Isosteres of peptides: boron analogs as dipolar forms of α‐amino acids – a theoretical study

Modification of peptides to produce peptidomimetics is of great interest, with the aim of designing potent, selective, and metabolically stable analogs having certain conformational properties. Organoboranes have been reported in the literature with a wide range of therapeutic applications. One of the therapeutically important class of molecules is amine‐carboxyboranes derived from amino acids by replacement of the Cα atom of an amino acid/peptide by boron. The conformational preferences of these peptides, with respect to backbone ω, ?, and ψ torsion angles, have been investigated by theoretical calculations. The amide bond in these molecules has the same geometry in the ground and transition states as the natural peptides. However, the boron isosteres of glycine and alanine peptides are less structured than their natural derivatives, but are distinguished by structures with a positive value for the ? angle, which is normally disfavored for natural peptides. This property could be used to build peptides with a geometry not usually seen in natural peptides. Copyright © 2007 John Wiley & Sons, Ltd.     

Pattern Search Method for Discrete <Emphasis Type="Italic">L</Emphasis><Subscript>1</Subscript>–Approximation

We propose a pattern search method to solve a classical nonsmooth optimization problem. In a deep analogy with pattern search methods for linear constrained optimization, the set of search directions at each iteration is defined in such a way that it conforms to the local geometry of the set of points of nondifferentiability near the current iterate. This is crucial to ensure convergence. The approach presented here can be extended to wider classes of nonsmooth optimization problems. Numerical experiments seem to be encouraging. This work was supported by M.U.R.S.T., Rome, Italy.     

The spectrum of BSA(v, 3, λ; α) with α = 2,3

In this article, a kind of auxiliary design BSA^* for constructing BSAs is introduced and studied. Two powerful recursive constructions on BSAs from 3‐IGDDs and BSA^*s are exploited. Finally, the necessary and sufficient conditions for the existence of a BSA(v, 3, λ; α) with α = 2, 3 are established. © 2006 Wiley Periodicals, Inc. J Combin Designs 15: 61–76, 2007     

Characterization of reduced iso‐α‐acids derived from hops (Humulus lupulus) by NMR

Reduced forms of iso‐α‐acids (isohumulones), used in modern beer brewing were separated and characterized by ¹H and ¹³C NMR spectroscopy. Components from mixtures of rho‐iso‐α‐acids, tetrahydro‐iso‐α‐acids, and hexahydro‐iso‐α‐acids were isolated using high‐performance liquid chromatography (HPLC) and analyzed by use of one‐ and two‐dimensional NMR experiments. The data presented assign the identities of the main peaks in the HPLC traces for the reduced iso‐α‐acids. Previous tentative assignments regarding the cis and trans configurations and the structures of the acyl residues of the reduced iso‐α‐acids were confirmed and extensive NMR assignments were made. Furthermore, the previously unknown stereochemistry in the C‐4 side‐chain of the rho‐ and hexahydro‐iso‐α‐acids was assigned. Copyright © 2003 John Wiley & Sons, Ltd.     

On the Patterson–Sullivan Measure for Geometrically Finite Groups Acting on Complex or Quaternionic Hyperbolic Space

The goal of this paper is to provide a tool, the Global Measure Formula, that will facilitate the study of the limit set of discrete geometrically finite groups of isometries of the rank one symmetric spaces. We consider the shadow of a ball from a fixed reference point onto the boundary, and prove a formula that describes the measure of the shadow in terms of the center of the shadowed ball, generalizing a result from real hyperbolic geometry.     

A Nonlinear Drift - Diffusion System with Electric Convection Arising in Electrophoretic and Semiconductor Modeling

A multi-dimensional transient drift-diffusion model for (at most) three charged particles, consisting of the continuity equations for the concentrations of the species and the Poisson equation for the electric potential, is considered. The diffusion terms depend on the concentrations. Such a system arises in electrophoretic modeling of three species (neutrally, positively and negatively charged) and in semiconductor theory for two species (positively charged holes and negatively charged electrons). Diffusion terms of degenerate type are also possible in semiconductor modeling. For the initial boundary value problem with mixed Dirichlet - Neumann boundary conditions and general reaction rates, a global existence result is proved. Uniqueness of solutions follows in the Dirichlet boundary case if the diffusion terms are uniformly parabolic or if the initial and boundary densities are strictly positive. Finally, we prove that solutions exist which are positive uniformly in time and globally bounded if the reaction rates satisfy appropriate growth conditions.     

Theoretical study of cyclization of 2′-hydroxychalcone

The isomerization mechanism of 2′(OH)chalcone (1) in flavanone (2) was studied. The calculations were performed with the semiempirical method AM1, using totally optimized molecular geometries. A 6-step mechanism including several equilibrium states was proposed. It was concluded that: (a) At the conformational equilibrium of 1 there could be 43.9% of s-cis conformer; (b) The acid dissociation of 1 trans-s-trans is considerable; (c) The E_E, ΔH_f and net charges show that the rotation of ring A of 1 and the formation of ring C of 2 occurs without greater impairments; (d) Although the keto structure is the most stable one, the enolate of 2 is present in the reaction medium; (e) The conversion of enol of 2 in the keto form would be the limiting step of the analyzed isomerization rate.     

Quantization of collective regular structures of particles

The theory of many-body systems constitutes one of the most complex part of quantum mechanics. Closed results are not readily available and approximations become extremely involved. It is, therefore, of considerable interest that the quantization of certain simple collective motions of particles can describe the energies of atoms, nuclei and particle models rather well. We describe here the most elementary examples of such structures.Dedicated to H. Walther, a great scientist and who demonstrated among many other things the regular shapes of atomic particles, the subject of this essay     

聚醚醚酮链结构与反应的模型化合物的量子化学研究

利用ＡＭ１方法对聚醚醚酮模型化合物全优化，结果为：芳环平均相互扭转角为３３．０度，桥键角１１７．０－１１８．０度，其分子结构拓扑图形表明：所有苯环（核）为平面构型，但其内角扭曲；其氢原子对苯环构型无实质性贡献，在更长链的计算中，冻结苯核与氢原子也得出满意结果，根据Ｍｕｌｌｉｋｅｎ键序与电荷讨论了醚交换与磺化反应。