Equimatchable factor-critical graphs

A simple graph G(X, E) is factor-critical if the induced subgraph 〈X – x〉 admits a perfect matching for every vertex x of G. It is equimatchable if every maximal matching of G is maximum. The equimatchable non-factor-critical graphs have been studied by Lesk, Plummer, and Pulleyblank. In this paper, we study the equimatchable factor-critical graphs; in particular we show that if such a graph is two-connected, it is hamiltonian.     

Importance of palladium-carbon bond energies in direct arylation of polyfluorinated benzenes

Fagnou et al. reported direct arylation reactions that use palladium catalysts to couple Ar(1)-X to Ar(2)-H with the aid of a coordinated base. These reactions are particularly favourable for polyfluorinated arenes Ar(2)-H (see S. I. Gorelsky, D. Lapointe and K. Fagnou, J. Am. Chem. Soc. 2008, 130, 10848). In this paper, we show by means of a DFT analysis how the energetics and activation energies vary with fluorine substitution and examine the structures of intermediates and transition states. The reactant is modelled by Pd(OAc)(Ph)(PMe(3))(DMA) (DMA = dimethylacetamide). The sequence consists of (a) replacement of DMA by arene, (b) Concerted Deprotonation Metallation (CMD), (c) decoordination of AcOH, (d) reductive elimination of biaryl. Many of the variations are dominated by the number of fluorine substituents ortho to the C-H bond and fall into three groups labelled accordingly: Set0Fo, Set1Fo, and Set2Fo. In the first step a coordinated solvent is replaced by the arene. The arenes of Set0Fo and Set1Fo coordinate in a conventional η(2)-CH=CH mode, whereas the arenes of Set2Fo coordinate in an η(1)-CH mode assisted by an OH-C hydrogen bond from the coordinated acetate. Both the energy barriers to CMD and the product energies fall into the three typical sets with the highest barrier and highest product energy being for Set0Fo. They correlate more satisfactorily with the variations in Pd-C bond energies than with the C-H acidities. The barriers to reductive elimination from Pd(Ph)(Ar(F))(PMe(3))(AcOH) increase systematically from Set0Fo to Set2Fo as the Pd-C bond becomes stronger in a regular fashion from Set0Fo to Set2Fo. Again there is a strong correlation between the energy barriers to reductive elimination and the Pd-C bond energies. It is found overall that the key aspects of the reactions are: (a) the lowering of the energy of the CMD step by the ortho fluorine substituents, (b) the regioselective activation of C-H bonds ortho to fluorine which is also determined at the CMD step, (c) the decoordination of AcOH, which maintains the transition state for reductive elimination at low Gibbs free energy. The presence of fluorine increases the effectiveness of the reaction in the sense of points a and b via the increasing strength of the palladium-carbon bond.     

Branch-and-price approach for the multi-skill project scheduling problem

This work introduces a procedure to solve the multi-skill project scheduling problem (MSPSP) (Néron and Baptista, International symposium on combinatorial, optimization (CO’2002), 2002). The MSPSP mixes both the classical resource constrained project scheduling problem and the multi-purpose machine model. The aim is to find a schedule that minimizes the completion time (makespan) of a project, composed of a set of activities. In addition, precedence relations and resources constraints are considered. In this problem, resources are staff members that master several skills. Thus, a given number of workers must be assigned to perform each skill required by an activity. Practical applications include the construction of buildings, as well as production and software development planning. We present a column generation approach embedded within a branch-and-price (B&P) procedure that considers a given activity and time-based decomposition approach. Obtained results show that the proposed B&P procedure is able to reach optimal solutions for several small and medium sized instances in an acceptable computational time. Furthermore, some previously open instances were optimally solved.     

Methods to Study Naphthenate Formation in w/o Emulsions by the Use of a Tetraacid Model Compound

Precipitation of naphthenate salts is normally a problem in the processing of acidic crude oils. In this study, the goal was to find suitable methods to investigate the interfacial reaction between tetraacid and calcium under emulsified conditions. Two different systems have been studied depending on composition and applied shear. The influence of inhibitors has been investigated and the same inhibitor was found to be the most effective one regardless of the system. Depletion of tetraacid in the oil phase was analyzed with UV-vis and HPLC. Interfacial area and droplet size in the emulsions were measured with fluorescence microscope and pulse-field gradient NMR. Since this reaction takes place over the interface, the investigation clearly documents, the importance of the total interfacial area of the emulsified system.     

Algorithmes stochastiques à bruit dépendant

We introduce different ways of modeling the dependency of the input noise of stochastic algorithms. We are aimed to prove that such innovations allow us to use the ODE (ordinary differential equation) method. Illustrations in the linear regression framework and in the law of the large number for triangular arrays of weighted dependent random variables are also given. We have aimed to provide results easy to check in practice. To cite this article: P. Doukhan, O. Brandière, C. R. Acad. Sci. Paris, Ser. I 337 (2003).     

Structural Aspects of 5‐methylthio‐1‐oxa‐6,6a δIV‐dithia‐2‐azapentalenes

Alkylation of 5‐[1‐hydroxyiminoalkyl]‐1,2‐dithiole‐3‐thiones using methyl iodide in the presence of sodium hydroxide gives derivatives which may be considered as being 5‐methylthio‐1‐oxa‐6,6a δ^IV‐dithia‐2‐azapentalenes with quantitative yields. The structure of oxadithiazapentalene attributed to the alkylation products is founded on X‐ray analysis and NMR and IR data.     

Iridium-catalyzed hydrogenation of N-heterocyclic compounds under mild conditions by an outer-sphere pathway

A new homogeneous iridium catalyst gives hydrogenation of quinolines under unprecedentedly mild conditions-as low as 1 atm of H(2) and 25 °C. We report air- and moisture-stable iridium(I) NHC catalyst precursors that are active for reduction of a wide variety of quinolines having functionalities at the 2-, 6-, and 8- positions. A combined experimental and theoretical study has elucidated the mechanism of this reaction. DFT studies on a model Ir complex show that a conventional inner-sphere mechanism is disfavored relative to an unusual stepwise outer-sphere mechanism involving sequential proton and hydride transfer. All intermediates in this proposed mechanism have been isolated or spectroscopically characterized, including two new iridium(III) hydrides and a notable cationic iridium(III) dihydrogen dihydride complex. DFT calculations on full systems establish the coordination geometry of these iridium hydrides, while stoichiometric and catalytic experiments with the isolated complexes provide evidence for the mechanistic proposal. The proposed mechanism explains why the catalytic reaction is slower for unhindered substrates and why small changes in the ligand set drastically alter catalyst activity.     

A rapid and reversible colorimetric assay for the characterization of aminated solid surfaces

The covalent immobilization of synthetic or natural macromolecular compounds containing amino groups onto polystyrene (PS) solid surfaces is of great interest in diagnostic applications. A sensitive assay allowing the determination of reactive end groups is therefore a powerful tool for predicting the performance of the active surface. Recently, we reported the use of the Coomassie brilliant blue (CBB) colorimetric reagent to quantify protonated groups (N⁺) in linear and dendritic structures in solution (Coussot et al., Polym Int 58(5):511–518, 2009). In this work, a simple method using CBB dye for the characterization of PS aminated solid surfaces is developed. The proposed amino density estimation by colorimetric assay (ADECA) method is based on the reversible complexation of the dye with the N⁺ groups on solid surfaces. The assay measures the released dye thanks to the use of a unique sodium carbonate–methanol buffer. Thereby, for the first time, the same surface can be used for characterization and for further coupling applications. A surface density of four N⁺ groups per square nanometer can be measured in PS microwell format, the whole characterization being done within 30 min. Performances of this new colorimetric-based method are detailed. The ADECA method is further demonstrated to be useful for the characterization of aminated polypropylene and glass materials with various sizes and shapes.