Total Synthesis of Mycinolide IV and Path‐Scouting for Aldgamycin N

Proof‐of‐concept is provided that a large estate of 16‐membered macrolide antibiotics can be reached by a “unified” approach. The key building block was formed on scale by an asymmetric vinylogous Mukaiyama aldol reaction; its alkene terminus was then converted either into the corresponding methyl ketone by Wacker oxidation or into a chain‐extended aldehyde by catalyst‐controlled branch‐selective asymmetric hydroformylation. These transformations ultimately opened access to two structurally distinct series of macrolide targets. Notable late‐stage maneuvers comprise a rare example of a ruthenium‐catalyzed redox isomerization of an 1,3‐enyne‐5‐ol into a 1,3‐diene‐5‐one derivative, as well as the elaboration of a tertiary propargylic alcohol into an acyloin by trans‐hydrostannation/Chan‐Lam‐type coupling. Moreover, this case study illustrates the underutilized possibility of forging complex macrolactone rings by transesterification under essentially neutral conditions

Detection of interstellar H_2D^+ emission

We report the detection of the 1_{10}-1_{11} ground state transition of ortho-H_2D^+ at 372.421 GHz in emission from the young stellar object NGC 1333 IRAS 4A. Detailed excitation models with a power-law temperature and density structure yield a beam-averaged H_2D^+ abundance of 3 x 10^{-12} with an uncertainty of a factor of two. The line was not detected toward W 33A, GL 2591, and NGC 2264 IRS, in the latter source at a level which is 3-8 times lower than previous observations. The H_2D^+ data provide direct evidence in support of low-temperature chemical models in which H_2D^+ is enhanced by the reaction of H_3^+ and HD. The H_2D^+ enhancement toward NGC 1333 IRAS 4A is also reflected in the high DCO^+/HCO^+ abundance ratio. Simultaneous observations of the N_2H^+ 4-3 line show that its abundance is about 50-100 times lower in NGC 1333 IRAS 4A than in the other sources, suggesting significant depletion of N_2. The N_2H^+ data provide independent lower limits on the H_3^+ abundance which are consistent with the abundances derived from H_2D^+. The corresponding limits on the H_3^+$ column density agree with recent near-infrared absorption measurements of H_3^+ toward W 33A and GL 2591.Comment: Standard AAS LaTeX format (15 pages + 2 figures

Revisiting the analytical solution approach to mixing-limited equilibrium multicomponent reactive transport using mixing ratios: identification of basis, fixing an error, and dealing with multiple minerals

Multicomponent reactive transport involves the solution of a system of nonlinear coupled partial differential equations. A number of methods have been developed to simplify the problem. In the case where all reactions are in instantaneous equilibrium and the mineral assemblage is constant in both space and time, de Simoni et al. (2007) provide an analytical solution that separates transport of aqueous components and minerals using scalar dissipation of Multicomponent reactive transport involves the solution of a system of nonlinear coupled partial differential equations. A number of methods have been developed to simplify the problem. In the case where all reactions are in instantaneous equilibrium and the mineral assemblage is constant in both space and time, de Simoni et al. (2007) provide an analytical solution that separates transport of aqueous components and minerals using scalar dissipation of "mixing ratios" between a number of boundary/initial solutions. In this approach, aqueous speciation is solved in conventional terms of primary and secondary species, and the mineral dissolution/precipitation rate is given in terms of the scalar dissipation and a chemical transformation term, both involving the secondary species associated with the mineral reaction. However, the identification of the secondary species is nonunique, and so it is not clear how to use the approach in general, a problem that is keenly manifest in the case of multiple minerals which may share aqueous ions. We address this problem by developing an approach to identify the secondary species required in the presence of one or multiple minerals. We also remedy a significant error in the de Simoni et al. (2007) approach. The result is a fixed and extended de Simoni et al. (2007) approach that allows construction of analytical solutions to multicomponent equilibrium reactive transport problems in which the mineral assemblage does not change in space or time and where the transport is described by closed-form solutions of the mixing ratios

Syzygies of torsion bundles and the geometry of the level l modular variety over M_g

We formulate, and in some cases prove, three statements concerning the purity or, more generally the naturality of the resolution of various rings one can attach to a generic curve of genus g and a torsion point of order l in its Jacobian. These statements can be viewed an analogues of Green's Conjecture and we verify them computationally for bounded genus. We then compute the cohomology class of the corresponding non-vanishing locus in the moduli space R_{g,l} of twisted level l curves of genus g and use this to derive results about the birational geometry of R_{g, l}. For instance, we prove that R_{g,3} is a variety of general type when g>11 and the Kodaira dimension of R_{11,3} is greater than or equal to 19. In the last section we explain probabilistically the unexpected failure of the Prym-Green conjecture in genus 8 and level 2.Comment: 35 pages, appeared in Invent Math. We correct an inaccuracy in the statement of Prop 2.

The new small-angle neutron scattering instrument SANS-1 at MLZ—characterization and first results

AbstractA thorough characterization of the key features of the new small-angle neutron scattering instrument SANS-1 at MLZ, a joint project of Technische Universität München and Helmholtz Zentrum Geesthacht, is presented. Measurements of the neutron beam profile, divergency and flux are given for various positions along the instrument including the sample position, and agree well with Monte Carlo simulations of SANS-1 using the program McStas. Secondly, the polarization option of SANS-1 is characterized for a broad wavelength band. A key feature of SANS-1 is the large accessible Q-range facilitated by the sideways movement of the detector. Particular attention is hence paid to the effects that arise due to large scattering angles on the detector where a standard cos3 solid angle correction is no longer applicable. Finally the performance of the instrument is characterized by a set of standard samples

Prerequisites for setting up management system in municipal retail trade

The relevance of the problem is determined by the number of complex problems that exist in present Samara municipal retail trade system, which is manifested in the lack of regulation, a glut of sales area, poorly developed infrastructure. The purpose of this article is to form a quantitative base for determining the municipal needs in the floor space. Leading method to study this problem is the method of empirical observations and mathematical modeling. The study results: the article contains the analysis of sales area availability on the example in the urban district and presents a quantitative method to determine predictive values for retail trade turnover. Practical significance: the paper is aimed to develop managerial decisions in the sphere of municipal trade regulation. © 2016 Suraeva et al

Revisiting the analytical solution approach to mixing-limited equilibrium multicomponent reactive transport using mixing ratios: identification of basis, fixing an error, and dealing with multiple minerals

Multicomponent reactive transport involves the solution of a system of nonlinear coupled partial differential equations. A number of methods have been developed to simplify the problem. In the case where all reactions are in instantaneous equilibrium and the mineral assemblage is constant in both space and time, de Simoni et al. (2007) provide an analytical solution that separates transport of aqueous components and minerals using scalar dissipation ofPeer ReviewedPostprint (published version

Evaluating inputs for organic farming – a new system. Proposals of the ORGANIC INPUTS EVALUATION project

This volume contains proposals for criteria for evaluation of plant protection products, fertilisers and soil conditioners1 to be used in organic agriculture. These ideas were developed in the course of the European Union (EU) Concerted Action project ‘ORGANIC INPUTS EVALUATION’ (QLK5-CT-2002-02565). For more information on this project see the end of this volume or visit the project website www.organicinputs.org. The documents in this volume are proposals elaborated by the project consortium and external experts. They were discussed with a broader audience at a public conference held in Brussels on October 13, 2005, and have been amended accordingly. Our proposals also include a “criteria matrix”, which is in Microsoft Excel format, and therefore stands as a separate file. The criteria matrix is discussed in section 5, but we strongly recommend that you consult the original document. To illustrate the use of the matrix, we have further prepared two case studies, which are also separate Excel files. All of these files are contained on the CD, and can also be downloaded from the project website. Currently, Regulation 2092/91 is under revision. We hope that our ideas can be incorporated into the regulation during this revision! In addition, we strongly encourage national institutions to make use of our proposals at the national level

A VLA Search for Water Masers in Six HII Regions: Tracers of Triggered Low-Mass Star Formation

We present a search for water maser emission at 22 GHz associated with young low-mass protostars in six HII regions -- M16, M20, NGC 2264, NGC 6357, S125, and S140. The survey was conducted with the NRAO Very Large Array from 2000 to 2002. For several of these HII regions, ours are the first high-resolution observations of water masers. We detected 16 water masers: eight in M16, four in M20, three in S140, and one in NGC 2264. All but one of these were previously undetected. No maser emission was detected from NGC 6357 or S125. There are two principle results to our study. (1) The distribution of water masers in M16 and M20 does not appear to be random but instead is concentrated in a layer of compressed gas within a few tenths of a parsec of the ionization front. (2) Significantly fewer masers are seen in the observed fields than expected based on other indications of ongoing star formation, indicating that the maser-exciting lifetime of protostars is much shorter in HII regions than in regions of isolated star formation. Both of these results confirm predictions of a scenario in which star formation is first triggered by shocks driven in advance of ionization fronts, and then truncated approximately 10^5 years later when the region is overrun by the ionization front.Comment: 30 pages, 20 figures, 3 tables. Accepted for publication by ApJ. Full resolution figures and PS and PDF versions with full-res figures available at http://eagle.la.asu.edu/healy/preprints/hhc0

Star Formation in Massive Protoclusters in the Monoceros OB1 Dark Cloud

We present far-infrared, submillimetre, and millimetre observations of bright IRAS sources and outflows that are associated with massive CS clumps in the Monoceros OB1 Dark Cloud. Individual star-forming cores are identified within each clump. We show that combining submillimetre maps, obtained with SCUBA on the JCMT, with HIRES-processed and modelled IRAS data is a powerful technique that can be used to place better limits on individual source contributions to the far-infrared flux in clustered regions. Three previously categorized "Class I objects" are shown to consist of multiple sources in different evolutionary stages. In each case, the IRAS point source dominates the flux at 12 and 25 microns. In two cases, the IRAS point source is not evident at submillimetre wavelengths. The submillimetre sources contribute significantly to the 60 and 100 micron fluxes, dominating the flux in the 100 micron waveband. Using fluxes derived from our technique, we present the spectral energy distribution and physical parameters for an intermediate-mass Class 0 object in one of the regions. Our new CO J=2-1 outflow maps of the three regions studied indicate complex morphology suggestive of multiple driving sources. We discuss the possible implications of our results for published correlations between outflow momentum deposition rates and "source" luminosities, and for using these derived properties to estimate the ratio of mass ejection rates to mass accretion rates onto protostars.Comment: 12 pages, 11 gzipped gif figures, LaTex file and MNRAS style files, accepted by MNRAS, v2: reference typos and author affiliation have been correcte