Asymmetric synthesis of the AB ring system of lactonamycin

[reaction: see text] An enantiospecific synthesis of the AB fragment of lactonamycin (5) is achieved in eight steps from dimethyl D-tartrate. Ester enolate chemistry features prominently in the sequence.     

Enhanced two-photon absorption with novel octupolar propeller-shaped fluorophores derived from triphenylamine

[structure: see text] Novel octupolar fluorophores derived from the symmetrical functionalization of a triphenylamine core with strong acceptor peripheral groups via phenylene-ethynylene linkers have been synthesized and shown to exhibit high fluorescence quantum yields, very large TPA cross-sections in the red-NIR region, and suitable photostability.     

Full orthogonality between Dde and Fmoc: the direct synthesis of PNA--peptide conjugates

New deprotection conditions for the Dde amine protecting group that are fully orthogonal to Fmoc are described and successfully applied to the dual synthesis of PNA-peptide conjugates.     

Triterpenoid saponins from leaves of Hedera pastuchowii

Five new triterpenoid saponins, pastuchoside A (1), B (3), C (5), D (7) and E (9), were isolated from the leaves of Hedera pastuchowii. They have oleanolic acid or hederagenin as aglycone. The structures were established by NMR spectroscopy including gs (gradient selected)-COSY, gs-HSQC, gs-HSQC-TOCSY and gs-HMBC experiments, and mass spectrometry (ESI-HR-MS). Heptaoside saponins, compounds 1 and 3, are described for the first time in the genus Hedera.     

Modeling continuous aqueous two-phase systems for control purposes

A mathematical model was proposed to allow the analysis of steady-state and transient behaviors of single-stage continuous aqueous two-phase systems. Since the complete system of simultaneous equations contains more equations than unknown variables, a program based on the method of least squares was developed to solve the problem. The methodology was tested using a system composed of thaumatin, sodium chloride, and a contaminant protein. A poly(ethylene-glycol)/phosphate salt/water system was selected to isolate the thaumatin. For the steady-state and transient operations, a constrained optimization procedure--from the Matlab Optimization Toolbox (MathWork, Inc.)--was implemented after recasting the system of equations as a minimization problem. Euler's method was used in the transient case to discretize the differential equations. The steady-state concentrations agreed with published data. An input-output model based on a 4% step change decrease in the inlet stream flow rate showed that output variables such as concentrations of sodium chloride and phosphate salt settled to their final values in different time periods. The proposed analysis may be helpful in the dynamic control of large-scale commercial extractor units using advanced control schemes.     

Comparison of Simple Particle-Radiation Coupling Models Applied on a Plasma Black Process

The effect of soot formation on the radiative heat transfer inside a plasma reactor for carbon black synthesis has been modelled. For this purpose, three methods to quantify the soot volume fraction have been tested and evaluated: (1) Assuming local thermodynamic equilibrium, (2) assuming instantaneous conversion of the hydrocarbon and (3) using a single-step soot model. These approaches have been studied using a two-dimensional axis-symmetric and a three-dimensional steady computational fluid dynamics (CFD) model based on the commercial software FLUENT (v.5.6). The CFD model includes turbulence effects (by standard k– model), an electric arc sub-model to describe the time-average and spatial-average Lorentz forces and ohmic heating generated by the three-phase power-supply, methane transport in a nitrogen plasma and radiation calculations. The calculations show that for the simulated operating conditions the resulting temperature distributions obtained are very similar with the three methods in spite of major differences in the treatment of particle formation in the different methods.     

Isothermal titration calorimetry of supramolecular polymers

A method to characterize the self-association of supramolecular polymers by isothermal titration calorimetry (ITC) has been designed. Association constants in the range 10(4)-10(6) dm(3) mol(-1) have been successfully determined from the heat exchange occurring when a supramolecular polymer solution is injected into a calorimetric cell containing pure solvent. Very good agreement with literature values has been obtained. Compared to other techniques (such as NMR or Fourier transform infrared spectroscopy), the use of ITC presents several advantages: (i) the enthalpy of association is obtained together with the association constant from the same experiment, (ii) the measurements can be performed in almost any solvent, and (iii) systems with higher association constants can be characterized.     

Frequency specificity of distortion-product otoacoustic emissions produced by high-level tones despite inefficient cochlear electromechanical feedback

Distortion product otoacoustic emissions (DPOAEs) are thought to stem from the outer hair cells (OHCs) around the normally narrow place tuned to the primary tone stimuli. They are thus said to be frequency-specific: their local absence should accurately pinpoint local OHC damage. Yet the influence of impaired tuning on DPOAE frequency specificity is poorly documented. Mice with local damage to OHCs were examined. Their DPOAEs were frequency-specific in that audiometric notches were accurately tracked. The same cochleae were further impaired by ischemia or furosemide injection inducing strial dysfunction with flat loss of sensitivity and tuning, while the preexisting pattern of damaged OHCs remained unaltered. Despite the loss of cochlear activity, DPOAEs produced by high-level (> or =70 dB SPL) primaries remained large in about the same interval where they had been initially normal, i.e., that with nondamaged OHCs, albeit with a slight frequency shift, of -1.1 kHz on average. Thus, the ability of DPOAEs to map structurally intact OHCs cannot be a mere consequence of cochlear tuning as it largely persists in its absence. The key element for this correct mapping is likely part of intact OHC structures (e.g., stereocilia bundles) and must have some tuning of its own.     

Optically driven spin memory in n-doped InAs-GaAs quantum dots

We show that the spin state of the resident electron in an n-doped self-assembled InAs-GaAs quantum dot can be written and read using nonresonant, circularly polarized optical pumping. A simple theoretical model is presented and accounts for the remarkable dynamics producing counterpolarized photoluminescence.     

Iodine(III)-mediated generation of nitrogen-tethered orthoquinol acetates for the construction of oxygenated indole,quinoline, and phenanthridine alkaloid motifs

Functionalized indole and quinoline derivatives are conveniently prepared from nitrogen-tethered 2-methoxyphenols via phenyliodine(III) diacetate mediated oxidative acetoxylation, followed by a fluoride- or base-induced intramolecular nucleophilic addition reaction. This regioselective Michael-type addition step is further discussed in view of the rearrangement of orthoquinol acetate intermediates into paraquinol acetates that is sometimes observed in situ. Application of this methodology to the synthesis of a functionalized phenanthridine, and its potential for the construction of polyoxygenated lycorine-type alkaloid skeleta are here described.