Tandem mass spectrometry for the characterisation of sulphated-phosphorylated analogues of the carbohydrate-protein linkage region of proteoglycans

Carbohydrate-protein linkage region of proteoglycans is a key oligosaccharide structure because their sulphated and/or phosphorylated analogues control the biosynthesis of glucosaminoglycans or galactosaminoglycans. Therefore, synthesised sulphated and/or phosphorylated analogues were characterised by tandem mass spectrometry in the negative-ion mode. Results demonstrated that the product ion profile was characterised by glycosidic and cross-ring cleavages depending on the position and the type of the charged group (sulphate, phosphate or carboxylate). When the above compounds were sulphated and phosphorylated, the ion found at m/z 79 was the only one that demonstrated a phosphate group on the structure. The data also suggested that when a sodium cation was present in a sulphated and phosphorylated structure, the phosphate group in most cases was neutralised by the sodium cation, and therefore cleaved off the molecule, while the sulphate group was carrying the negative charge.     

Hydrogen-bond accepting strength of protonated nicotine

Recent crystal structures of nicotine bound to the acetylcholine binding protein (AChBP) ended a long debate confirming that the pyridine nitrogen of nicotine is indeed hydrogen-bonded to receptor residues through a bridging water molecule. Here, we describe the first direct experimental evaluation of the hydrogen-bond affinity of the nicotinium pyridine nitrogen. The equilibrium constant of its association with a phenol is 1 order of magnitude greater than the association of the acetylcholine carbonyl oxygen.     

Lipschitz continuity of state functions in some optimal shaping

We prove local Lipschitz continuity of the solution to the state equation in two kinds of shape optimization problems with constraint on the volume: the minimal shaping for the Dirichlet energy, with no sign condition on the state function, and the minimal shaping for the first eigenvalue of the Laplacian. This is a main first step for proving regularity of the optimal shapes themselves.Received: 11 November 2003, Accepted: 10 May 2004, Published online: 8 February 2005Mathematics Subject Classification (2000): 49Q10, 35R35, 49K20, 35J20     

Divisors,spin sums and the functional equation of the Zeta-Riemann function

Summary Let <InlineEquation ID=IE"1"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"2"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"3"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"4"><EquationSource Format="TEX"><![CDATA[$]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>S_n$, $n=1,2\dots$ be the sequence of partial sums of independent spin random variables. We show that the distribution value of the divisors of $S_n$, is intimately related to the Zeta-Riemann function via the functional equation and Theta elliptic functions.     

Spirophosphoranylation d'α-aminoacides—I : Preparation et tautomerie

New spirophosphoranes have been prepared by reaction of &alpha-aminoacids with tricoordinate phosphorus substrates. In one case, 1i, an equilibrium chain-cycle P^IIIP^v has been observed.     

Spatially homogeneous random evolutions

Spatially homogeneous random evolutions arise in the study of the growth of a population in a spatially homogeneous random environment. The random evolution is obtained as the solution of a bilinear stochastic evolution equation. The main results are concerned with the asymptotic behavior of the solution for large times. In particular, conditions for the existence of a stationary random field are established. Furthermore space-time renormalization limit theorems are obtained which lead to either Gaussian or non-Gaussian generalized processes depending on the case under consideration.     

Atomic-absorption spectrophotometric determination of ultramicro amounts of selenium(IV) and total selenium in sulphuric acid

Summary Ultramicro amounts of selenium in sulphuric acid are determined by a new atomic absorption spectrophotometric method. Selenium(IV) is directly determined ater extraction into toluene with an aromatic o-diamine and addition of nickel(II) prior to atomization; the determination of total selenium (0, IV and VI) needs a treatment of the sample with selected oxidizing and reducing agents.In the studied samples, total selenium (0.003–0.022 g of Se in 1 ml sulphuric acid) is present only in the tetravalent state. The detection limit of the method is 0.003 g of selenium.

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Atomabsorptions-spektralphotometrische Bestimmung von Ultramikromengen Selen(IV) und Gesamtselen in Schwefelsäure

Zusammenfassung Selen(IV) kann direkt bestimmt werden nach Toluolextraktion der mit einem aromatischen o-Diamin behandelten Lösung und Zusatz von Nickel(II). Die Bestimmung von Gesamtselen (0, IV, VI) erfordert eine Vorbehandlung mit Perchlor- bzw. Salpetersäure und Wasserstoffperoxid. Die Nachweisgrenze des Verfahrens beträgt 0,003 g Se. In den untersuchten Proben war das Gesamtselen (0,003–0,022 g/ml) nur als Se(IV) vorhanden.