Some Applications of Isopropenyl Acetate To O-, N-and C-Acetylation

New procedures for the preparation of drugs and drug intermediates (isosorbide-5-nitrate, diltiazem) and intermediates of potential drugs using isopropenyl acetate are described.     

Dielectric relaxation of poly(ester-ether-carbonate) multiblock terpolymers

The dielectric properties of a series of poly(ester-ether-carbonate) multiblock terpolymers have been investigated as a function of ether and carbonate composition in the frequency range of 10³–10⁶ Hz. The degree of polymerization of the samples was determined by viscosimetry measurements. The weight fraction, degree of crystallinity, and melting temperatures were characterized by means of x-ray diffraction and DSC methods. Dielectric behavior has been discussed in terms of Havriliak-Negami formulation. The variation of the dielectric properties with temperature has been associated with two relaxation processes: a) the -relaxation process observed at low temperature, which is associated to local motion of polar groups attached to both the soft and the hard segments, and b) the process assigned to long-range molecular motions above the glass transition temperature.     

Monomers and polymers from plant oils via click chemistry reactions

As a consequence of the depleting of fossil reserves and environmental issues, today, plant oils and fatty acids derived therefrom have a respectable status within the polymer chemistry community. However, maximizing the benefits of these renewable feedstocks requires the utilization of sustainable and efficient chemical transformations. The emergence of click chemistry concept and especially the renaissance of thiol‐ene addition reaction have had an impact on the way to make plant oil‐derived polymers. This highlight discusses the applicability and success of thiol‐ene addition and other click reactions in the transformation of oleochemicals into monomers and polymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013     

Electronuclear multiconfiguration time‐dependent hartree calculations on the confined H atom with mobile electron and nucleus

A multiconfiguration time‐dependent Hartree method oriented toward calculations of a non‐Born‐Oppenheimer nature has been applied to the calculation of the dynamical properties of a confined H atom. The calculation is fully six‐dimensional and does not take into account constraints arising from linear or angular momentum conservation. The orbital evolution is monitored and the energy level spectrum of the system, as well as the dependence of the results on the decomposition of the Hamiltonian and on the correlation between radial degrees of freedom, is determined. © 2012 Wiley Periodicals, Inc.     

Aβ40 and Aβ42 amyloid fibrils exhibit distinct molecular recycling properties

A critical aspect to understanding the molecular basis of Alzheimer's disease (AD) is the characterization of the kinetics of interconversion between the different species present during amyloid-β protein (Aβ) aggregation. By monitoring hydrogen/deuterium exchange in Aβ fibrils using electrospray ionization mass spectrometry, we demonstrate that the Aβ molecules comprising the fibril continuously dissociate and reassociate, resulting in molecular recycling within the fibril population. Investigations on Aβ40 and Aβ42 amyloid fibrils reveal that molecules making up Aβ40 fibrils recycle to a much greater extent than those of Aβ42. By examining factors that could influence molecular recycling and by running simulations, we show that the rate constant for dissociation of molecules from the fibril (k(off)) is much greater for Aβ40 than that for Aβ42. Importantly, the k(off) values obtained for Aβ40 and Aβ42 reveal that recycling occurs on biologically relevant time scales. These results have implications for understanding the role of Aβ fibrils in neurotoxicity and for designing therapeutic strategies against AD.     

General approach to glycosidase inhibitors. Enantioselective synthesis of deoxymannojirimycin and swainsonine

[reaction: see text] Deoxymannojirimycin (2) and swainsonine (4) have been synthesized from each enantiomer of the same bicyclic carbamate precursor 7. The key intermediate was prepared by a simple and efficient three-step synthesis involving RCM of the diene 8, which in turn is easily accessible in any configuration from enantiomerically enriched 2,3-epoxy-4-penten-1-ol 9.     

New phosphite-oxazoline ligands for efficient Pd-catalyzed substitution reactions

We have designed and synthesized a new family of readily available highly modular phosphite-oxazoline ligands for the Pd-catalyzed asymmetric allylic substitution reactions. The introduction of a pi-acceptor flexible bulky biphenyl phosphite moiety in the ligand design is highly adventitious in the product outcome. Thus, this ligand series affords excellent reaction rates (TOF's up to >2400 mol.(mol.h)-1) and enantioselectivities (ee's up to >99%) and, at the same time, shows a broad scope for different substrate types.     

Electron capture ionization of explosives with a microflow rate particle beam interface

A method for the analysis of four widely used explosives based on reversed-phase liquid chromatography coupled to a quadrupole mass spectrometer is presented. A microflow rate particle beam interface was employed that offers simplified operation procedures and improved interfacing performance. A positive role played by the reduced size of the aerosol droplets generated by the microflow rate interface is outlined in this work. Greater vaporization efficiency and negligible thermal decomposition were observed for the selected compounds in the ion source of the mass spectrometer. Electron capture ionization allowed specific and sensitive determination of the analytes. Detection limits that ranged between 60 and 200 pg and had a signal-to-noise ratio of 5:1 were obtained in selected ion monitoring mode after column elution.