Coherence-polarization mixing in resonance gratings

We show, using rigorous diffraction theory, that resonance gratings can be used to transfer partial spatial correlation to partial polarization even if the incident light beam is fully polarized. The phenomenon is based on the fact that either of the two orthogonal polarization components can be coupled into the leaky waveguide mode, leading to a strong phase delay, while the other one is reflected without being coupled into the grating. Numerical demonstrations are based on a Gaussian Schell-model beam and a grating analysis performed by rigorous Fourier modal method.     

Total syntheses of angelicoin A, hericenone J, and hericenol A via migratory prenyl- and geranylation-aromatization sequences

A five-step synthesis of the natural product angelicoin A using a late stage highly regioselective palladium(0)-catalyzed decarboxylative prenyl migration and aromatization sequence as the key step is reported. The method was extended with geranyl migration in eight-step total syntheses of hericenone J and hericenol A from geraniol.     

Identification of isomeric 5‐hydroxytryptophan‐ and oxindolylalanine‐containing peptides by mass spectrometry

Cells continuously produce reactive oxidative species that can modify all cellular components. In proteins, for example, cysteine, methionine, tryptophan (Trp), and tyrosine residues are particularly prone to oxidation. Here, we report two new approaches to distinguish two isomeric oxidation products of Trp residues, i.e. 5‐hydroxytryptophan (5‐HTP) and oxindolylalanine (Oia) residues, in peptides. First, 2‐nitrobenzenesulfenyl chloride, known to derivatize Trp residues in position 2 of the indole ring, was used to label 5‐HTP residues. The mass shift of 152.98 m/z units allowed identifying 5‐HTP‐ besides Trp‐containing peptides by mass spectrometry, whereas Oia residues were not labeled. Second, fragmentation of the Oia‐ and 5‐HTP‐derived immonium ions at m/z 175.08 produced ions characteristic for each residue that allowed their identification even in the presence of y₁ ions at m/z 175.12 derived from peptides with C‐terminal arginine residues. The pseudo MS³ spectra acquired on a quadrupole time‐of‐flight hybrid mass spectrometer displayed two signals at m/z 130.05 and m/z 132.05 characteristic for Oia‐containing peptides and a group of six signals (m/z 103.04, 120.04, 130.04, 133.03, 146.04, and 148.04) for 5‐HTP‐cointaining peptides. In both cases, the relative signal intensities appeared to be independent of the sequence providing a specific fingerprint of each oxidative modification. Copyright © 2012 John Wiley & Sons, Ltd.     

Overcharging of polyelectrolyte complexes by the guest polyelectrolyte studied by fluorescence spectroscopy

Polyion complexes (PICs) of anionic block copolymer poly(ethylene oxide)-block-poly(sodium methacrylate), PEO-block-(PMA)Na, and a cationic homopolymer, poly((methacryloyloxyethyl)trimethylammonium chloride), PMOTAC, have been studied by fluorescence spectroscopy. Pyrene and naphthalene singly labeled block copolymers were used with two different sodium methacrylate block lengths. The chain exchange between the stoichiometric PICs at the equilibrium state and the formation of the negatively charged PICs on addition of excess PEO-block-(PMA)Na to stoichiometric PIC solution were of interest. The chain exchange between the stoichiometric complexes was observed to occur via two mechanisms. The faster chain exchange occurs via insertion and expulsion of single chains, while merging and splitting of the PIC particles is behind the slower chain exchange event. Incorporation of an excess amount of the guest polyion into a stoichiometric PIC took place on further addition of the PEO-block-(PMA)Na. The same mechanisms were recognized in the overcharging process of the PICs as in the chain exchange between the stoichiometric PICs.     

Fitting-Attitude Analyses: The Dual-Reason Analysis Revisited

Classical fitting-attitude analyses understand value in terms of its being fitting, or more generally, there being a reason to favour the bearer of value. Recently, such analyses have been interpreted as referring to two reason-notions rather than to only one. The idea is that the properties of the object provide reason not only for a certain kind of favouring(s) vis-à-vis the object, but the very same properties should also figure in the intentional content of the favouring; the agent should favour the object on account of those properties that provide reason for favouring the object in the first place. While this expansion of the original proposal might seem intuitive given that favourings are discerning attitudes, it is nonetheless argued that proponents of the fitting-attitude analysis are in fact not served by such an expansion of the classical analysis. The objections raised here are relevant not only for advocates and critics of fitting-attitude analyses, but for anyone interested in the relation between normative reasons and motivation.     

A Simple Efficient Synthesis of 5,8-Isoquinolinedione

5,8-Isoquinolinedione was synthesized from 5-hydroxyisoquinoline by nitrosation at C-8, reduction of the nitroso group and oxidation of the resultant 5-hydroxy-8-aminoisoquinoline.     

Cohesive zone model for a transverse breathing crack in a rotor

The breathing mechanism of a transversely cracked rotor and its influence on a rotor system that appears due to the shaft weight is studied. This breathing mechanism is based on experimental and simulation result for the crack shape reported in the literature. If the crack depth is small, the crack closure line is a straight line while for larger crack depths the crack closure becomes more curved. For both cases, a method is proposed for the evaluation of the stiffness losses in the cross section that contains the crack. This method is based on a cohesive zone model (CZM) instead of linear elastic fracture mechanics (LEFM) approach, because LEFM is valid only for the fully open crack and cannot be extended to other intermediate situations. As the crack is closed, the stress intensity factor (SIF) will not appear at the boundary between the closed cracked areas and the open cracked areas. The CZM is developed for mode-I plane strain conditions and accounts explicitly for triaxiality of the stress state by using constitutive relations. The proposed model gives more realistic results than models based on LEFM for the stiffness losses of the crack rotor system for a wide range of the crack depth. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)