Sur une construction de Bruck et Reilly

The definition of repetitive semigroups introduced in [6] being recalled, let A be a semigroup and Θ an endomorphism of A. It is shown that if A is repetitive and ΘA is finite, then the semigroup obtained from A and Θ by the Bruck-Reilly construction (in its general form) [9] is also repetitive.      

Double C-H activation during functionalization of phenyl(methyl)ketene on iridium(I) using alkynes. synthesis of 1,4-dien-3-ones

Under the influence of an Ir(I) metal fragment, the methyl group of phenyl(methyl)ketene undergoes two C-H activations in reacting with internal alkynes, giving metallacycles 3 in 86-94% yield. Treatment of 3 with CO liberates 1,4-dien-3-ones 5 in 81-93% yield, along with CO complex 4. A possible mechanism for the very selective double C-H activation-alkyne coupling is discussed.     

Generation of optical vector beams with a diffractive optical element interferometer

We present a novel approach to generating radially and azimuthally polarized vector beams that utilize an interferometer constructed from two identical diffractive optical elements. The measured polarization properties of four vector beam states and their phase relationships are in good agreement with theoretical expectations. This interferometer is passively phase stable and robust, making it suitable for linear and nonlinear optical (superresolution) microscopy.     

Ion soft-landing into liquids: Protein identification,separation, and purification with retention of biological activity

Protein ions, after mass spectrometric separation, can be soft-landed into liquid surfaces with preservation of their native structures. Retention of biological activity is strongly favored in glycerol-based surfaces but not in self-assembled monolayer solid surfaces. Soft-landing efficiency for multiply-charged hexokinase ions was found to be some four times higher for a glycerol/fructose liquid surface than for a fluorinated self-assembled monolayer surface. Soft-landing into liquid surfaces is also shown to allow (1) protein purification, (2) on-surface identification of the soft-landed material using MALDI, and (3) protein identification by in-surface tryptic digestion. Pure lysozyme was successfully isolated from different mixtures including an oxidized, partially decomposed batch of the protein and a partial tryptic digest. Liquid glycerol/carbohydrate mixtures could be used directly to record MALDI spectra on the soft-landed compounds provided they were fortified in advance with traditional MALDI matrices such as p-nitroaniline and alpha-cyano-4-hydroxycinnamic acid. Various proteins were soft-landed and detected on-target using these types of liquid surface. Soft-landing of multiply-charged lysozyme ions onto fluorinated self-assembled monolayer surfaces was found to occur with a limited amount of neutralization, and trapped multiply-charged ions could be desorbed from the surface by laser desorption. Initial data is shown for a new approach to protein identification that combines top-down and bottom-up approaches by utilizing protein ion soft-landing from a protein mixture, followed by tryptic digestion of the landed material and detection of characteristic tryptic fragments by MALDI.     

Protein recognition using synthetic surface-targeted agents

The design of synthetic agents to disrupt protein-protein interactions has received relatively little attention in recent years. In this review we describe strategies for targeting different types of protein surfaces using mimetics of protein secondary or tertiary structure. In this way strong and selective binding to a protein surface has be achieved and disruption of clinically important protein-protein interactions has been demonstrated in models of human disease.     

Inflation versus cyclic predictions for spectral tilt

We present a nearly model-independent estimate that yields the predictions of a class of simple inflationary and ekpyrotic or cyclic models for the spectral tilt of the primordial density inhomogeneities that enables us to compare the two scenarios. Remarkably, we find that the two produce an identical result, n(s) approximately 0.95. For inflation, the same estimate predicts a ratio of tensor to scalar contributions to the low l multipoles of the microwave background anisotropy of T/S approximately 20%; the tensor contribution is negligible for ekpyrotic or cyclic models, as shown in earlier papers.     

Efficient N-demethylation of opiate alkaloids using a modified nonclassical Polonovski reaction

A modified Polonovski reaction has been employed to N-demethylate several opiate alkaloids in moderate to high yield. This method provides an alternative to traditional N-demethylation procedures which utilize toxic reagents such as cyanogen bromide or expensive reagents such as vinyl chloroformate. The current synthesis involves N-oxide formation, isolation of the corresponding N-oxide hydrochloride, and an FeSO(4).7H(2)O mediated Polonovski reaction to afford the desired secondary amine.     

Absolute potassium cation affinities (PCAs) in the gas phase

The potassium cation affinities (PCAs) of 136 ligands (20 classes) in the gas phase were established by hybrid density functional theory calculations (B3-LYP with the 6-311+G(3df,2p) basis set). For these 136 ligands, 70 experimental values are available for comparison. Except for five specific PCA values-those of phenylalanine, cytosine, guanine, adenine (kinetic-method measurement), and Me(2)SO (by high-pressure mass spectrometric equilibrium measurement)-our theoretical estimates and the experimental affinities are in excellent agreement (mean absolute deviation (MAD) of 4.5 kJ mol(-1)). Comparisons with previously reported theoretical PCAs are also made. The effect of substituents on the modes of binding and the PCAs of unsubstituted parent ligands are discussed. Linear relations between Li+/Na+ and K+ affinities suggest that for the wide range of ligands studied here, the nature of binding between the cations and a given ligand is similar, and this allows the estimation of PCAs from known Li+ and/or Na+ affinities. Furthermore, empirical equations relating the PCAs of ligands with their dipole moments, polarizabilities (or molecular weights), and the number of binding sites were established. Such equations offer a simple method for estimating the PCAs of ligands not included in the present study.