Expedient and Diastereodivergent Assembly of Terpenoid Decalin Subunits having Quaternary Stereocenters through Organocatalytic Robinson Annulation of Nazarov Reagent

We report an expedient approach to highly functionalized cis‐ and trans‐decalines that could function as key structural subunits toward the synthesis of various classes of terpenoids. Key to the strategy is an organocatalyzed Robinson annulation reaction of the Nazarov reagent that affords chiral enone building blocks with high enantioselectivities. The quaternary carbon stereogenic center can direct the subsequent reactions and allow the rapid and diastereoconvergent assembly of complex decalines with contiguous stereocenters.     

Synthesis,Characterization, and Application of Platinum(II) Complexes Incorporating Racemic and Optically Active 4‐Chloro‐5‐Methyl‐1‐Phenyl‐1,2,3,6‐Tetrahydrophosphinine Ligand

An efficient resolution method was elaborated for the preparation of (+)‐4‐chloro‐5‐methyl‐1‐phenyl‐1,2,3,6‐tetrahydrophosphinine oxide using the acidic Ca²⁺ salt of (–)‐O,O‐di‐p‐toluoyl‐(2R,3R)‐tartaric acid. Crystal structure of the diastereomeric complex was evaluated by single crystal X‐ray analysis. Beside this, the absolute P‐configuration was also determined by a circular dichroism (CD) spectroscopic study including theoretical calculations. The tetrahydrophosphinine oxide was then converted to the corresponding platinum complex whose stereostructure was investigated by high‐level quantum chemical calculations. The Pt complex was tested as a catalyst in the hydroformylation of styrene.     

Effect of polymer molecular weight on the polymer/surfactant interaction

A thermodynamic analysis of the interaction between fourteen different molar mass poly(ethylene oxide)s (PEO) and sodium dodecyl sulfate (SDS) based on the measured surfactant-binding isotherms is given. The surfactant-binding isotherms were determined by the potentiometric method in the presence of 0.1 M inert electrolyte (NaBr). It was found that there is no PEO/SDS complex formation if M(PEO) < 1000. In the molecular weight range 1000 < M(PEO) < 8000, the critical aggregation concentration (cac) and the surfactant aggregation number are decreasing as the polymer molecular weight increases. The saturated bound surfactant amount is proportional to the number concentration of the polymer in this molecular weight range. If M(PEO) exceeds approximately 8000, the cac does not depend on the polymer molar mass, and the saturated bound amount of the surfactant becomes proportional to the mass concentration of the polymer. It was also observed that independently of the polymer molecular weight the surfactant aggregation number increases as the equilibrium surfactant monomer concentration increases from the cac to the critical micellar concentration (cmc). Finally, it was demonstrated that only one polymer molecule is involved in the complex formation independently of the polymer molecular weight.     

Treating singularities present in the Sutcliffe-Tennyson vibrational Hamiltonian in orthogonal internal coordinates

Two methods are developed, when solving the related time-independent Schrodinger equation (TISE), to cope with the singular terms of the vibrational kinetic energy operator of a triatomic molecule given in orthogonal internal coordinates. The first method provides a mathematically correct treatment of all singular terms. The vibrational eigenfunctions are approximated by linear combinations of functions of a three-dimensional nondirect-product basis, where basis functions are formed by coupling Bessel-DVR functions, where DVR stands for discrete variable representation, depending on distance-type coordinates and Legendre polynomials depending on angle bending. In the second method one of the singular terms related to a distance-type coordinate, deemed to be unimportant for spectroscopic applications, is given no special treatment. Here the basis set is obtained by taking the direct product of a one-dimensional DVR basis with a two-dimensional nondirect-product basis, the latter formed by coupling Bessel-DVR functions and Legendre polynomials. With the basis functions defined, matrix representations of the TISE are set up and solved numerically to obtain the vibrational energy levels of H3+. The numerical calculations show that the first method treating all singularities is computationally inefficient, while the second method treating properly only the singularities having physical importance is quite efficient.     

Simple and condensed β-lactams-I : The application of diketene in β-lactam synthesis. The synthesis and functional group manipulations of diethyl 3-acetyl-4-oxoazetidine-2,2-dicarboxylates

Acylation of the N-substituted diethyl aminomalonates 3a–3d with diketene furnished the ring tautomers 6a–6d of the expected acetoacetyl derivatives 5. By treatment with iodine and sodium ethoxide compounds 6a–6d are smoothly converted into the β-lactam derivatives 2a–2d. Deethoxycarbonylation of the ethylene ketals 7a–7d of the latter furnishes mixtures of the corresponding diastereomeric monoesters 8 and10. The ethoxycarbonyl groups of the trans esters 8 are more reactive than those of the cis isomers 10. This permits, under appropriate conditions, selective alkaline hydrolysis and NaBH₄ reduction of the trans esters 8 in the presence of the cis esters 10. Reduction of the cis ester 10c under more forceful conditions furnishes the trans hydroxymethyl derivative 11c.     

Synthesis of benzopyran derivatives,XV Preparation of arylsulfonyloxy-2,2-dimethyl-2H-chromenes

Summary Arylsulfonyloxy-2,2-dimethyl-2H-chromenes (26–35) have been synthesized by reduction of arylsulfonyloxy-2,2-dimethyl-4-chromanones (6–15) followed by dehydration.

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Synthese von Benzopyranderviaten. 15. Mitt.: Darstellung von Arylsulfonyloxy-2,2-dimethyl-2H-chromenen

Zusammenfassung Reduktion von Arylsulfonyloxy-2,2-dimethyl-4-chromanonen (6–15) und anschließende Dehydratisierung liefert Arylsulfonyloxy-2,2-dimethyl-2H-chromene (26–35).

     

Improved solubilization of surface proteins from Listeria monocytogenes for 2-DE

Solubilization of bacterial surface (cell wall and membrane-associated) proteins for 2-DE is challenging, particularly in the case of Gram-positive bacteria. This is primarily due to strong protein association with the cell wall peptidoglycan and protein hydrophobicity. We solubilized surface proteins for 2-DE from the Gram-positive pathogen Listeria monocytogenes using mutanolysin, which digests cell wall peptidoglycan, and one of three different mixtures of zwitterionic detergent and chaotropes: (i) CHAPS/urea, (ii) amidosulfobetaine-14 (ASB-14)/urea/thiourea (iii) N-decyl-N,N'-dimethyl-3-ammonio-1-propanesulfonate/urea/thiourea. Cell lysis with mutanolysin followed by solubilization with ASB-14/urea/thiourea gave the highest overall protein yield with the best 2-DE resolution. Protein spot identification by MALDI-TOF/TOF-MS analysis revealed 29 characterized surface proteins of L. monocytogenes, 17 of which have not previously been reported on the surface proteome map. This is the first report describing the successful solubilization and 2-DE of L. monocytogenes proteins bound to the cell surface via an LPXTG motif or by a hydrophobic tail. The increase in surface proteome coverage obtained by mutanolysin and ASB-14/urea/thiourea solubilization suggests the utility of this method for future analytical and comparative studies of surface proteins from Listeria, and possibly other Gram-positive bacteria, using 2-DE proteomic analysis. An updated 2-DE reference map of L. monocytogenes surface proteins is presented.     

Editorial

The credit crisis is a complex societal problem in which many phenomena and actors are involved. If one wants to analyze the causes of this problem, try to stabilize the situation and prevent new fall backs, a multi-disciplinary approach is prescribed. A careful analysis based on the scientific methodology of societal complexity is needed in order to find how the credit crisis happened and how new crises can be prevented. Theories of multiple disciplines must be used by a multi disciplinary team to analyze the situation and to find sustainable options. This process can be accomplished by following the Compram Methodology of DeTombe. The Compram Methodology provides a framework for policy making which includes many methods and tools. The Compram Methodology is specialized to handle complex interdisciplinary world-wide problems and to offer a step-by-step approach of analyzing the problem, finding and implementing sustainable interventions and evaluating the effects. The Compram Methodology offers a bird’s-eye view on the complexity of the problem and gives directions to policy makers to build their decisions on using a multi-disciplinary, multi-actor approach. In this article the credit crisis is discussed in relation with the Compram Methodology. Aspects of the credit crisis are described with an emphasis on the role of the actors. Based on the Compram Methodology directions can be provided for handling the credit crisis and avoiding future similar problems.     

A Verified Optimization Technique to Locate Chaotic Regions of Hénon Systems

We present a new verified optimization method to find regions for Hénon systems where the conditions of chaotic behaviour hold. The present paper provides a methodology to verify chaos for certain mappings and regions. We discuss first how to check the set theoretical conditions of a respective theorem in a reliable way by computer programs. Then we introduce optimization problems that provide a model to locate chaotic regions. We prove the correctness of the underlying checking algorithms and the optimization model. We have verified an earlier published chaotic region, and we also give new chaotic places located by the new technique.     

Modular Group Algebras with Almost Maximal Lie Nilpotency Indices

Let be a field of positive characteristic and the group algebra of a group . It is known that, if is Lie nilpotent, then its upper (and lower) Lie nilpotency index is at most , where is the order of the commutator subgroup. The authors previously determined those groups for which this index is maximal and here they determine the groups for which it is `almost maximal', that is, it takes the next highest possible value, namely .Presented by V. Dl a b.Dedicated to Professor Vjacheslav Rudko on his 65th birthday.The research was supported by OTKA No. T 037202, No. T 038059 and Italian National Research Project “Group Theory and Application.”