The European Chemical Society (EuChemS)

The European Chemical Society (EuChemS) coordinates the work of almost all the European Chemical Societies. As an organization, it provides an independent and authoritative voice on all matters relating to chemistry, and try to place chemistry at the heart of policy in Europe. Furthermore, EuChemS seeks to develop its members through various activities, workshops and awards. Particularly, EuChemS has fostered growth in its young members through the European Young Chemists′ Network. Beyond Europe, EuChemS has collaborated with various organizations in bringing chemistry out of the lab and into society in building a sustainable future for everyone.PostprintPeer reviewe

Determination of the Baryon Density from Large Scale Galaxy Redshift Surveys

We estimate the degree to which the baryon density, $\Omega_{b}$, can be determined from the galaxy power spectrum measured from large scale galaxy redshift surveys, and in particular, the Sloan Digital Sky Survey. A high baryon density will cause wiggles to appear in the power spectrum, which should be observable at the current epoch. We assume linear theory on scales $\geq 20h^{-1}Mpc$ and do not include the effects of redshift distortions, evolution, or biasing. With an optimum estimate of $P(k)$ to $k\sim 2\pi/(20 h^{-1} Mpc)$, the $1 \sigma$ uncertainties in $\Omega_{b}$ are roughly 0.07 and 0.016 in flat and open ($\Omega_{0}=0.3$) cosmological models, respectively. This result suggests that it should be possible to test for consistency with big bang nucleosynthesis estimates of $\Omega_{b}$ if we live in an open universe.Comment: 23 Pages, 10 Postscript figure

Magic of alpha : the chemistry of a remarkable bidentate phosphine, 1,2-bis(di-tert-butylphosphinomethyl)benzene

We thank the Fonds der Chemischen Industrie for a Kekulé Fellowship for a studentship and the Deutsche Forschungsgemeinschaft (DFG, project number 424535516) for support (J.V.). We are also very grateful to Lucite International for funding the work in St Andrews that is contained in this review.The bidentate phosphine ligand 1,2-bis(di-tert-butylphosphinomethyl)benzene (1,2-DTBPMB) has been reported over the years as being one of, if not the, best ligands for achieving the alkoxycarbonylation of various unsaturated compounds. Bonded to palladium, the ligand provides the basis for the first step in the commercial (Alpha) production of methyl methacrylate as well as very high selectivity to linear esters and acids from terminal or internal double bonds. The present review is an overview covering the literature dealing with the 1,2-DTBPMB ligand: from its first reference, its catalysis, including the alkoxycarbonylation reaction and its mechanism, its isomerization abilities including the highly selective isomerizing methoxycarbonylation, other reactions such as cross-coupling, recycling approaches, and the development of improved, modified ligands, in which some tert-butyl ligands are replaced by 2-pyridyl moieties and which show exceptional rates for carbonylation reactions at low temperatures.PostprintPeer reviewe

Synthesis of pharmaceutical drugs from cardanol derived from cashew nut shell liquid

Authors thank the EPSRC for the critical mass grant ‘Clean Catalysis for Sustainable Development’ (EP/J018139/1), Sasol Technology, UK for a case studentship (Y. S.).Cardanol from cashew nut shell liquid extracted from cashew nut shells was successfully converted into various useful pharmaceutical drugs, such as norfenefrine, rac-phenylephrine, etilefrine and fenoprofene. 3-Vinylphenol, the key intermediate for the synthesis of these drugs, was synthesised from cardanol by ethenolysis to 3-non-8-enylphenol followed by isomerising ethenolysis. The metathesis reaction worked very well using DCM, but the greener solvent, 2-methyl tetrahydrofuran, also gave very similar results. Hydroxyamination of 3-vinylphenol with an iron porphyrin catalyst afforded norfenefrine in over 70% yield. Methylation and ethylation of norfenefrine afforded rac-phenylephrine and etilefrine respectively. A sequence of C–O coupling, isomerising metathesis and selective methoxycarbonylation afforded fenoprofene in good yield. A comparison of the routes described in this paper with some standard literature syntheses of 3-vinylphenol and of the drug molecules shows significant environmental advantages in terms of precursors, yields, number of steps, conditions and the use of catalysts. The Atom Economy of our processes is generally similar or significantly superior to those of the literature processes mainly because the side products produced during synthesis of 3-vinylphenol (1-octeme, 1,4-cyclohexadiene and propene) are easily separable and of commercial value, especially as they are bio-derived. The E Factor for the production of 2-vinylphenol by our process is also very low compared with those of previously reported syntheses.Publisher PDFPeer reviewe

Lake-size dependency of wind shear and convection as controls on gas exchange

High-frequency physical observations from 40 temperate lakes were used to examine the relative contributions of wind shear (u*) and convection (w*) to turbulence in the surface mixed layer. Seasonal patterns of u* and w* were dissimilar; u* was often highest in the spring, while w * increased throughout the summer to a maximum in early fall. Convection was a larger mixed-layer turbulence source than wind shear (u */w*-1 for lakes* and w* differ in temporal pattern and magnitude across lakes, both convection and wind shear should be considered in future formulations of lake-air gas exchange, especially for small lakes. © 2012 by the American Geophysical Union.Jordan S. Read, David P. Hamilton, Ankur R. Desai, Kevin C. Rose, Sally MacIntyre, John D. Lenters, Robyn L. Smyth, Paul C. Hanson, Jonathan J. Cole, Peter A. Staehr, James A. Rusak, Donald C. Pierson, Justin D. Brookes, Alo Laas, and Chin H. W

A Global lake ecological observatory network (GLEON) for synthesising high-frequency sensor data for validation of deterministic ecological models

A Global Lake Ecological Observatory Network (GLEON; www.gleon.org) has formed to provide a coordinated response to the need for scientific understanding of lake processes, utilising technological advances available from autonomous sensors. The organisation embraces a grassroots approach to engage researchers from varying disciplines, sites spanning geographic and ecological gradients, and novel sensor and cyberinfrastructure to synthesise high-frequency lake data at scales ranging from local to global. The high-frequency data provide a platform to rigorously validate processbased ecological models because model simulation time steps are better aligned with sensor measurements than with lower-frequency, manual samples. Two case studies from Trout Bog, Wisconsin, USA, and Lake Rotoehu, North Island, New Zealand, are presented to demonstrate that in the past, ecological model outputs (e.g., temperature, chlorophyll) have been relatively poorly validated based on a limited number of directly comparable measurements, both in time and space. The case studies demonstrate some of the difficulties of mapping sensor measurements directly to model state variable outputs as well as the opportunities to use deviations between sensor measurements and model simulations to better inform process understanding. Well-validated ecological models provide a mechanism to extrapolate high-frequency sensor data in space and time, thereby potentially creating a fully 3-dimensional simulation of key variables of interest

The clustering of galaxies in the SDSS-III Baryon Oscillation Spectroscopic Survey: Analysis of potential systematics

We analyze the density field of galaxies observed by the Sloan Digital Sky Survey (SDSS)-III Baryon Oscillation Spectroscopic Survey (BOSS) included in the SDSS Data Release Nine (DR9). DR9 includes spectroscopic redshifts for over 400,000 galaxies spread over a footprint of 3,275 deg^2. We identify, characterize, and mitigate the impact of sources of systematic uncertainty on large-scale clustering measurements, both for angular moments of the redshift-space correlation function and the spherically averaged power spectrum, P(k), in order to ensure that robust cosmological constraints will be obtained from these data. A correlation between the projected density of stars and the higher redshift (0.43 < z < 0.7) galaxy sample (the `CMASS' sample) due to imaging systematics imparts a systematic error that is larger than the statistical error of the clustering measurements at scales s > 120h^-1Mpc or k < 0.01hMpc^-1. We find that these errors can be ameliorated by weighting galaxies based on their surface brightness and the local stellar density. We use mock galaxy catalogs that simulate the CMASS selection function to determine that randomly selecting galaxy redshifts in order to simulate the radial selection function of a random sample imparts the least systematic error on correlation function measurements and that this systematic error is negligible for the spherically averaged correlation function. The methods we recommend for the calculation of clustering measurements using the CMASS sample are adopted in companion papers that locate the position of the baryon acoustic oscillation feature (Anderson et al. 2012), constrain cosmological models using the full shape of the correlation function (Sanchez et al. 2012), and measure the rate of structure growth (Reid et al. 2012). (abridged)Comment: Matches version accepted by MNRAS. Clarifications and references have been added. See companion papers that share the "The clustering of galaxies in the SDSS-III Baryon Oscillation Spectroscopic Survey:" titl

The clustering of galaxies in the SDSS-III Baryon Oscillation Spectroscopic Survey: measurements of the growth of structure and expansion rate at z=0.57 from anisotropic clustering

We analyze the anisotropic clustering of massive galaxies from the Sloan Digital Sky Survey III Baryon Oscillation Spectroscopic Survey (BOSS) Data Release 9 (DR9) sample, which consists of 264,283 galaxies in the redshift range 0.43 < z < 0.7 spanning 3,275 square degrees. Both peculiar velocities and errors in the assumed redshift-distance relation ("Alcock-Paczynski effect") generate correlations between clustering amplitude and orientation with respect to the line-of-sight. Together with the sharp baryon acoustic oscillation (BAO) standard ruler, our measurements of the broadband shape of the monopole and quadrupole correlation functions simultaneously constrain the comoving angular diameter distance (2190 +/- 61 Mpc) to z=0.57, the Hubble expansion rate at z=0.57 (92.4 +/- 4.5 km/s/Mpc), and the growth rate of structure at that same redshift (d sigma8/d ln a = 0.43 +/- 0.069). Our analysis provides the best current direct determination of both DA and H in galaxy clustering data using this technique. If we further assume a LCDM expansion history, our growth constraint tightens to d sigma8/d ln a = 0.415 +/- 0.034. In combination with the cosmic microwave background, our measurements of DA, H, and growth all separately require dark energy at z > 0.57, and when combined imply \Omega_{\Lambda} = 0.74 +/- 0.016, independent of the Universe's evolution at z<0.57. In our companion paper (Samushia et al. prep), we explore further cosmological implications of these observations.Comment: 19 pages, 11 figures, submitted to MNRAS, comments welcom

Cosmological Constraints from the Clustering of the Sloan Digital Sky Survey DR7 Luminous Red Galaxies

We present the power spectrum of the reconstructed halo density field derived from a sample of Luminous Red Galaxies (LRGs) from the Sloan Digital Sky Survey Seventh Data Release (DR7). The halo power spectrum has a direct connection to the underlying dark matter power for k <= 0.2 h/Mpc, well into the quasi-linear regime. This enables us to use a factor of ~8 more modes in the cosmological analysis than an analysis with kmax = 0.1 h/Mpc, as was adopted in the SDSS team analysis of the DR4 LRG sample (Tegmark et al. 2006). The observed halo power spectrum for 0.02 < k < 0.2 h/Mpc is well-fit by our model: chi^2 = 39.6 for 40 degrees of freedom for the best fit LCDM model. We find \Omega_m h^2 * (n_s/0.96)^0.13 = 0.141^{+0.009}_{-0.012} for a power law primordial power spectrum with spectral index n_s and \Omega_b h^2 = 0.02265 fixed, consistent with CMB measurements. The halo power spectrum also constrains the ratio of the comoving sound horizon at the baryon-drag epoch to an effective distance to z=0.35: r_s/D_V(0.35) = 0.1097^{+0.0039}_{-0.0042}. Combining the halo power spectrum measurement with the WMAP 5 year results, for the flat LCDM model we find \Omega_m = 0.289 +/- 0.019 and H_0 = 69.4 +/- 1.6 km/s/Mpc. Allowing for massive neutrinos in LCDM, we find \sum m_{\nu} < 0.62 eV at the 95% confidence level. If we instead consider the effective number of relativistic species Neff as a free parameter, we find Neff = 4.8^{+1.8}_{-1.7}. Combining also with the Kowalski et al. (2008) supernova sample, we find \Omega_{tot} = 1.011 +/- 0.009 and w = -0.99 +/- 0.11 for an open cosmology with constant dark energy equation of state w.Comment: 26 pages, 19 figures, submitted to MNRAS. The power spectrum and a module to calculate the likelihoods is publicly available at http://lambda.gsfc.nasa.gov/toolbox/lrgdr/ . v2 fixes abstract formatting issu

Synthesis of bifunctional monomers by the palladium-catalyzed carbonylation of cardanol and its derivatives

The authors thank the Royal Society Leverhulme Africa Program for funding this project.A 1,2-bis(di-tert-butylphosphinomethyl)benzene-modified palladium catalyst has been used to synthesize bifunctional monomers of different chain lengths from cardanol. Short-chain derivatives of cardanol, such as (E)-3-(dodec-8-enyl)phenol; HOPhC12-ene, (E)-3-(undec-8-enyl)phenol; HOPhC11-ene, (E)-3-(dec-8-enyl)phenol; HOPhC10-ene, and 3-(non-8-enyl)phenol; HOPhC9-ene, were synthesized by the metathesis of cardanol with symmetrical internal alkenes. These derivatives were methoxycarbonylated to produce monomers with different chain lengths such as methyl-16-(3-hydroxyphenyl)hexadecanoate; HOPhC15COOMe, methyl-13-(3-hydroxyphenyl)tridecanoate; HOPhC12COOMe, methyl-12-(3-hydroxyphenyl)dodecanoate; HOPhC11COOMe, methyl-11-(3-hydroxyphenyl)undecanoate; HOPhC10COOMe, and methyl-10-(3-hydroxyphenyl)decanoate; HOPhC9COOMe, respectively. Polymerization of the synthesized monomers produced oligomers that consist of up to seven monomer units as confirmed by MALDI-TOF-MS. Lactone formation was also observed in some cases under polymerization conditions.PostprintPostprintPeer reviewe