Allylic Benzoate Reductions: A Study on Stereospecificity

Herein we report results from experiments aimed at better understanding SmI2(H2O)n reductions of allylic benzoates adjacent to a trisubstituted alkene. When flanked by both a chelating group and stereodirecting group, these reactions can occur with complete regioselectivity and good diastereoselectivity (up to 90:10). Initial experiments suggested that the reaction was stereospecific to alkene geometry. However, further experimentation has revealed that the alkene stereospecificity is substrate dependent. For instance, if the geminal alkene substituents are alkyl, results show the reaction to be stereospecific, but if one of the substituents is a phenyl group the reaction is still stereoselective but not stereospecific. This was demonstrated through the synthesis and subsequent SmI2(H2O)n reduction of a series of cis- and trans-allylic benzoate isomers followed by careful analysis of the product mixtures by 1H NMR. To explain these results our current working hypothesis is based on formation of an η3-organosamarium bicyclic intermediate. In some cases, C-C bond rotation in the pi-allyl intermediate relieves steric strain, leading to a loss in stereospecificity

Analysis of the giant genomes of Fritillaria (Liliaceae) indicates that a lack of DNA removal characterizes extreme expansions in genome size.

This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.Plants exhibit an extraordinary range of genome sizes, varying by > 2000-fold between the smallest and largest recorded values. In the absence of polyploidy, changes in the amount of repetitive DNA (transposable elements and tandem repeats) are primarily responsible for genome size differences between species. However, there is ongoing debate regarding the relative importance of amplification of repetitive DNA versus its deletion in governing genome size. Using data from 454 sequencing, we analysed the most repetitive fraction of some of the largest known genomes for diploid plant species, from members of Fritillaria. We revealed that genomic expansion has not resulted from the recent massive amplification of just a handful of repeat families, as shown in species with smaller genomes. Instead, the bulk of these immense genomes is composed of highly heterogeneous, relatively low-abundance repeat-derived DNA, supporting a scenario where amplified repeats continually accumulate due to infrequent DNA removal. Our results indicate that a lack of deletion and low turnover of repetitive DNA are major contributors to the evolution of extremely large genomes and show that their size cannot simply be accounted for by the activity of a small number of high-abundance repeat families.Thiswork was supported by the Natural Environment ResearchCouncil (grant no. NE/G017 24/1), the Czech Science Fou nda-tion (grant no. P501/12/G090), the AVCR (grant no.RVO:60077344) and a Beatriu de Pinos postdoctoral fellowshipto J.P. (grant no. 2011-A-00292; Catalan Government-E.U. 7thF.P.)

The C-Band All-Sky Survey (C-BASS): design and capabilities

The C-Band All-Sky Survey (C-BASS) is an all-sky full-polarization survey at a frequency of 5 GHz, designed to provide complementary data to the all-sky surveys of WMAP and Planck, and future CMB B-mode polarization imaging surveys. The observing frequency has been chosen to provide a signal that is dominated by Galactic synchrotron emission, but suffers little from Faraday rotation, so that the measured polarization directions provide a good template for higher frequency observations, and carry direct information about the Galactic magnetic field. Telescopes in both northern and southern hemispheres with matched optical performance are used to provide all-sky coverage from a ground-based experiment. A continuous-comparison radiometer and a correlation polarimeter on each telescope provide stable imaging properties such that all angular scales from the instrument resolution of 45 arcmin up to full sky are accurately measured. The northern instrument has completed its survey and the southern instrument has started observing. We expect that C-BASS data will significantly improve the component separation analysis of Planck and other CMB data, and will provide important constraints on the properties of anomalous Galactic dust and the Galactic magnetic field

The C-Band All-Sky Survey (C-BASS): Constraining diffuse Galactic radio emission in the North Celestial Pole region

The C-Band All-Sky Survey C-BASS is a high-sensitivity all-sky radio survey at an angular resolution of 45 arcmin and a frequency of 4.7 GHz. We present a total intensity 4.7 GHz map of the North Celestial Pole (NCP) region of sky, above declination +80 deg, which is limited by source confusion at a level of ~0.6 mK rms. We apply the template-fitting (cross-correlation) technique to WMAP and Planck data, using the C-BASS map as the synchrotron template, to investigate the contribution of diffuse foreground emission at frequencies ~20-40 GHz. We quantify the anomalous microwave emission (AME) that is correlated with far-infrared dust emission. The AME amplitude does not change significantly (<10%) when using the higher frequency C-BASS 4.7 GHz template instead of the traditional Haslam 408 MHz map as a tracer of synchrotron radiation. We measure template coefficients of $9.93\pm0.35$ and $9.52\pm0.34$ K per unit $\tau_{353}$ when using the Haslam and C-BASS synchrotron templates, respectively. The AME contributes $55\pm2\,\mu$K rms at 22.8 GHz and accounts for ~60% of the total foreground emission. Our results suggest that a harder (flatter spectrum) component of synchrotron emission is not dominant at frequencies >5 GHz; the best-fitting synchrotron temperature spectral index is $\beta=-2.91\pm0.04$ from 4.7 to 22.8 GHz and $\beta=-2.85\pm0.14$ from 22.8 to 44.1 GHz. Free-free emission is weak, contributing ~$7\,\mu$K rms (~7%) at 22.8 GHz. The best explanation for the AME is still electric dipole emission from small spinning dust grains.Comment: 18 pages, 6 figures, version matches version accepted by MNRA

Alkenones as a promising green alternative for waxes in cosmetics and personal care products

© The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Cosmetics 5 (2018): 34, doi:10.3390/cosmetics5020034.The move toward green, sustainable, natural products has been growing in the cosmetic and personal care industry. Ingredients derived from marine organisms and algae are present in many cosmetic products. In this study, a new green ingredient, a wax (i.e., long-chain alkenones) derived from Isochyrsis sp., was evaluated as an alternative for cosmetic waxes. First, the melting point was determined (71.1–77.4 °C), then the alkenones’ thickening capability in five emollients was evaluated and compared to microcrystalline wax and ozokerite. Alkenones were compatible with three emollients and thickened the emollients similarly to the other waxes. Then, lipsticks and lip balms were formulated with and without alkenones. All products remained stable at room temperature for 10 weeks. Lipstick formulated with alkenones was the most resistant to high temperature. Finally, alkenones were compared to three cosmetic thickening waxes in creams. Viscosity, rheology, and stability of the creams were evaluated. All creams had a gel-like behavior. Both viscosity and storage modulus increased in the same order: cream with alkenones < cetyl alcohol < stearic acid < glyceryl monostearate. Overall, alkenones’ performance was comparable to the other three waxes. Alkenones can thus offer a potential green choice as a new cosmetic structuring agent.This research was funded by the Washington Research Foundation and a private donor from friends of the Woods Hole Oceanographic Institution, grant number N-126478

C-Band All-Sky Survey: A First Look at the Galaxy

We present an analysis of the diffuse emission at 5 GHz in the first quadrant of the Galactic plane using two months of preliminary intensity data taken with the C-Band All Sky Survey (C-BASS) northern instrument at the Owens Valley Radio Observatory, California. Combining C-BASS maps with ancillary data to make temperature-temperature plots we find synchrotron spectral indices of $\beta = -2.65 \pm 0.05$ between 0.408 GHz and 5 GHz and $\beta = -2.72 \pm 0.09$ between 1.420 GHz and 5 GHz for $-10^{\circ} < |b| < -4^{\circ}$, $20^{\circ} < l < 40^{\circ}$. Through the subtraction of a radio recombination line (RRL) free-free template we determine the synchrotron spectral index in the Galactic plane ($|b| < 4^{\circ}$) to be $\beta = -2.56 \pm 0.07$ between 0.408 GHz and 5 GHz, with a contribution of $53 \pm 8$ per cent from free-free emission at 5\,GHz. These results are consistent with previous low frequency measurements in the Galactic plane. By including C-BASS data in spectral fits we demonstrate the presence of anomalous microwave emission (AME) associated with the HII complexes W43, W44 and W47 near 30 GHz, at 4.4 sigma, 3.1 sigma and 2.5 sigma respectively. The CORNISH VLA 5 GHz source catalogue rules out the possibility that the excess emission detected around 30\;GHz may be due to ultra-compact HII regions. Diffuse AME was also identified at a 4 sigma level within $30^{\circ} < l < 40^{\circ}$, $-2^{\circ} < b < 2^{\circ}$ between 5 GHz and 22.8 GHz.Comment: 16 pages, 9 figures, submitted to MNRAS, referee's corrections made, awaiting for final approval for publicatio

Eukaryotic genome size databases

Three independent databases of eukaryotic genome size information have been launched or re-released in updated form since 2005: the Plant DNA C-values Database (), the Animal Genome Size Database () and the Fungal Genome Size Database (). In total, these databases provide freely accessible genome size data for >10 000 species of eukaryotes assembled from more than 50 years' worth of literature. Such data are of significant importance to the genomics and broader scientific community as fundamental features of genome structure, for genomics-based comparative biodiversity studies, and as direct estimators of the cost of complete sequencing programs

Fluorochemicals from fluorspar via a phosphate-enabled mechanochemical process that bypasses HF

All fluorochemicals-including elemental fluorine and nucleophilic, electrophilic, and radical fluorinating reagents-are prepared from hydrogen fluoride (HF). This highly toxic and corrosive gas is produced by the reaction of acid-grade fluorspar (>97% CaF2) with sulfuric acid under harsh conditions. The use of fluorspar to produce fluorochemicals via a process that bypasses HF is highly desirable but remains an unsolved problem because of the prohibitive insolubility of CaF2. Inspired by calcium phosphate biomineralization, we herein disclose a protocol of treating acid-grade fluorspar with dipotassium hydrogen phosphate (K2HPO4) under mechanochemical conditions. The process affords a solid composed of crystalline K3(HPO4)F and K2-xCay(PO3F)a(PO4)b, which is found suitable for forging sulfur-fluorine and carbon-fluorine bonds

THE MASSIVE AND DISTANT CLUSTERS OF WISE SURVEY. III. SUNYAEV-ZEL'DOVICH MASSES OF GALAXY CLUSTERS AT z ~ 1

We present CARMA 30 GHz Sunyaev–Zel'dovich (SZ) observations of five high-redshift (z [> over ~] 1), infrared-selected galaxy clusters discovered as part of the all-sky Massive and Distant Clusters of WISE Survey (MaDCoWS). The SZ decrements measured toward these clusters demonstrate that the MaDCoWS selection is discovering evolved, massive galaxy clusters with hot intracluster gas. Using the SZ scaling relation calibrated with South Pole Telescope clusters at similar masses and redshifts, we find these MaDCoWS clusters have masses in the range M[subscript 200] ≈ 2-6 X 10[superscript 14] M[subscript ʘ. Three of these are among the most massive clusters found to date at z [> over ~] 1, demonstrating that MaDCoWS is sensitive to the most massive clusters to at least z = 1.3. The added depth of the AllWISE data release will allow all-sky infrared cluster detection to z ≈ 1.5 and beyond

Genome-wide association mapping of date palm fruit traits

Date palms (Phoenix dactylifera) are an important fruit crop of arid regions of the Middle East and North Africa. Despite its importance, few genomic resources exist for date palms, hampering evolutionary genomic studies of this perennial species. Here we report an improved long-read genome assembly for P. dactylifera that is 772.3 Mb in length, with contig N50 of 897.2 Kb, and use this to perform genome-wide association studies (GWAS) of the sex determining region and 21 fruit traits. We find a fruit color GWAS at the R2R3-MYB transcription factor VIRESCENS gene and identify functional alleles that include a retrotransposon insertion and start codon mutation. We also find a GWAS peak for sugar composition spanning deletion polymorphisms in multiple linked invertase genes. MYB transcription factors and invertase are implicated in fruit color and sugar composition in other crops, demonstrating the importance of parallel evolution in the evolutionary diversification of domesticated species