Synthesis of a 56 component library of sugar beta-peptides

Many biological processes of vital importance are triggered by the molecular recognition of small carbohydrate units by proteins and receptors thus leading to the belief that carbohydrates could act as candidates for the design of new drugs. We have developed a new useful synthetic approach, which can be applied in a combinatorial manner, giving access to 1,1-di-substituted pyrans projecting amide side chains in both the alpha- and beta-directions. Thus, treatment of the readily accessible hemiketal (1) with TFA followed by trimethylsilyl trifluoromethanesulfonate (TMSOTf) in the presence of a nitrile gives dihydrooxazinones (2) via a new type of modified intramolecular Ritter reaction. The dihydrooxazinones (2) can either be isolated or used directly in reactions with a broad variety of amines. Final deprotection furnishes the 1,1-di-substituted sugar beta-peptides having the general structure (4).     

A Study of picosecond dehalogenation of chlorobenzene anions in liquids by positronium inhibition measurements

Radiation chemistry and results of Ps yields indicate that the following processes occur in the positron spur in solution of halogen-substituted hydrocarbons, RX_n: e⁺ + e^? → Ps, e^? + RX _n → (RX_n)^? → RX_n?1 + X^?, e⁺ + (RX_n)^? → Ps + RX_n, e⁺ + X^? → [X^?, e⁺]. Hence the trapped electron can form Ps only if (RX _n)^? is stable or has a lifetime that is longer than o comparable to the Ps formation time. Previous studies have shown that some of the strongly chlorinated benzenes (n = 4.5 give reasonable inhibition in benzene but not in linear hydrocarbons. The reason is very probably that the dechlorination time is much shorter in benzene than in saturated hydrocarbons because Cl^? is more strongly solvated in benzene than in non-aromatic hydrocarbons. To test those ideas further we have begun detailed studies of solutions of the possible “intermediate” inhibitors, viz. 1,2,3,5- and 1,2,4,5-C₆H₂Cl₄, in mixtures of C₆H₆/C₆H₁₄ different methyl-substituted benzene aniline, anisole, dioxane and ethylbenzene. The results are discussed and interpreted in terms of the spur model. The Ps inhibition efficiency of the two isomeric forms of tetrachlorobenzene studied, appears most probably to depend on intramolecular electron transfer with subsequent dehalogenation of the molecular anion on a picosecond timescale. The divergence in inhibitor efficiency obtained for the chlorobenzenes when dissolved in aromatic solvents compared to the same solutes when dissolved in a saturated alkane appears most probably to be caused by complex formation between the initially formed chlorobenzene anion and benzene molecules, which permits a rapid relaxation of the molecular anion with subsequent bond stretching and expulsion of the chloride anion.     

Thermodynamic properties of a two-site Hubbard model with orbital degeneracy

Exact numerical solutions are obtained for a two-site doubly degenerate Hubbard model with 2, 3 or 4 electrons to study the effect of intra-atomic exchange interaction on the ground state and the thermodynamic properties. Some properties of macroscopic systems are reproduced qualitatively. The condition of having the Hamiltonian rotationally invariant in spin space gets important with increasing electron density.     

Phase transitions in lattice gas models for water

Water-like lattice gases on the triangular and body-centered cubic lattices are investigated. Molecules may reside on the lattice sites in either of two possible orientations, a hydrogen bond being formed between molecules on neighboring sites if they have the proper orientation with respect to one another. For a range of chemical potential at sufficiently low temperatures, the models are shown to have an ordered phase consisting of an open, hydrogen-bonded, icelike structure. The models are shown to be transitionfree at sufficiently high temperature, indicating the existence of a critical point.Research supported in part by the U.S. National Science Foundation, Grant CHE-7726177, and by The Robert A. Welch Foundation, Grant P-446.     

Intraoperative contrast-enhanced MR-imaging as predictor of tissue damage during cryoablation of porcine liver

This study evaluate intraoperative Magnetic Resonance Imaging (MRI) as predictor of tissue damage following cryoablation of porcine liver with and without concomitant hepatic vascular inflow occlusion.Inflow occlusion was used during freezing in 6 of 12 pigs included. The volumes of the procedural ice-balls were estimated from MR images. Immediately after thawing contrast (MnDPDP) enhanced MRI was performed to estimate the volume of the cryolesion. Four days after ablation MRI was repeated of the in-vivo and the ex-vivo liver. Photography was performed of the sliced liver specimens to estimate the volumes of the lesions. The intraoperative volume of the cryolesion as shown by contrast enhanced MRI corresponded well to the ice-ball volume for lesions made without vascular occlusion (difference 0.3 +/- 0.9 cm(3), p = 0.239). For lesions made during occlusion the volume of the intraoperative cryolesion was larger than the corresponding ice-ball (difference 7.5 +/- 3.3 cm(3), p = 0.003). The volume of the cryolesions as estimated from histopathology four days after freezing and contrast enhanced MRI immediately after freezing corresponded well for lesions made with (difference -2.6 +/- 4.5 cm(3), p = 0.110) and without vascular occlusion (difference -0.5 +/- 2.3 cm(3), p = 0.695).Intraoperative MnDPDP-enhanced MRI of the cryolesion is predictive of the tissue damage induced during cryoablation of porcine liver. The procedural ice-ball is not, if induced during inflow occlusion.     

Directional synthesis of a dye-linked conducting homopolymer

We report a new synthesis of a 10,20-diphenyl-5,15-bis(4-cyanophenyl)porphyrin (1) and its reduction to give 10,20-diphenyl-5,15-bis(4-formylphenyl)porphyrin (2). When the conducting polymer poly(2',5'-dioctyl-4,4' '-terphenylenecyanovinylene) was prepared in the presence of 2, we obtained a three-domain structure, compound 3, consisting of two homopolymer blocks (J domains) with the porphyrin dye molecule (P domain) in the middle. The JPJ assembly was subjected to photophysical studies where we showed that the J domain could serve as a light-harvesting antenna for the P domain.     

Weyl-Heisenberg frames for subspaces of

A Weyl-Heisenberg frame

for allows every function to be written as an infinite linear combination of translated and modulated versions of the fixed function . In the present paper we find sufficient conditions for to be a frame for , which, in general, might just be a subspace of . Even our condition for to be a frame for is significantly weaker than the previous known conditions. The results also shed new light on the classical results concerning frames for , showing for instance that the condition A>0$">is not necessary for to be a frame for . Our work is inspired by a recent paper by Benedetto and Li, where the relationship between the zero-set of the function and frame properties of the set of functions is analyzed.

     

Finite-dimensional approximation of the inverse frame operator

A frame in a Hilbert space allows every element in to be written as a linear combination of the frame elements, with coefficients called frame coefficients. Calculations of those coefficients and many other situations where frames occur, requires knowledge of the inverse frame operator. But usually it is hard to invert the frame operator if the underlying Hilbert space is infinite dimensional. In the present paper we introduce a method for approximation of the inverse frame operator using finite subsets of the frame. In particular this allows to approximate the frame coefficients (even inl ²) using finite-dimensional linear algebra. We show that the general method simplifies in the important cases of Weil-Heisenberg frames and wavelet frames.