Use of monomer fraction data in the parametrization of association theories

Association theories such as the CPA (cubic-plus-association), NRHB (non-random hydrogen bonding) equations of state and the various variants of SAFT (statistical associating fluid theory) have been extensively applied to phase equilibrium calculations. Such models can also be used for estimating the monomer fraction of hydrogen bonding compounds and their mixtures. Monomer fraction data are obtained from spectroscopic measurements and they are available for a few compounds such as pure water and alcohols as well as for some alcohol–alkane and similar mixtures. These data are useful for an understanding of the capabilities and limitations of association models. The purpose of this work is two-fold: (i) to compare the performance of three models, CPA, NRHB and sPC-SAFT, in predicting the monomer fraction of water, alcohols and mixtures of alcohol-inert compounds and (ii) to investigate whether “improved” model parameters can be obtained if monomer fraction data are included in the parameter estimation together with vapor pressures and liquid densities. The expression “improved” implies parameters which can represent several pure compound properties as well as monomer fraction data for pure compounds and mixtures. The accuracy of experimental monomer fraction data is discussed, as well as the role of monomer fraction data in clarifying which association scheme should be used in these equations of state. The results reveal that the investigated association models (CPA, sPC-SAFT and NRHB) can predict, at least qualitatively correct, monomer fractions of associating compounds and mixtures. Only, small differences are observed between the models. In addition, it has been shown that, using a suitable association scheme, a single set of parameters can describe satisfactorily vapor pressures, liquid densities and monomer fractions of water and alcohols. The 4C scheme is the best choice for water, while for methanol there is small difference between the 2B and 3B association schemes.     

Air‐Stable {(C5H5)Co} Catalysts for [2+2+2] Cycloadditions

Cobalt cyclopentadienyl complexes incorporating a fumarate and a CO ligand (see picture) efficiently catalyze inter‐ and intramolecular [2+2+2] cycloadditions of alkynes, nitriles, and/or alkenes to give benzenes, pyridines, or 1,3‐cyclohexadienes. Unlike catalysts such as [CpCo(CO)₂] or [CpCo(C₂H₄)₂] (Cp=C₅H₅), they are air‐stable, easy to handle, compatible with microwave conditions, and do not necessarily require irradiation to be active.

     

Interplay of Interactions Governing the Dynamic Conversions of Acyclic and Macrocyclic Helicates

Systemic change : A system of transformations between helical structures was observed to be governed by interactions mediated by the electronic effects of substituents, entropic effects, the conformational preferences of organic building blocks, and the coordinative preferences of the metal ion. All of these effects were important, but all must be considered together to allow the prediction of the product observed (see scheme).

     

Carbonylation of C−N Bonds in Tertiary Amines Catalyzed by Low‐Valent Iron Catalysts

The first iron catalysts able to promote the formal insertion of CO into the C?N bond of amines are reported. Using low‐valent iron complexes, including K₂[Fe(CO)₄], amides are formed from aromatic and aliphatic amines, in the presence of an iodoalkane promoter. Inorganic Lewis acids, such as AlCl₃ and Nd(OTf)₃, have a positive influence on the catalytic activity of the iron salts, enabling the carbonylation at a low pressure of CO (6 to 8 bars).     

L-arginine binding to human inducible nitric oxide synthase: an antisymmetric funnel route toward isoform-specific inhibitors?

Nitric oxide (NO) is an important signaling molecule produced by a family of enzymes called nitric oxide synthases (NOS). Because NO is involved in various pathological conditions, the development of potent and isoform-selective NOS inhibitors is an important challenge. In the present study, the dimer of oxygenase domain of human iNOS (iNOSoxy) complexed to its natural substrate L-arginine (L-Arg) and both heme and tetrahydro-L-biopterin (BH4) cofactors was studied through multiple molecular dynamics simulations. Starting from the X-ray structure available for that complex (PDB: 1NSI ), a 16 ns equilibration trajectory was first obtained. Twelve dynamics of slow extraction of L-Arg out from the iNOSoxy active site were then performed. The steered molecular dynamics (SMD) approach was used starting from three different points of the reference trajectory for a total simulation time of 35 ns. A probable unbinding/binding pathway of L-Arg was characterized. It was suggested that a driving force directed the substrate toward the heme pocket. Key intermediate steps/residues along the access route to the active site were identified along this "funnel shape" pathway and compared to existing data. A quasi-normal mode analysis performed on the SMD data suggested that large collective motions of the protein may be involved in L-Arg binding and that opening the route to the active site in one monomer promoted an inverse, closing motion in the second monomer. Finally, our findings might help to rationalize the design of human iNOS isoform competitive inhibitors.     

Etude dans la série des pyrrolidinones. IV. Formation de quelques dérivés de l'acide L méthylène bis N-(oxo-5 pyrrolidine carboxylique-2)

Starting from the readily available 5-oxo-2-carboxypyrrolidine, methylene-bis-(N-5-oxo-2-carboxypyrrolidine) was prepared and transformed into a diamine, then into two isomeric diols, which cyclised into one ether. The meso configuration has been assigned for this ether. The reduction of both diols and ether was complete and gave rise to methylene-bis-N-pyrrolidine.     

Functional molecules in electronic circuits

Molecular electronics is a fascinating field of research contributing to both fundamental science and future technological achievements. A promising starting point for molecular devices is to mimic existing electronic functions to investigate the potential of molecules to enrich and complement existing electronic strategies. Molecules designed and synthesized to be integrated into electronic circuits and to perform an electronic function are presented in this article. The focus is set in particular on rectification and switching based on molecular devices, since the control over these two parameters enables the assembly of memory units, likely the most interesting and economic application of molecular based electronics. Both historical and contemporary solutions to molecular rectification are discussed, although not exhaustively. Several examples of integrated molecular switches that respond to light are presented. Molecular switches responding to an electrochemical signal are also discussed. Finally, supramolecular and molecular systems with intuitive application potential as memory units due to their hysteretic switching are highlighted. Although a particularly attractive feature of molecular electronics is its close cooperation with neighbouring disciplines, this article is written from the point of view of a chemist. Although the focus here is largely on molecular considerations, innovative contributions from physics, electro engineering, nanotechnology and other scientific disciplines are equally important. However, the ability of the chemist to correlate function with structure, to design and to provide tailor-made functional molecules is central to molecular electronics.