An in-depth investigation into the temperature dependence of the mass spectra of an Au82Si18 liquid metal field emitter

The mass spectra of the beam emitted by a Au₈₂Si₁₈ eutectic molten metal ion source are investigated in detail as a function of emitter temperature. At the conclusion of the work it emerges that while Au⁺, Si⁺, and Si⁺⁺ are the result of direct field-evaporation from the liquid surface, Au⁺⁺ forms by the post-ionisation of Au⁺. Cluster ions are most probably the product of droplet break-up. PACS  07.77.Ka; 32.10.Bi; 61.25.Mv     

Asymmetric sulfur ylide mediated aziridination: application in the synthesis of the side chain of taxol

[reaction: see text] Sulfur ylide methodology has been used to construct the Taxol side chain with a high degree of enantioselectivity via a trans-aziridine followed by stereospecific rearrangement of the trans-benzoylaziridine into a trans-oxazoline.     

Sine-Gordon Theory for the Equation of State of Classical Hard-Core Coulomb Systems. I. Low Fugacity Expansion

We present an exact field theoretical representation of the statistical mechanics of classical hard-core Coulomb systems. This approach generalizes the usual sine-Gordon theory valid for point-like charges or lattice systems to continuous Coulomb fluids with additional short-range interactions. This formalism is applied to derive the equation of state of the restricted primitive model of electrolytes in the low fugacity regime up to order ρ^5/2 (ρ number density). We recover the results obtained by Haga by means of Mayer graphs expansions.     

Synthesis of unnatural 2- and 3-deoxyfuranose analogues

This Letter describes the synthesis of two racemic analogues of unnatural 3′-deoxy and 2′-deoxy sugars, where a phosphorus atom replaces the carbon atom in the 2′- or 3′-position. Two methods of four- and 5-steps were developed affording these new unnatural sugar analogues.     

Chemical labeling and enrichment of nitrotyrosine-containing peptides

Protein tyrosine nitration (PTN) is a post-translational modification of proteins associated with a number of inflammatory diseases. While PTN is rather selective (not all proteins are modified and within a protein, only certain tyrosines are subject to nitration), no consensus sequence has been identified. Since PTN is a low-abundance post-translational modification, it is necessary to enrich modified proteins and/or to detect them with high selectivity and sensitivity. Until now this has been mostly accomplished with anti-nitrotyrosine antibodies in combination with two-dimensional gel electrophoresis and mass spectrometry. We propose a chemical labeling approach designed to allow enrichment of tyrosine-nitrated peptides independent of the sequence context, which is a potential shortcoming of antibody-based approaches. In this procedure, all amines are blocked by acetylation followed by conversion of nitrotyrosine to aminotyrosine and biotinylation of aminotyrosine. The entire reaction sequence is performed in a single buffer with no need for sample cleanup or pH changes thereby reducing sample loss. Free biotin is subsequently removed with a strong cation exchanger, the labeled peptides are enriched on an immobilized avidin column and the enriched peptides analyzed by LC-MS/MS. As a proof of concept, this method was successfully applied to the enrichment of tyrosine-nitrated angiotensin II in a tryptic digest of bovine serum albumin (BSA). The approach presented here is well adapted to peptide analysis, for instance in shotgun proteomics.     

Asymmetric Palladium-Assisted Alkylation of Alkenes

Palladium-promoted alkylation of alkenes using chiral sulfoxide-containing carbanions and chiral lithiated oxazolines results in asymmetric induction (AI) ranging from 3–5% (1,5 induction), 20–40% (1,3 induction) to 44–52% (1,4 induction). No general trend allowing predictions of results was found. With 1-hexene, attack at C(1) is almost exclusive but propene gives a mixture of attack at C(1) and C(2). The use of a chiral ligand together with malonate anion also leads to some asymmetric induction (ca. 20%).     

Topological Entropy and Secondary Folding

A convenient measure of a map or flow’s chaotic action is the topological entropy. In many cases, the entropy has a homological origin: it is forced by the topology of the space. For example, in simple toral maps, the topological entropy is exactly equal to the growth induced by the map on the fundamental group of the torus. However, in many situations the numerically computed topological entropy is greater than the bound implied by this action. We associate this gap between the bound and the true entropy with ‘secondary folding’: material lines undergo folding which is not homologically forced. We examine this phenomenon both for physical rod stirring devices and toral linked twist maps, and show rigorously that for the latter secondary folds occur.     

Regular subsets of valued fields and Bhargava’s v-orderings

We generalize notions and results obtained by Amice for regular compact subsets S of a local field K and extended by Bhargava to general compact subsets of K. Considering any ultrametric valued field K and subsets S that are regular in a generalized sense (but not necessarily compact), we show that they still have strong properties such as having v-orderings ${\{a_n\}_{n\geq0}}$ which satisfy a generalized Legendre formula, which are very well ordered and well distributed sequences in the sense of Helsmoortel and which remain v-orderings when a finite number of the initial terms of the sequence are deleted.     

An articulatory basis for the labial-to-coronal effect: /pata/ seems a more stable articulatory pattern than /tapa/

This paper investigates the coordination between the jaw, the tongue tip, and the lower lip during repetition with rate increase of labial-to-coronal (L(a)C(o)) consonant-vowel-consonant-vowel disyllables (e.g., /pata/) and coronal-to-labial (C(o)L(a)) ones (e.g., /tapa/) by French speakers. For the two types of disyllables: (1) the speeding process induces a shift from two jaw cycles per disyllable to a single cycle; (2) this shift modifies the coordination between the jaw and the constrictors, and (3) comes with a progression toward either a L(a)C(o) attractor [e.g., (/pata/ or /tapa/) --> /patá/ --> /ptá/] or a C(o)L(a) one (e.g., /pata/ or /tapa/ --> /tapá/ --> /tpá/). Yet, (4) the L(a)C(o) attractor is clearly favored regardless of the initial sequencing. These results are interpreted as evidence that a L(a)C(o) CVCV disyllable could be a more stable coordinative pattern for the lip-tongue-jaw motor system than a C(o)L(a) one. They are discussed in relation with the so-called LC effect that is the preference for L(a)C(o) associations rather than C(o)L(a) ones in CV.CV disyllables in both world languages and infants' first words.     

Impact of bidirectional charge transfer and molecular distortions on the electronic structure of a metal-organic interface

Interface energetics are of fundamental importance in organic and molecular electronics. By combining complementary experimental techniques and first-principles calculations, we resolve the complex interplay among several interfacial phenomena that collectively determine the electronic structure of the strong electron acceptor tetrafluoro-tetracyanoquinodimethane chemisorbed on copper. The combination of adsorption-induced geometric distortion of the molecules, metal-to-molecule charge transfer, and molecule-to-metal back transfer leads to a net increase of the metal work function.