procedure is in the spirit of well-known local search metaheuristics, but the neighborhoods are obtained through the introduction in the MIP model of completely general linear inequalities called local branching cuts. The new solution strategy is exact in nature, though it is designed to improve the heuristic behavior of the MIP solver at hand. It alternates high-level strategic branchings to define the solution neighborhoods, and low-level tactical branchings to explore them. The result is a completely general scheme aimed at favoring early updatings of the incumbent solution, hence producing high-quality solutions at early stages of the computation. The method is analyzed computationally on a large class of very difficult MIP problems by using the state-of-the-art commercial software ILOG-Cplex 7.0 as the black-box tactical MIP solver. For these instances, most of which cannot be solved to proven optimality in a reasonable time, the new method exhibits consistently an improved heuristic performance: in 23 out of 29 cases, the MIP solver produced significantly better incumbent solutions when driven by the local branching paradigm. Mathematics Subject Classification (2000):90C06, 90C10, 90C11, 90C27, 90C59     

An additive bounding procedure for the asymmetric travelling salesman problem

In this paper, new lower bounds for the asymmetric travelling salesman problem are presented, based on spanning arborescences. The new bounds are combined in an additive procedure whose theoretical performance is compared with that of the Balas and Christofides procedure (1981). Both procedures have been imbedded in a simple branch and bound algorithm and experimentally evaluated on hard test problems.     

Transforming nonlocality into a frequency dependence: a shortcut to spectroscopy

Measurable spectra are often derived from contractions of many-body Green's functions. One calculates hence more information than needed. Here we present and illustrate an in principle exact approach to construct effective potentials and kernels for the direct calculation of electronic spectra. In particular, a dynamical but local and real potential yields the spectral function needed to describe photoemission. We discuss for model solids the frequency dependence of this "photoemission potential" stemming from the nonlocality of the corresponding self-energy.     

From Kerr to Heisenberg

In this paper, we consider the space-time of a charged mass endowed with an angular momentum. The geometry is described by the exact Kerr–Newman solution of the Einstein equations. The peculiar symmetry, though exact, is usually described in terms of the gravito-magnetic field originated by the angular momentum of the source. A typical product of this geometry is represented by the generalized Sagnac effect. We write down the explicit form for the right/left asymmetry of the times of flight of two counter-rotating light beams along a circular trajectory. Letting the circle shrink to the origin the asymmetry stays finite. Furthermore it becomes independent both from the charge of the source (then its electromagnetic field) and from Newton’s constant: it is then associated only to the symmetry produced by the gravitomagnetic field. When introducing, for the source, the spin of a Fermion, the lowest limit of the Heisenberg uncertainty formula for energy and time appears.