LETTER: BTZ Black Hole from (3+1) Gravity

We propose an approach for constructing spatial slices of (3+1) spacetimes with cosmological constant but without a matter content, which yields (2+1) vacuum with solutions. The reduction mechanism from (3+1) to (2+1) gravity is supported on a criterion in which the Weyl tensor components are required to vanish together with a dimensional reduction via an appropriate foliation. By using an adequate reduction mechanism from the Plebaski–Carter[A] solution in (3+1) gravity, the (2+1) BTZ solution can be obtained.     

Warm Inflation and Scalar Perturbations of the Metric

A second-order expansion for the quantum fluctuations of the matter field was considered in the framework of the warm inflation scenario. The friction and Hubble parameters were expanded by means of a semiclassical approach. The fluctuations of the Hubble parameter generates fluctuations of the metric. These metric fluctuations produce an effective term of curvature. The power spectrum for the metric fluctuations can be calculated on the infrared sector.     

Bifurcating reactions: distribution of products from energy distribution in a shared reactive mode

Bifurcating reactions yield two different products emerging from one single transition state and are therefore archetypal examples of reactions that cannot be described within the framework of the traditional Eyring''s transition state theory (TST). With the growing number and importance of these reactions in organic and biosynthetic chemistry, there is also an increasing demand for a theoretical tool that would allow for the accurate quantification of reaction outcome at low cost. Here, we introduce such an approach that fulfils these criteria, by evaluating bifurcation selectivity through the energy distribution within the reactive mode of the key transition state. The presented method yields an excellent agreement with experimentally reported product ratios and predicts the correct selectivity for 89% of nearly 50 various cases, covering pericyclic reactions, rearrangements, fragmentations and metal-catalyzed processes as well as a series of trifurcating reactions. With 71% of product ratios determined within the error of less than 20%, we also found that the methodology outperforms three other tested protocols introduced recently in the literature. Given its predictive power, the procedure makes reaction design feasible even in the presence of complex non-TST chemical steps.

Reactive Mode Composition Factor (RMCF) analysis is a powerful tool to forecast the product distribution of bifurcating reactions through analysis of the kinetic energy distribution within the first transition state traversed by the reacting system.     

Exploring the nitro group reduction in low-solubility oligo-phenylenevinylene systems: Rapid synthesis of amino derivatives

Abstract

A small series of amino oligo-phenylenevinylenes (OPVs) were successfully synthesized from their nitro-analogs in a rapid, simple, and highly efficient fashion employing a sodium sulfide/pyridine system as a reducing agent. In this research, classic and sustainable reduction methodologies including NH₄HCO₂/Zn and a choline chloride/tin (II) chloride deep eutectic solvent (DES) were also evaluated, showing degradation products, incomplete reactivity, and product isolation difficulties in all cases. The straightforward Na₂S/pyridine synthetic protocol proved to maintain the E-E stereochemistry of the OPV backbone that has been previously assembled by the Mizoroki–Heck cross-coupling reaction. Also, the optoelectronic properties were determined and discussed, considering the amino group insertion in these conjugated systems as a contribution for future construction of novel materials with applications in supramolecular electronics, light harvesting, and photocatalysis.     

Synthesis and characterization of materials prepared via the copolymerization of ethylene with 1‐octadecene and norbornene using a [(π‐cyano‐nacnac)Cp] zirconium complex

[3‐Cyano‐2‐(2,6‐diisopropylphenyl)aminopent‐2‐en‐4‐(phenylimine)tris (pentafluorophenyl)borate](η⁵‐C₅H₅)ZrCl₂, [(B(C₆F₅)₃‐ NC‐nacnac)CpZrCl₂], precatalyst ( 2 ) can be treated with low concentrations of methylaluminoxane (MAO) to generate active sites capable of copolymerizing ethylene with 1‐octadecene or norbornene under mild conditions. A series of poly(ethylene‐co‐octadecene) and poly(ethylene‐co‐norbornene) copolymers were prepared, and their properties were characterized by NMR, differential scanning calorimetry, and mechanical analysis. The results show that this system produced poly(ethylene‐co‐octadecene) copolymers with a branching content of about 8 mol %. However, upon increasing the comonomer concentration, a drastic reduction in the M_n of the product is observed concomitant with an increase in comonomer incorporation. This leads to a gradual decrease in Young's modulus and stress at break, indicating an increase in the “softness” of the copolymer. In the case of copolymerizations of ethylene and norbornene, the catalytic system ( 2 /MAO) shows a substantial decrease in reactivity in the presence of norbornene and generates copolymer chains in which 5–10 mol % norbornene is in blocks. We also observe that ethylene norbornene copolymers exhibit a high degree of alternating insertions (close to 50%), as determined by NMR spectroscopy. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Tandem reduction + cyclization of ortho-substituted cinnamic esters

Conjugate reduction of ortho-substituted cinnamic esters by Stryker’s reagent to form copper enolates, followed by intramolecular aldol-type cyclization, successfully generated indane and tetralin rings in one pot efficiently. This tandem reaction is generally diastereoselective and provides good yields.     

Modeling hydration properties and temperature developments of early-age concrete pavement using calorimetry tests

This research aims to evaluate the calorimetry tests for characterizing cement hydration properties and predicting temperature developments of the early-age Portland cement concrete pavement (PCCP). Analytical models are studied to simulate hydration properties, using the measured heat evolution data from both the isothermal and semi-adiabatic tests. HIPERPAV III^® engineering software with these analytical models embedded is used to predict temperature developments of the early-age PCCP. Results show that the maximum hydration time parameter τ corresponds to the maximum activation energy E_a. Semi-adiabatic tests result in a lower hydration shape parameter β yet a higher hydration time parameter τ than isothermal tests. As results, the simulated degree of hydration based on semi-adiabatic tests is higher at the early hours, but lower at later hours compared to that based on isothermal tests. This effect is also reflected from the simulated temperature developments of the early-age PCCP. Three engineering projects in this research show that predicted temperatures of the PCCP using hydration parameters determined from semi-adiabatic tests better match actual measurements than that from isothermal tests.     

A serendipitous one-step conversion of 3H-1,2-dithiole-3-thione to (E)-3-[1-(alkylthio)alkylidene]-3H-1,2-dithiole: an experimental and theoretical study

In the course of our studies on 3 $H$ -1,2-dithiole-3-thione synthesis, a serendipitous reactivity with $\alpha $ -haloketones, in the presence of excess of potassium iodide, has been observed. Instead of the expected reaction of the nucleophile in a remote point of the molecule, we have obtained a product resulted from the electrophile character of the thiocarbonyl moiety on the 3-position of the 1,2-dithiole. In order to obtain an efficient protocol in terms of energy efficiency, this methodology was studied under conventional and microwave heating with similar or better results in the latter conditions. Simplicity and great efficiency in this one-step transformation are some of the advantages of this reaction. Moreover, the results can be explained according to the Pearson’s hard and soft acid base theory.     

An edge-swap heuristic for generating spanning trees with minimum number of branch vertices

This paper presents a new edge-swap heuristic for generating spanning trees with a minimum number of branch vertices, i.e. vertices of degree greater than two. This problem was introduced in Gargano et al. (Lect Notes Comput Sci 2380:355–365, 2002) and has been called the minimum branch vertices problem by Cerulli et al. (Comput Optim Appl 42:353–370, 2009). The heuristic starts with a random spanning tree and iteratively reduces the number of branch vertices by swapping tree edges with edges not currently in the tree. It can be easily implemented as a multi-start heuristic. We report on extensive computational experiments comparing single-start and multi-start variants on our heuristic with other heuristics previously proposed in the literature.