Formal Total Synthesis of Kendomycin by Way of Alkyne Metathesis/Gold Catalysis

In an attempt to study the ability of the latest generation of alkyne metathesis catalysts to process sterically hindered substrates, two different routes to the bacterial metabolite kendomycin (1) were explored. Whereas the cyclization of the overcrowded arylalkyne 39 and related substrates turned out to be impractical or even impossible, ring closure of the slightly relaxed diyne 45 was achieved in excellent yield under notably mild conditions with the aid of the molybdenum alkylidyne 2 endowed with triphenylsilanolate ligands. The resulting cycloalkyne 46 was engaged into a gold-catalyzed hydroalkoxylation, which led to benzofuran 47 that had already previously served as a late-stage intermediate en route to 1

Period changes in six semi-detached Algol-type binaries

Six semi-detached Algol-type binaries lacking a period analysis were chosen to test for a presence of a third body. The O-C diagrams of these binaries were analyzed with the least-squares method by using all available times of minima. Also fourteen new minima, obtained from our observations, were included in the present research. The light-time effect was adopted as a main factor for the detailed description of the long-term period changes. Third bodies were found with orbital periods from 46 up to 84 years, and eccentricities from 0.0 to 0.78 for the selected binaries. The mass functions and the minimal masses of such bodies were also calculated.Comment: 14 pages, 8 figure

The Masses Of The B-Stars In The High Galactic Latitude Eclipsing Binary IT Lib

A number of blue stars which appear to be similar to Population I B-stars in the star forming regions of the galactic disk are found more than 1 kpc from the galactic plane. Uncertainties about the true distances and masses of these high latitude B-stars has fueled a debate as to their origin and evolutionary status. The eclipsing binary IT Lib is composed of two B-stars, is approximately one kiloparsec above the galactic plane, and is moving back toward the plane. Observations of the light and velocity curves presented here lead to the conclusion that the B-stars in this system are massive young main-sequence stars. While there are several possible explanations, it appears most plausible that the IT Lib system formed in the disk about 30 million years ago and was ejected on a trajectory taking it to its present position.Comment: 26 pages, 3 figures, accepted for publication in the PASP (January 2003

Radial Velocity Studies of Close Binary Stars.IV

Radial-velocity measurements and sine-curve fits to the orbital velocity variations are presented for the fourth set of ten close binary systems: 44 Boo, FI Boo, V2150 Cyg, V899 Her, EX Leo, VZ Lib, SW Lyn, V2377 Oph, Anon Psc (GSC 8-324), HT Vir. All systems are double-lined spectroscopic binaries with only two of them not being contact systems (SW Lyn and GSC 8-324) and with five (FI Boo, V2150 Cyg, V899 Her, EX Leo, V2377 Oph) being the recent photometric discoveries of the Hipparcos satellite project. Five of the binaries are triple-lined systems (44 Boo, V899 Her, VZ Lib, SW Lyn, HT Vir). Three (or possibly four) companions in the triple-lined systems show radial-velocity changes during the span of our observations suggesting that these are in fact quadruple systems. Several of the studied systems are prime candidates for combined light and radial-velocity synthesis solutions.Comment: aastex5.0, 5 figures in PS; submitted to Astron.

Tidal disruption of NEAs - a case of P\v{r}\'ibram

This work studies the dynamical evolution of a possible meteor stream along the orbit of the P\v{r}\'{i}bram meteorite, which originated in the tidal disruption of the putative rubble-pile-like parent body during a close approach to the Earth. We assumed the disruption at the time when the ascending or descending node of the parent orbit was close to the Earth's orbit. In the last 5000 years, the P\v{r}\'{i}bram orbit has crossed the Earth orbit twice. It happened about 4200 years and 3300 years ago. In both cases, we modeled the release of particles from the simplified model of rotating asteroid, and traced their individual orbital evolution to the current date. It takes several hundred years to spread released meteoroids along the entire orbit of the parent body. Even today, the stream would be relatively narrow. Considering a model parent body with physical parameters of the asteroid Itokawa, the complete disintegration of the object produced 3.8$\times10^{11}$ meteoroid particles with diameter $\geq$ 1\,cm. The meteor activity observed from the Earth is revealed and justification of follow-up observation during suggested activity of the shower in the first two weeks of April is discussed. The Earth's tidal forces would disintegrate a fraction of NEA population into smaller objects. We evaluate the upper limit of mass of disintegrated asteroids within the mean NEA lifetime and the contribution of disrupted matter to the size distribution of the NEA.Comment: 8 pages, 10 figure

Radial Velocity Studies of Close Binary Stars.III

Radial velocity measurements and simple sine-curve fits to the orbital velocity variations are presented for the third set of ten contact binary systems: CN And, HV Aqr, AO Cam, YY CrB, FU Dra, RZ Dra, UX Eri, RT LMi, V753 Mon, OU Ser. All systems but two are contact, double-line spectroscopic binaries with four of them (YY CrB, FU Dra, V753 Mon, OU Ser) being the recent discoveries of the Hipparcos satellite project. The most interesting object is V753 Mon with the mass-ratio closest to unity among all contact systems (q = 0.970 pm 0.003) and large total mass ((M1+M2)sin^3i = 2.93 pm 0.06). Several of the studied systems are prime candidates for combined light and radial-velocity synthesis solutions.Comment: submitted for publication in Astronomical Journal; 3 figures, 2 table

Genomic Mining for Aspergillus Natural Products

SummaryThe genus Aspergillus is renowned for its ability to produce a myriad of bioactive secondary metabolites. Although the propensity of biosynthetic genes to form contiguous clusters greatly facilitates assignment of putative secondary metabolite genes in the completed Aspergillus genomes, such analysis cannot predict gene expression and, ultimately, product formation. To circumvent this deficiency, we have examined Aspergillus nidulans microarrays for expressed secondary metabolite gene clusters by using the transcriptional regulator LaeA. Deletion or overexpression of laeA clearly identified numerous secondary metabolite clusters. A gene deletion in one of the clusters eliminated the production of the antitumor compound terrequinone A, a metabolite not described, from A. nidulans. In this paper, we highlight that LaeA-based genome mining helps decipher the secondary metabolome of Aspergilli and provides an unparalleled view to assess secondary metabolism gene regulation

Epileptic monocular nystagmus and ictal diplopia as cortical and subcortical dysfunction

AbstractWe present the case of a patient with ictal monocular nystagmus and ictal diplopia who became seizure-free after resection of a right frontal focal cortical dysplasia (FCD), type 2B. Interictal neuroophthalmological examination showed several beats of a monocular nystagmus and a spasm of the contralateral eye. An exclusively ictal monocular epileptic nystagmus could be an argument for an exclusively cortical involvement in monocular eye movement control. The interictal findings in our patient, however, argue for an irregular ictal activation of both the cortical frontal eye field and the brainstem

Secretion of iron(III)-reducing metabolites during protein acquisition by the ectomycorrhizal fungus paxillus involutus

The ectomycorrhizal fungus Paxillus involutus decomposes proteins using a two-step mechanism, including oxidation and proteolysis. Oxidation involves the action of extracellular hydroxyl radicals (•OH) generated by the Fenton reaction. This reaction requires the presence of iron(II). Here, we monitored the speciation of extracellular iron and the secretion of iron(III)-reducing metabolites during the decomposition of proteins by P. involutus. X-ray absorption spectroscopy showed that extracellular iron was mainly present as solid iron(III) phosphates and oxides. Within 1 to 2 days, these compounds were reductively dissolved, and iron(II) complexes were formed, which remained in the medium throughout the incubation. HPLC and mass spectrometry detected five extracellular iron(III)-reducing metabolites. Four of them were also secreted when the fungus grew on a medium containing ammonium as the sole nitrogen source. NMR identified the unique iron(III)-reductant as the diarylcyclopentenone involutin. Involutin was produced from day 2, just before the elevated •OH production, preceding the oxidation of BSA. The other, not yet fully characterized iron(III)-reductants likely participate in the rapid reduction and dissolution of solid iron(III) complexes observed on day one. The production of these metabolites is induced by other environmental cues than for involutin, suggesting that they play a role beyond the Fenton chemistry associated with protein oxidation