NMR and EPR structural delineation of copper(II) complexes formed by kanamycin A in water

The complexes formed by kanamycin A at three different pH values (5.5, 7.4 and 12.0) were investigated by NMR and EPR spectroscopy. Paramagnetic relaxation contributions to proton relaxation rates were measured using a combination of the TOCSY sequence with the inversion recovery experiment in order to gain signal resolution in the bulk region. Measured contributions were converted into distances and used for structural determination by restrained simulated annealing where all possible chair and boat conformations of the rings were taken into account. The interaction of the Cu(II) ion with the nitrogen of the C ring is apparent at all pH values. At higher pH also the amino group of ring A starts to be involved in the metal coordination sphere. This is accompanied by a switch in conformation of ring C. Structures are consistent with the involvement in the coordination sphere either of the 2' or 4' hydroxyl oxygens at pH 5.5 and the 5 and the 6' hydroxyl oxygens (or the ring oxygen) at pH 12.0.     

Newton-Like Iteration Based on a Cubic Polynomial for Structured Matrices

We recall Newtons iteration for computing the inverse or Moore–Penrose generalized inverse of a matrix. Then we specialize this approach to the case of structured matrices where all input, output and intermediate auxiliary matrices are represented in a compressed form, via their short displacement generators. We design a new Newton-like iteration based on a cubic polynomial and show its effectiveness by some numerical experiments for matrices from the Toeplitz-like class and the Cauchy-like class.     

Γ-Limit of Periodic Obstacles

We compute the -limit of a sequence obstacle functionals in the case of periodic obstacles.     

Numerical Representations of Interval Orders

In the framework of the analysis of orderings whose associated indifference relation is not necessarily transitive, we study the structure of an interval order and its representability through a pair of real-valued functions. We obtain a list of characterizations of the existence of a representation, showing that the three main techniques that have been used in the literature to achieve numerical representations of interval orders are indeed equivalent.     

A free boundary problem in an absorbing porous material with saturation dependent permeability

We prove a well posedness result for a free boundary problem describing the filtration of an incompressible viscous fluid in a porous medium containing water absorbing granules.?The location of the wetting front (the free boundary) is described by a Stefan like problem for a parabolic equation which is coupled with an hyperbolic equation describing the absorption kinetic of the granules. Received December 1999     

Enantiopure α-imino glyoxylate: a versatile substrate for the spontaneous asymmetric synthesis of unnatural hydroxyaryl glycinates

A novel synthesis of useful enantiomerically pure arylglycinates via spontaneous reaction between phenol or naphthol derivatives and enantiopure α-imino glyoxylate in the absence of an acid catalyst is reported. A library of enantiopure substituted phenol or naphthol glycinates was obtained in good yields and high diastereoselectivities. Diastereoisomerically pure aryl glycinates were obtained by direct flash chromatography separation of the crude reaction mixture. The free OH moiety of the phenols or naphthols contributed to the activation of the imino group to form an intermolecular hydrogen bond and promoted the reaction in the absence of an acid catalyst, as shown in the transition state reported. The diastereoselectivity is due to thermodynamic control in the addition step.     

Gradient bounds for minimizers of free discontinuity problems related to cohesive zone models in fracture mechanics

In this note we consider a free discontinuity problem for a scalar function, whose energy depends also on the size of the jump. We prove that the gradient of every smooth local minimizer never exceeds a constant, determined only by the data of the problem.     

A highly efficient stereocontrolled synthesis of (S)-2′,6′-dimethyltyrosine [(S)-DMT]

A new, practical and very convenient stereocontrolled synthesis of (S)-2′,6′-dimethyltyrosine [(S)-Dmt] 4 was accomplished in a good yield, starting from the chiral synthon 1,4-N,N-[(S)-phenylethyl]-piperazine-2,5-dione 1. The procedure, which is an extension of our original strategy and occurs with a high level of stereoselectivity (>98%), is simple and inexpensive allowing us to prepare the unnatural α-aminoacid (S)-Dmt also on a multi-gram scale.     

Continuous Utility Representation Theorems in Arbitrary Concrete Categories

In this paper the continuous utility representation problem will be discussed in arbitrary concrete categories. In particular, generalizations of the utility representation theorems of Eilenberg, Debreu and Estévez and Hervés will be presented that also hold if the codomain of a utility function is an arbitrary totally ordered set and not just the real line. In addition, we shall prove and apply a general result on the characterization of structures that have the property that every continuous total preorder has a continuous utility representation. Finally, generalizations of the utility representation theorems of Debreu and Eilenberg will be discussed that are valid if we consider arbitrary binary relations and allow a utility function to have values in an arbitrary totally ordered set.