Ab initio study on the kinetics of hydrogen abstraction for the H+alkene-->H2+alkenyl reaction class

Kinetics of the hydrogen abstraction reaction class of the H+alkene has been studied using the reaction class transition state theory (RC-TST) combined with the linear energy relationship (LER) and the barrier height grouping (BHG) approach. The rate constants for the reference reaction, H+C2H4, were obtained by the canonical variational transition state theory (CVT) with the small curvature tunneling (SCT) correction in the temperature range of 300-3000 K. Combined with these data, both the RC-TST/LER, where only reaction energy is needed, and RC-TST/BHG, where no other information is needed, are found to be promising methods for predicting rate constants for a large number of reactions in this reaction class. Our analysis indicates that less than 50% systematic errors on the average exist in the predicted rate constants using the RC-TST/LER or RC-TST/BHG method while in comparison to explicit rate calculations the differences are less than 100% or a factor of 2 on the average.     

Approximating the chance-constrained capacitated vehicle routing problem with robust optimization

4OR - The Capacitated Vehicle Routing Problem (CVRP) is a classical combinatorial optimization problem that aims to serve a set of customers, using a set of identical vehicles, satisfying the...     

Syntheses of (<Emphasis Type="Italic">E</Emphasis>)- and (<Emphasis Type="Italic">Z</Emphasis>)-3-styrylchromones

Several (E)- and (Z)-3-styrylchromones were prepared by two different methodologies, the Wittig reaction of chromone-3-carboxaldehyde with benzylic ylides and the Knoevenagel condensation of chromone-3-carboxaldehyde with phenylacetic acids in the presence of potassium tert-butoxide under microwave irradiation. The Knoevenagel reaction followed by a decarboxylation offered an efficient and diastereoselective method for preparing (E)-3-styrylchromones in a shorter reaction time. It was also demonstrated that phenylacetic acid can also be substituted with success by phenylmalonic acid. The stereochemistry of all products was assigned by NMR experiments. Correspondence: Artur M. S. Silva, Chemistry Department, University of Aveiro, 3810-193 Aveiro, Portugal.     

Syntheses of (E)- and (Z)-3-styrylchromones

Several (E)- and (Z)-3-styrylchromones were prepared by two different methodologies, the Wittig reaction of chromone-3-carboxaldehyde with benzylic ylides and the Knoevenagel condensation of chromone-3-carboxaldehyde with phenylacetic acids in the presence of potassium tert-butoxide under microwave irradiation. The Knoevenagel reaction followed by a decarboxylation offered an efficient and diastereoselective method for preparing (E)-3-styrylchromones in a shorter reaction time. It was also demonstrated that phenylacetic acid can also be substituted with success by phenylmalonic acid. The stereochemistry of all products was assigned by NMR experiments.     

Experimental measurements and theoretical calculations of the chemical shifts and coupling constants of three azines (benzalazine, acetophenoneazine and cinnamaldazine)

Three azines, two of them doubly labeled with (15)N, have been studied by multinuclear magnetic resonance in solution and in the solid state. The spectral parameters obtained by iterative analyses have been compared with DFT/B3LYP calculated values (absolute shieldings and coupling constants). The agreement is generally good. Some anomalies have been discussed in relation to the structure of these compounds.     

IR and NMR spectra, intramolecular hydrogen bonding and conformations of mercaptothiacalix[4]arene molecules and their para-tert-butyl-derivative

It is demonstrated that the introduction of p-tert-butyl groups dramatically influences the conformational behaviour of the mercaptothiacalix[4]arene molecules. Quantum-chemical computations in combination with IR and NMR spectroscopy prove that, in contrast to closely related calixarenes, the 1,3-alternate becomes a dominant conformer of p-tert-butyl-mercaptothiacalix[4]arene not only in crystal, but also in solutions and in vacuum. It is shown that the title molecules form essentially non-cooperative intramolecular hydrogen bonds: their SH groups are intramolecularly H-bonded solely to the sulfide groups bridging thiophenolic units. The enthalpy of this bonding, evaluated from Iogansen’s rule, amounts to ca. 1.5 kcal mol⁻¹ per one SH···S bond, which about four times smaller than the enthalpies of cooperative intramolecular H-bonds formed by related calixarenes and thiacalixarenes. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Supramolecular adducts of native and permethylated β-cyclodextrins with (2,2′-dipyridylamine)chlorido(1,4,7-trithiacyclononane)ruthenium(II) chloride: solid-state and biological activity studies

The complex [([9]aneS₃)Ru^II(dipa)Cl]Cl (1, where dipa = 2,2′-dipyridylamine) was included into native β-cyclodextrin (β-CD) and permethylated β-CD (TRIMEB) by co-dissolution followed by solvent removal. Two adducts were obtained with a 1:1 host:guest stoichiometry. Solid-state studies of the guest comprised collecting the single-crystal structure of its 3.5 hydrate form and also powder diffraction on the remaining bulk material, showing it is isotypical with the harvested crystal for X-ray analysis. Solid-state studies of the cyclodextrin adducts were carried out by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), ¹³C{¹H} CP/MAS NMR and FTIR spectroscopies. Biological studies on 1 and its adducts comprised the evaluation of the shift caused by 1 on the melting temperature of DNA (ΔT _m), as well as the evaluation of cytotoxicity by the MTT assay on the osteosarcoma MG-63 cell line.     

Improved branch-cut-and-price for capacitated vehicle routing

The best performing exact algorithms for the capacitated vehicle routing problem developed in the last 10 years are based in the combination of cut and column generation. Some authors only used cuts expressed over the variables of the original formulation, in order to keep the pricing subproblem relatively easy. Other authors could reduce the duality gaps by also using a restricted number of cuts over the master LP variables, stopping when the pricing becomes prohibitively hard. A particularly effective family of such cuts are the subset row cuts. This work introduces a technique for greatly reducing the impact on the pricing of these cuts, thus allowing much more cuts to be added. The newly proposed branch-cut-and-price algorithm also incorporates and combines for the first time (often in an improved way) several elements found in previous works, like route enumeration and strong branching. All the instances used for benchmarking exact algorithms, with up to 199 customers, were solved to optimality. Moreover, some larger instances with up to 360 customers, only considered before by heuristic methods, were solved too.     

Experimental study of an impinging jet with different swirl rates

A stereo PIV technique using advanced pre- and post-processing algorithms is implemented for the experimental study of the local structure of turbulent swirling impinging jets. The main emphasis of the present work is the analysis of the influence of swirl rate on the flow structure. During measurements, the Reynolds number was 8900, the nozzle-to-plate distance was equal to three nozzle diameters and the swirl rate was varied from 0 to 1.0. For the studied flows, spatial distributions of the mean velocity and statistical moments (including triple moments) of turbulent pulsations were measured.

The influence of the PIV finite spatial resolution on the measured dissipation rate and velocity moments was analyzed and compared with theoretical predictions. For this purpose, a special series of 2D PIV measurements was carried out with vector spacing up to several Kolmogorov lengthscales.

All terms of the axial mean momentum and the turbulent kinetic energy budget equations were obtained for the cross-section located one nozzle diameter from the impinging plate. For the TKE budget, the dissipation term was directly calculated from the instantaneous velocity fields, thereby allowing the pressure diffusion term to be found as a residual one. It was found that the magnitude of pressure diffusion decreased with the growth of the swirl rate. In general, the studied swirling impinging jets had a greater spread rate and a more rapid decay in absolute velocity when compared to the non-swirling jet.     

Novel bis-(3-cyano-2-pyridones) derivatives: synthesis and fluorescent properties

Research on Chemical Intermediates - Novel substituted bis-(3-cyano-2-pyridone) derivatives were prepared via a powerful method using enaminonitriles push–pull dienes as key building blocks....