Selective separations of peptides with sequence deletions, single amino acid polymorphisms, and/or epimeric centers using macrocyclic glycopeptide liquid chromatography stationary phases

Separating closely related peptides (those differing by one or two amino acids or the chirality of a single amino acid) can be challenging using reversed-phase liquid chromatography (LC), ion-exchange LC, or using ion-pairing agents. Also, the mobile phases that give the best separations in these modes may not be electrospray ionization mass spectrometry (ESI-MS) compatible. Forty-two peptides from 11 peptide families were separated on three macrocyclic glycopeptide stationary phases in reverse-phase mode using ESI-MS-compatible mobile phases. The peptide classes studied were angiotensin, bradykinin, alpha-bag cell factor, beta,gamma-bag cell factor, beta-casomorphin, dynorphin, enkephalin, leucokinin, lutinizing hormone releasing hormone, neurotinsin, substance P, and vasopressin. High selectivity was observed for single amino acid substitutions (achiral and chiral) regardless of the position of the substitution in the sequence. Mobile phase optimization, its effect on peptide elution behavior, and chromatographic efficiency is also discussed. Using LC-ESI-MS, a 2 ng limit of detection was obtained, two orders of magnitude lower than the UV detection limit.     

More on countably compact,locally countable spaces

Following [5], aT ₃ spaceX is called good (splendid) if it is countably compact, locally countable (andω-fair).G(κ) (resp.S(κ)) denotes the statement that a good (resp. splendid) spaceX with |X|=κ exists. We prove here that (i) Con(ZF)→Con(ZFC+MA+2 ^ω is big+S(κ) holds unlessω=cf(κ)<κ); (ii) a supercompact cardinal implies Con(ZFC+MA+2suω>_ω+₁+┐G(ω_ω+₁); (iii) the “Chang conjecture” (ω_ω+₁),→(ω ₁,ω) implies ┐S(κ) for allκ≧k≧ω_ω; (iv) ifP addsω ₁ dominating reals toV iteratively then, in , we haveG(λ^ω) for allλ. Research supported by Hungarian National Foundation for Scientific Research grant no. 1805.     

Neue Zugänge zu einigen aromatischen Retinoiden

New Approaches to Some Aromatic Retinoids Starting from 2,3,5-trimethylphenol ( 2 ), two pathways to ethyl (all-E)-9-(4-methoxy-2,3,6-trimethylphenyl)-3,7-dimethylnona-2,4,6,8-tetraenoate ( 1 ) and to some of its (Z)-isomers have been developed. The first one is based on a Pd(O)-catalyzed arylation of (Z)-3-methylpent-2-en-4-yn-l-ol ( 6 ) with 4-bromo-2,3,5-trimethylanisol ( 5 ). The acetylenic C₁₅?alcohol 9 was transformed into the corresponding acetylenic phosphonium salt 10 , which was catalytically hydrogenated to the olefinic Wittig salt. Wittig olefination led, then, to the (6Z, 8Z)- and (4Z, 6Z, 8Z)-isomers, 7 and 8 , respectively. In a second approach, Friedel-Crafts reaction of 3-methylpent-l-en-4-yn-3-ol with the 2,3,5-trimethylanisol gave a C₁₅-intermediate with a terminal C?C bond in the side chain. After deprotonation and reaction with a C₅ aldehyd, the corresponding C₂₀-intermediate could be isolated in high yield. Finally, further conversion led predominantly to the (all-E)-retinoid, accompanied by its (9Z)- and (13Z)-isomers.     

Quasi-kernels and quasi-sinks in infinite graphs

Given a directed graph G=(V,E) an independent set A⊂V is called quasi-kernel (quasi-sink) iff for each point v there is a path of length at most 2 from some point of A to v (from v to some point of A). Every finite directed graph has a quasi-kernel. The plain generalization for infinite graphs fails, even for tournaments. We study the following conjecture: for any digraph G=(V,E) there is a a partition (V₀,V₁) of the vertex set such that the induced subgraph G[V₀] has a quasi-kernel and the induced subgraph G[V₁] has a quasi-sink.     

How To Split Antichains In Infinite Posets*

A maximal antichain A of poset P splits if and only if there is a set B ⊂ A such that for each p ∈ P either b ≤ p for some b ∈ B or p ≤ c for some c ∈ A\B. The poset P is cut-free if and only if there are no x < y < z in P such that [x,z]_P = [x,y]_P ∪ [y,z]_P . By [1] every maximal antichain in a finite cut-free poset splits. Although this statement for infinite posets fails (see [2])) we prove here that if a maximal antichain in a cut-free poset “resembles” to a finite set then it splits. We also show that a version of this theorem is just equivalent to Axiom of Choice. We also investigate possible strengthening of the statements that “A does not split” and we could find a maximal strengthening. * This work was supported, in part, by Hungarian NSF, under contract Nos. T37846, T34702, T37758, AT 048 826, NK 62321. The second author was also supported by Bolyai Grant.     

Inclusive and exclusive measurements in the projectile breakup of 7Li

The inclusive and exclusive measurements were carried out for ⁷Li projectile breakup on ²⁷Al target at 48 MeV. In the inclusive data we have observed a broad peak around the beam velocity for alphas and tritons. The exclusive data for alpha-triton coincidences show good agreement with the post-form DWBA theory of breakup reactions.     

The Interaction of the Supersonic Plasma-Jet with the Substrate in the RF Plasma-Chemical Reactor

Although the plasma-chemical processes and properties of the deposited thin film can strongly depend on the interaction of the supersonic plasma jet channel with the substrate, up to now the study of this phenomenon has not yet been done. We decided to study this interaction by means of CCD camera. The presented results indicate that the light intensity recorded close to the substrate can be used as a measure of the intensity of plasma-chemical deposition processes on the substrate surface.     

Backscatter from a limestone seafloor at 2-3.5 kHz: measurements and modeling

Physics-based interface scattering models for the seafloor [H.-H. Essen, J. Acoust. Soc. Am. 95, 1299-1310 (1994); Gragg et al., ibid. 110, 2878-2901 (2001)] exhibit features in their predicted grazing angle dependence. These features have a strong dependence on the assumed composition and roughness of the bottom. Verifying such predictions requires data that cover a wide range of grazing angles and involve minimal sub-bottom penetration. Such measurements were performed in the frequency band 2-3.5 kHz over an exposed limestone bottom off the Carolina coast during the second Littoral Warfare Advanced Development Focused Technology Experiment of 1996 (LWAD FTE 96-2). Direct-path bottom scattering strengths were obtained in shallow water (198-310 m deep) for grazing angles from 8 degrees to 75 degrees using data fusion from multiple experimental geometries coupled with careful signal processing. The processing included corrections for the surface-reflected path, other multipaths, and characteristics of the reverberation decay observed over the pulse duration at higher grazing angles. The resulting frequency and grazing-angle dependences exhibit trends consistent with theoretical predictions, and geoacoustic parameters obtained by inversion are consistent with values expected for limestone.