Quantification of carbohydrate structures in size fractionated aquatic humic substances by two-dimensional nuclear magnetic resonance

Two-dimensional phase sensitive C,H correlation spectra were successfully applied to the quantification of carbohydrate substructures in aquatic humic substance (HS) fractions obtained by tangential flow multistage ultrafiltration (TFMSTUF) of a selected bog water HS (HO13, German Research Program DFG-ROSIG) as well as a river HS (Suwannee River Fulvic Acid Reference of the International Humic Substances Society, IHSS). It turns out that after size fractionation the HS samples give very well resolved C,H-correlation spectra which offer a great potential for substructure quantification. Details of the combined substructure quantification technique, novel in HS characterization, are presented. The results of the combined procedure point out that carbohydrate moieties predominantly occur in higher molecular mass fractions (> 10 kDa) of isolated HS.     

Ueber die Diffusion der Kolloide I

Ohne Zusammenfassungnach Versuchen von H. Kasarnowski.     

Numerical Kähler-Einstein Metric on the Third del Pezzo

The third del Pezzo surface admits a unique Kähler-Einstein metric, which is not known in closed form. The manifold’s toric structure reduces the Einstein equation to a single Monge-Ampère equation in two real dimensions. We numerically solve this nonlinear PDE using three different algorithms, and describe the resulting metric. The first two algorithms involve simulation of Ricci flow, in complex and symplectic coordinates respectively. The third algorithm involves turning the PDE into an optimization problem on a certain space of metrics, which are symplectic analogues of the “algebraic” metrics used in numerical work on Calabi-Yau manifolds. Our algorithms should be applicable to general toric manifolds. Using our metric, we compute various geometric quantities of interest, including Laplacian eigenvalues and a harmonic (1,1)-form. The metric and (1,1)-form can be used to construct a Klebanov-Tseytlin-like supergravity solution.     

Hyperfine Field in Ferromagnetic CoPd Alloys

The magnetic hyperfine interaction of ⁶⁰Co in the completely miscible alloy Co _x Pd_1−x was investigated for different values of x by measuring the nuclear orientation of ⁶⁰Co as function of temperature and by nuclear magnetic resonance of the oriented ⁶⁰Co nuclei. A broad resonance signal of Gaussian shape could be observed down to x=60%. The dependence of the mean magnetic hyperfine field on the Co concentration was observed to be linear very similar to that of experimental values of the magnetic moment per atom in the literature. The magnetic hyperfine field and its broad distribution are discussed in a simple model with RKKY interaction. This revised version was published online in September 2006 with corrections to the Cover Date.     

Synthesis, structure, and reactivity of closo-2,3,4,5,6,7,8,9,10,11-decahydroxy-1,12-bis(sulfonic acid)-1,12-dicarbadodecaborane(12).

The reaction of closo-1,12-bis(lithio)-1,12-dicarbadodecaborane(12) (1,12-bis(lithio)-p-carborane) with SO(2) formed closo-1,12-bis(lithiosulfinato)-p-carborane (10) in nearly quantitative yield. The latter was converted to closo-1,12-bis(sulfinic acid)-p-carborane (13) via H(+)-exchange. The corresponding 1,12-bis(sulfonic acid) derivative of p-carborane (12) was obtained in high yield by treating 10 with SO(2)Cl(2) and subsequent AlCl(3) mediated hydrolysis of the closo-1,12-bis(chlorosulfonyl)-p-carborane intermediate. The exhaustive oxidation of 12 in hot aqueous H(2)O(2) (30%) afforded B-decahydroxy-1,12-bis(sulfonic acid)-p-carborane (15) in 40% yield. As a byproduct, closo-B-decahydroxy-1-sulfonic acid-p-carborane (14) was formed. Both 14 and 15 were also obtained from the hydroxylation of 10 and 13. Compound 14 was obtained directly in 88% yield by heating 1-sulfinic acid-p-carborane (17) in H(2)O(2) (30%). Compound 17 was synthesized from diphenylmethylsilyl-protected p-carborane by using the method employed in the synthesis of 13. The X-ray structures of 15, its disodium salt, and its dipotassium salt are presented and discussed. Exhaustive methylation of 15 with methyl triflate furnishes closo-B-decamethoxy-1,12-bis(methyl sulfonate)-p-carborane (20). The characterization of closomer 20 also includes its crystal structure determination.     

A New Two-Dimensional Pulse Sequence for T2* Measurements of Protons in C Isotopomers

A new two-dimensional pulse sequence for T₂* measurement of protons directly coupled to ¹³C spins is proposed. The sequence measures the tranverse relaxation time of heteronuclear proton single-quantum coherence under conditions of free precession and is therefore well suited to evaluate relaxation losses of proton magnetization during preparation delays of heteronuclear pulse experiments in analytical NMR. The relevant part of the pulse sequence can be inserted as a “building block” into any direct or inverse detecting H,C correlation pulse sequence if proton spin–spin relaxation is to be investigated. In this contribution, the building block is inserted into a HETCOR as well as into a HMQC pulse sequence. Experimental results for the HETCOR-based sequence are given.     

Fenchel Duality Theory and a Primal-Dual Algorithm on Riemannian Manifolds

Foundations of Computational Mathematics - This paper introduces a new notion of a Fenchel conjugate, which generalizes the classical Fenchel conjugation to functions defined on Riemannian...