First Concise Total Synthesis of 5‐Epi‐prelactone B

First short total synthesis of 5‐epi‐prelactone B has been achieved involving Sharpless asymmetric epoxidation and intramolecular hydride transfer reaction for formation of the aldol product by nonaldol chemistry as the key steps.     

Unconventional air-stable interdigitated bilayer formed by 2,3-disubstituted fatty acid methyl esters

A single-chain fatty acid methyl ester, racemic anti-3-fluoro-2-hydroxyeicosanoic acid methyl ester (beta-FHE), forms an unconventional air-stable interdigitated bilayer at the air-water interface. The interdigitated bilayer transferred onto solid substrate by the Langmuir-Blodgett (LB) technique keeps air-stable without any substrate modification or protein inclusion. There are two visible plateaus in the surface pressure-molecular area (pi-A) isotherms of beta-FHE Langmuir film during continuous compression. According to Brewster angle microscopy (BAM), grazing incidence X-ray diffraction (GIXD), X-ray reflectivity (XR), fluorescence microscopy (FM), and atomic force microscopy (AFM) measurements, the first plateau is attributed to the coexistence of liquid expanded (LE) and liquid condensed (LC) phases in the monolayer, while the second plateau is interpreted as the transition from LC monolayer to interdigitated bilayer. The coupling between tilt and curvature associated with the packing mismatch between headgroup and chain gives rise to buckling and folding of the monolayer, leading to the transition of the LC monolayer to a bilayer structure. The diffusion-limited aggregation (DLA) model is applied to describe the formation of the fractal structures of the bilayer as observed in the second plateau. In addition, the transition between monolayer and bilayer is reversible. The present works are interesting for understanding biological processes, for example, the behavior of lung surfactants.     

A facile and chemoselective conjugate reduction using polymethylhydrosiloxane (PMHS) and catalytic B(C6F5)3

A highly chemoselective conjugate reduction of electron-deficient Michael acceptors, including alpha,beta-unsaturated ketones, carboxylic esters, nitriles and nitro compounds with PMHS in the presence of catalytic B(C6F5)3 is described.     

Gold(III)-mediated aldol condensations provide efficient access to nitrogen heterocycles

Quinolines, dihydroquinolines, and aza-xanthones can be synthesized efficiently and under mild reaction conditions by means of a reaction sequence employing Au(III)-catalyzed aldol reactions as the key step.     

Temperature-dependent phase behavior and the crystal-forming nucleation process of ethyl 4-fluoro-2,3-dihydroxystearate monolayers

The phase behavior of enantiomeric compounds as well as mixtures of enantiopure and racemic diastereomers of ethyl 4-fluoro-2,3-dihydroxystearates has been investigated using surface pressure-area isotherms and Brewster angle microscopy (BAM). All mixtures exhibit a small plateau region within the surface pressure-area isotherm at 20 degrees C, whereas the enantiopure compound shows an isotherm behavior similar to that of fatty acids. Corresponding to the film balance measurements, the BAM images demonstrate different shapes of the domains within the coexistence region of the liquid-condensed/liquid-expanded phase. The domain structures of the monolayers were visualized after Langmuir-Blodgett transfer on mica sheets by scanning force microscopy (SFM). From the SFM images it becomes obvious that small crystallites are formed for all investigated compounds; however, their molecular assembly is diverse for different enantiomers. Variations in the phase behavior can be correlated with interactions between the polar molecular moieties and the subphase and altered intermolecular interactions. Molecular modeling calculations were applied to elucidate the structural organization of these intermolecular interactions. Ab initio calculations of the minima conformers of (S,S,R)- and (S,S,S)-ethyl 4-fluoro-2,3-dihydroxystearates have been performed to predict with the HARDPACK program the two-dimensional lattice structure based on the P1 space group. These calculations showed that intermolecular hydrogen bridges are crucial for the interactions within and between the molecules.     

Diverted organic synthesis (DOS): accessing a new, natural product inspired, neurotrophically active scaffold through an intramolecular Pauson-Khand reaction

Drawing inspiration from the impressive neurotrophic activity exhibited by the natural product paecilomycine A, we have designed a new natural product-like scaffold employing an intramolecular Pauson-Khand reaction. Several compounds based on the new designer scaffold exhibited promising neurotrophic activity and are worthy of further biological evaluation. Our findings also highlight the importance of a DOS strategy in creating useful therapeutical leads.     

Statistical mechanics of combinatorial auctions

Combinatorial auctions are formulated as frustrated lattice gases on sparse random graphs, allowing the determination of the optimal revenue by methods of statistical physics. Transitions between computationally easy and hard regimes are found and interpreted in terms of the geometric structure of the space of solutions. We introduce an iterative algorithm to solve intermediate and large instances, and discuss competing states of optimal revenue and maximal number of satisfied bidders. The algorithm can be generalized to the hard phase and to more sophisticated auction protocols.     

Effects of Bilateral Subthalamic Nucleus Stimulation and Medication on Parkinsonian Speech Impairment

This study aimed to assess quantitatively the effect of bilateral subthalamic nucleus (STN) stimulation and medication on hypokinetic parkinsonian dysarthria. Twelve Italian patients (11 males and 1 female) with idiopathic Parkinson's disease (mean age 60.29+/-7.50 years) and bilateral STN implantation were studied. Neurological assessments and acoustic recordings were performed in four clinical conditions combining stimulation and medication to assess the degree of motor disabilities and speech impairment. Acoustic analysis was performed by means of the Multidimensional Voice Program and the Advanced Motor Speech Profile (Kay Elemetrics, Lincoln Park, NJ). None of the evaluated parameters deteriorated after STN deep brain stimulation. STN stimulation significantly improved motor performances and vocal tremor and provided a major stability to glottal vibration. Effect of stimulation on these parameters was superior to that of levodopa. No significant variations were observed in perceptual evaluation and in acoustic parameters related to prosody, articulation, and intensity after either stimulation or medication. The improvement of acoustic parameters related to glottal vibration and voice tremor was not accompanied by a substantial effect on speech intelligibility. STN stimulation was more effective on global motor limb dysfunctions than on dysarthria, but we did not report negative consequences on speech.