Identification of wheat varieties and glutenin subunits: capillary electrophoresis and computer-assisted interpretation of results

Established and supported under the Australian Government’s Cooperative Research Centre Progra

Sustainable Solvent-Free Selective Oxidation of Benzyl Alcohol Using Ru(0) Supported on Alumina

The selective oxidation of primary alcohols into their corresponding carbonyl compounds is challenging because of the easy over oxidization to acids and esters. The traditional reaction requires large amounts of solvent and oxidant, causing serious environmental issues. Recently, several efforts have been made to transform the reaction into a more sustainable process. Here, we investigated the solvent-free oxidation of benzyl alcohol using air as a green oxidant in the presence of ruthenium supported on alumina and zirconia, thereby meeting atom economy and environmental requirements. The materials were extensively characterized and, in addition to their activity, selectivity, and reusability, the environmental sustainability of the process was assessed according to green chemistry metrics. XRD, TEM, and XPS analyses suggest that the formation of metallic Ru on the support plays a key role in the catalytic activity. Ru supported on alumina, after a reduction treatment, achieves good activity (62% conversion) and a complete selectivity in a very sustainable process (without a solvent and with air as oxidant), as indicated by the very low E-factor value. The formulation is very stable and maintains high activity after recycling

Experimental and Theoretical Investigation of Ion Pairing in Gold(III) Catalysts

The ion pairing structure of the possible species present in solution during the gold(III)-catalyzed hydration of alkynes: [(ppy)Au(NHC)Y]X2 and [(ppy)Au(NHC)X]X [ppy = 2-phenylpyridine, NHC = NHCiPr = 1,3-bis(2,6-di-isopropylphenyl)-imidazol-2-ylidene; NHC = NHCmes = 1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene X = Cl-, BF4-, OTf-; Y = H2O and 3-hexyne] are determined. The nuclear overhauser effect nuclear magnetic resonance (NMR) experimental measurements integrated with a theoretical description of the system (full optimization of different ion pairs and calculation of the Coulomb potential surface) indicate that the preferential position of the counterion is tunable through the choice of the ancillary ligands (NHCiPr, NHCmes, ppy, and Y) in [(ppy)Au(NHC)(3-hexyne)]X2 activated complexes that undergo nucleophilic attack. The counterion can approach near NHC, pyridine ring of ppy, and gold atom. From these positions, the anion can act as a template, holding water in the right position for the outer-sphere attack, as observed in gold(I) catalysts

Cosmological inference including massive neutrinos from the matter power spectrum: biases induced by uncertainties in the covariance matrix

Data analysis from upcoming large galaxy redshift surveys, such as Euclid and DESI will significantly improve constraints on cosmological parameters. To optimally extract the information from these galaxy surveys, it is important to control with a high level of confidence the uncertainty and bias arising from the estimation of the covariance that affects the inference of cosmological parameters. In this work, we are addressing two different but closely related issues: (i) the sampling noise present in a covariance matrix estimated from a finite set of simulations and (ii) the impact on cosmological constraints of the non-Gaussian contribution to the covariance matrix of the power spectrum. We focus on the parameter estimation obtained from fitting the matter power spectrum in real space, using the DEMNUni N-body simulations. Regarding the first issue, we adopt two different approaches to reduce the sampling noise in the precision matrix that propagates in the parameter space: on the one hand using an alternative estimator of the covariance matrix based on a non-linear shrinkage, NERCOME; and on the other hand employing a method of fast generation of approximate mock catalogs, COVMOS. We find that NERCOME can significantly reduce the noise induced on the posterior distribution of parameters, but at the cost of a systematic overestimation of the error bars on the cosmological parameters. We show that using a COVMOS covariance matrix estimated from a large number of realisations (10~000) results in unbiased cosmological constraints. Regarding the second issue, we quantify the impact on cosmological constraints of the non-Gaussian part of the power spectrum covariance purely coming from non-linear clustering. We find that when this term is neglected, both the errors and central values of the estimated parameters are affected for a scale cut \kmax > 0.2\ \invMpc.Comment: 21 pages, 2 appendices, 20 figures. Submitted to A&

Acetate Acetylacetonate Ampy Ruthenium(II) Complexes as Efficient Catalysts for Ketone Transfer Hydrogenation

The mixed acetate acetylacetonate (acac) ruthenium(II) phosphine complexes Ru(OAc)(acac)P2 [P2=(PPh3)2, Ph2P(CH2)4PPh2 (dppb)] were prepared by protonation of Ru(OAc)2(PPh3)2 with acetylacetone in dichloromethane. Reaction of the dppb derivative with 2-(aminomethyl)pyridine (ampy) affords the complex Ru(OAc)(acac)(ampy)(dppb), which converts to [Ru(acac)(ampy)(dppb)](OAc) in toluene at 90 \ub0C. In the former derivative the ampy ligand is monodentate and coordinates through the NH2-moiety. The isolated acac complexes are active catalysts for the transfer hydrogenation of ketones with loadings as low as 0.01 mol%, the ampy having a strong accelerating effect. Several aromatic and aliphatic ketone substrates are converted to their corresponding alcohols, and different electronic influences through substituents on acetophenone are tolerated

Preparation of Neutral trans - Cis [Ru(O2CR)2P2(NN)], Cationic [Ru(O2CR)P2(NN)](O2CR) and Pincer [Ru(O2CR)(CNN)P2] (P = PPh3, P2= diphosphine) Carboxylate Complexes and their Application in the Catalytic Carbonyl Compounds Reduction

The diacetate complexes trans-[Ru(\u3ba1-OAc)2(PPh3)2(NN)] (NN = ethylenediamine (en) (1), 2-(aminomethyl)pyridine (ampy) (2), 2-(aminomethyl)pyrimidine (ampyrim) (3)) have been isolated in 76-88% yield by reaction of [Ru(\u3ba2-OAc)2(PPh3)2] with the corresponding nitrogen ligands. The ampy-type derivatives 2 and 3 undergo isomerization to the thermodynamically most stable cationic complexes [Ru(\u3ba1-OAc)(PPh3)2(NN)]OAc (2a and 3a) and cis-[Ru(\u3ba1-OAc)2(PPh3)2(NN)] (2b and 3b) in methanol at RT. The trans-[Ru(\u3ba1-OAc)2(P2)2] (P2 = dppm (4), dppe (5)) compounds have been synthesized from [Ru(\u3ba2-OAc)2(PPh3)2] by reaction with the suitable diphosphine in toluene at 95 \ub0C. The complex cis-[Ru(\u3ba1-OAc)2(dppm)(ampy)](6) has been obtained from [Ru(\u3ba2-OAc)2(PPh3)2] and dppm in toluene at reflux and reaction with ampy. The derivatives trans-[Ru(\u3ba1-OAc)2P2(NN)] (7-16; NN = en, ampy, ampyrim, 8-aminoquinoline; P2 = dppp, dppb, dppf, (R)-BINAP) can be easily synthesized from [Ru(\u3ba2-OAc)2(PPh3)2] with a diphosphine and treatment with the NN ligands at RT. Alternatively these compounds have been prepared from trans-[Ru(OAc)2(PPh3)2(NN)] by reaction with the diphosphine in MEK at 50 \ub0C. The use of (R)-BINAP affords trans-[Ru(\u3ba1-OAc)2((R)-BINAP)(NN)] (NN = ampy (11), ampyrim (15)) isolated as single stereoisomers. Treatment of the ampy-type complexes 8-15 with methanol at RT leads to isomerization to the cationic derivatives [Ru(\u3ba2-OAc)P2(NN)]OAc (8a-15a; NN = ampy, ampyrim; P2 = dppp, dppb, dppf, (R)-BINAP). Similarly to 2, the dipivalate trans-[Ru(\u3ba1-OPiv)2(PPh3)2(ampy)] (18) is prepared from [Ru(\u3ba2-OPiv)2(PPh3)2] (17) and ampy in CHCl3. The pincer acetate [Ru(\u3ba1-OAc)(CNNOMe)(PPh3)2] (19) has been synthesized from [Ru(\u3ba2-OAc)2(PPh3)2] and HCNNOMe ligand in 2-propanol with NEt3 at reflux. In addition, the dppb pincer complexes [Ru(\u3ba1-OAc)(CNN)(dppb)] (CNN = AMTP (20), AMBQPh (21)) have been obtained from [Ru(\u3ba2-OAc)2(PPh3)2], dppb, and HAMTP or HAMBQPh with NEt3, respectively. The acetate NN and pincer complexes are active in transfer hydrogenation with 2-propanol and hydrogenation with H2 of carbonyl compounds at S/C values of up to 10000 and with TOF values of up to 160000 h-1

Expanded Vandermonde powers and sum rules for the two-dimensional one-component plasma

The two-dimensional one-component plasma (2dOCP) is a system of $N$ mobile particles of the same charge $q$ on a surface with a neutralising background. The Boltzmann factor of the 2dOCP at temperature $T$ can be expressed as a Vandermonde determinant to the power $\Gamma=q^{2}/(k_B T)$. Recent advances in the theory of symmetric and anti-symmetric Jack polymonials provide an efficient way to expand this power of the Vandermonde in their monomial basis, allowing the computation of several thermodynamic and structural properties of the 2dOCP for $N$ values up to 14 and $\Gamma$ equal to 4, 6 and 8. In this work, we explore two applications of this formalism to study the moments of the pair correlation function of the 2dOCP on a sphere, and the distribution of radial linear statistics of the 2dOCP in the plane

One Hundred Years of Observations of the Be Star HDE 245770 (the X-ray Binary A0535+26/V725 Tau): The End of an Active Phase

UBV observations of the X-ray binary system A0535+26/V725 Tau at the Crimean Station of the Sternberg Astronomical Institute in 1980-1998 are presented. Based on our and published data, we analyze the photometric history of the star from 1898.Comment: Translated from Pis'ma Astronomicheskii Zhurnal, Vol. 26, No. 1, 2000, pp. 13-2