Synthesis, multiphase characterization, and helicity control in chiral DACH-linked oligothiophenes

A new class of chiral oligothiophenes is described. Mono-, bi-, ter-, and quarterthiophenes have been linked to enantiopure trans-1,2-cyclohexanediamine (DACH) via diamino or diimino moieties. The stereochemistry of DACH, the type of linker, and oligothiophene size determine the conformational flexibility of these molecules and consequently their molecular and supramolecular helicity in solution and in the solid state. The case of diaminobis(bithiophene), which inverts helicity and shows chiral amplification in the transition from solution to film, is described in detail. Based on the combined use of circular dichroism in solution and in the solid state, single-crystal/thin-film X-ray diffraction, and polarized optical microscopy, a working mechanism has been proposed to explain this unexpected behavior.     

A perturbation method for evaluating nonlinear normal modes of a piecewise linear two-degrees-of-freedom system

The classical Lindstedt–Poincaré method is adapted to analyze the nonlinear normal modes of a piecewise linear system. A simple two degrees-of-freedom, representing a beam with a breathing crack is considered. The fundamental branches of the two modes and their stability are drawn by varying the severity of the crack, i.e., the level of nonlinearity. Results furnished by the asymptotic method give insight into the mechanical behavior of the system and agree well with numerical results; the existence of superabundant modes is proven. The unstable regions and the bifurcated branches are followed by a numerical procedure based on the Poincarè map.     

Postcritical Behavior of Cables Undergoing Two Simultaneous Galloping Modes

Abstract. A nonlinear two degree-of-freedom model, describing a flexible elastic suspended cable undergoing galloping oscillations, is analyzed. By using a perturbative approach, the critical conditions occuring for different values of the aerodynamic coefficients are described. Two different type of critical conditions, corresponding to simple or double Hopf bifurcations are found. The nonlinear postcritical behavior of single taut strings in 1:1 primary internal resonance is studied through the multiple scale perturbation method. In the double Hopf bifurcation case the influence of the detuning between the critical eigenvalues on the postcritical behavior is illustrated. It is found that quasi-periodic motions, which are likely to occur in the linear field when the two critical frequencies are incommensurable, are really unstable in the nonlinear range. Therefore, the postcritical behavior of the string consists of stable periodic motions for any detuning values.Sommario. Viene analizzato un modello non lineare a due gradi di libertrappresentativo di un cavo elastico flessibile sospeso alle estremite soggetto ad oscillazioni galoppanti. Utilizzando un approccio perturbativo, vengono descritte le condizioni critiche per differenti valori dei coefficienti aerodinamici. Sono presenti due diversi tipi di condizioni critiche, corrispondenti a biforcazioni di Hopf semplici e doppie. Attraverso il metodo perturbativo delle scale multiple viene studiato il comportamento post-critico non lineare di singole stringhe tese in risonanza interna primaria 1:1. Nel caso di biforcazione doppia di Hopf viene illustrata l'influenza del detuning tra gli autovalori critici sul comportamento post-critico. Si trova che i moti quasi-periodici, presenti in campo lineare quando le due frequenze critiche sono incommensurabili, sono in realtinstabili in campo non lineare. Quindi, il comportamento post-critico della stringa risulta composto da moti periodici stabili per un qualsiasi valore del detuning.     

Monotonely Cauchy locally-solid topologies

The lattice of monotonely Cauchy (=pre-Lebesgue) locally solid topologies on a given lattice-ordered group is studied. Indentifying topologies agreeing on order bounded sets this lattice becomes a complete Boolean algebra isomorphic to the subalgebra of the lattice's complemented members and realizable as a Boolean algebra of order projections. Some consequences of these results are indicated.Work done while Tim Traynor was visiting professor at University of Napoli sponsored by CNR-Italia.     

Electrochemistry of α, α'-dibromoketones: Reduction of 2,4-dibromo-1,5-diphenyl-1,4-pentadien-3-one (α,α'-dibromo-dibenzylidene acetone) at the mercury electrode

2,4-Dibromo-1,5-diphenyl-1,4-pentadien-3-one (VIII (PhCH=CBrCOCBr=CHPh, α, ga'-dibromodibenzylidene acetone) is electroreduced in “aprotic” dimethylformamide at the mercury electrode; E_1/2 of the first step is ?0.97 V vs. SCE; two electrons/molecule of VIII were transferred (c.p.e.) and two Br^?/molecule of VIII were released. The product was identified as cis-1,5-diphenyl-1-penten-4-yn-3-one(PhCH=CHCOC=CPh), which is the rearrangement product of an unstable dimethylenecyclopropanone. In MeOH solutions, electroreduction of VIII follows a different path, the first two-electron step being substituted by a four-electron step (c.p.e.), which furnishes 3,4-diphenyl-cyclopent-2-enone, XIII. XIII seems to be a rearrangement product of a cyclic precursor. Subsequent two-step reduction of this intermediate in MeOH affords finally 1,5-diphenylpentan-3-one(α, α'-dibenzylacetone).     

Homogenous redox catalysis competition between electron exchange and proton exchange

Whether proton exchange and nucleophilic substitution reactions can become competitive with electron exchange reactions in homogeneous redox catalysis processes due to the reduction of bromoesters has been evaluated.Electrochemical data have been correlated with the results of the analyses carried out in solution during, and at the end of, the catalytic reduction processes. Thus, it has been possible to obtain the values of γ (γ = c_RX/c_O, where c_RX is the substrate concentration and c_O that of the catalyst corresponding to pure catalysis conditions whereby only the electron-exchange reaction is observed.The hypothesis that the catalyst (9,10-diphenylanthracene) is dihydrogenated by the substrate according to DISP₂ mechanism is in agreement with the experiments.     

Stereoselective electrochemical carboxylation: 2-phenylsuccinates from chiral cinnamic acid derivatives

Chiral 2-phenyl succinic ester derivatives have been obtained under mild conditions, in short times and with satisfactory yields by electrochemical reduction of chiral cinnamic acid derivatives under a CO2 atmosphere. When 4R-(diphenylmethyl)-oxazolidin-2-one was used as a chiral auxiliary the two diastereoisomers could be easily separated by flash chromatography and the R-isomer was obtained as major product.     

A simple approach for coupling liquid chromatography and electron ionization mass spectrometry

A miniaturized, aerosol based interface for directly coupling a liquid chromatograph with a mass spectrometer is presented. The interface is entirely within the electron ionization (EI) source of the mass spectrometer and no additional, external devices are needed. This simple and effective approach exploits micro-flow nebulization technology providing a new interface suitable for a variety of applications of environmental and biological interest. The new interface provides necessary linearity, ruggedness, sensitivity, and reproducibility of response for trace level analysis, and readily interpretable mass spectra for unambiguous identification of unknown compounds of small to medium molecular weight.