Lipscomb's space

It is known that Lipscomb's space can be imbedded in Hilbert's space . Let be the imbedded version of endowed with the -induced topology. We show how to construct as the attractor of an iterated function system containing an infinite number of affine transformations of . In this way we answer an open question of J.C. Perry.

     

Structural and dynamical characterization of poly-gamma-glutamic acid-based cross-linked nanoparticles

This work describes the formation of water-soluble hydrophilic nanoparticles from biosynthetic poly-γ-glutamic acid (PGA). Nanoparticles were formed by cross-linking using 2,2′-(ethylenedioxy) diethylamine in the presence of water-soluble carbodiimide. The structure was determined by nuclear magnetic resonance spectroscopy and the particle size by transmission electron microscopy (TEM), size exclusion chromatography (SEC), and dynamic light-scattering (DLS) measurements. The results from TEM, SEC, and DLS reveal that the particle size depends on the ratio of cross-linking. Particle size values measured by TEM were between 20 and 90 nm. Formation of cross-linked nanoparticles results in a dramatic viscosity drop compared to the viscosity of the corresponding solution of the parent PGA. The viscosity and DLS experiments disclose an intriguing interplay between intrachain and interchain cross-linking of the polymer chains, depending on the cross-linker density and polymer concentration. The SEC measurements show that the retention time of the major portion of particles increase because of the higher cross-linking ratio. At moderate cross-linker concentration, intramolecular cross-linking is the dominant process, whereas at higher cross-linker densities, the interpolymer cross-linking plays an important role. As a result, large clusters are also formed.     

Spectral signatures and molecular origin of acid dissociation intermediates

The existence of a broad, mid-infrared absorption ranging from 1000 to 3000 cm(-1) is usually interpreted as a signature for the existence of protonated water networks. Herein, we use cryogenic mixtures of water and hydrogen fluoride (HF) and show experimental and computational evidence that similarly wide absorptions can be generated by a broad distribution of proton-shared and ion pair complexes. In the present case, we demonstrate that the broadening is mainly inhomogeneous, reflecting the fact that the topology of the first solvation shell determines the local degree of ionization and the shared-proton asymmetric stretching frequency within H2O x HF complexes. The extreme sensitivity of the proton transfer potential energy hypersurface to local hydrogen bonding topologies modulates its vibrational frequency from 2800 down to approximately 1300 cm(-1), the latter value being characteristic of solvation geometries that yield similar condensed-phase proton affinities for H2O and fluoride. By linking the local degree of ionization to the solvation pattern, we are able to propose a mechanism of ionization for HF in aqueous solutions and to explain some of their unusual properties at large concentrations. However, an important conclusion of broad scientific interest is our prediction that spectral signatures that are normally attributed to protonated water networks could also reveal the presence of strong hydrogen bonds between un-ionized acids and water molecules, with important consequences to spectroscopic investigations of biologically relevant proton channels and pumps.     

Conformational Effects of Regioisomeric Substitution on the Catalytic Activity of Copper/Calix[8]arene C−S Coupling

Functionalization of the phenolic rim of p-tert-butylcalix[8]arene with phenanthroline to create a cavity leads to formation of two regioisomers. Substitution of positions 1 and 5 produces the known C_2v-symmetric regioisomer 1,5-(2,9-dimethyl-1,10-phenanthroyl)-p-tert-butylcalix[8]arene ( L^1,5 ), while substitution of positions 1 and 4 produces the C_s-symmetric regioisomer 1,4-(2,9-dimethyl-1,10-phenanthroyl)-p-tert-butylcalix[8]arene ( L^1,4 ) described herein. [ Cu(L^1,4)I ] was synthesized from L^1,4 and CuI in good yield and characterized spectroscopically. To evaluate the effect of its cavity on catalysis, Ullmann-type C−S coupling was chosen as proof-of-concept. Selected aryl halides were used, and the results compared with the previously reported Cu(I)/ L^1,5 system. Only highly activated aryl halides generate the C−S coupling product in moderate yields with the Cu(I)/ L^1,4 system. To shed light on these observations, detailed computational investigations were carried out, revealing the influence of the calix[8]arene macrocyclic morphology on the accessible conformations. The L^1,4 regioisomer undergoes a deformation that does not occur with L^1,5 , resulting in an exposed catalytic center, presumably the cause of the low activity of the former system. The 1,4-connectivity was confirmed in the solid-state structure of the byproduct [ Cu(L^1,4 − H) (CH₃CN)₂] that features Cu(I) coordinated inside a cleft defined by the macrocyclic framework.     

Nash-Type Equilibria for Systems of Szulkin Functionals

In this paper the solutions of some systems of variational inequalities are obtained as Nash-type equilibria of the corresponding systems of Szulkin functionals. This is achieved by an iterative scheme based on Ekeland’s variational principle, whose convergence is proved via the vector technique involving inverse-positive matrices. An application to periodic solutions for a system of two second order ordinary differential equations with singular ?-Laplacians is included.     

Fixed Point Theorems Under Combined Topological and Variational Conditions

The new idea is to replace part of the conditions on the operator involved in the classical fixed point theorems of Schauder, Krasnoselskii, Darbo and Sadovskii, by assumptions upon the associated functional, in case that the fixed point equation has a variational form. Fixed points minimizing the associated functionals are obtained via Ekeland’s variational principle and the Palais–Smale compactness condition guaranteed by the topological properties of the nonlinear operators.     

Continuity of topological entropy for perturbation of time-one maps of hyperbolic flows

In this paper we derive necessary and sufficient homological and cohomological conditions for profinite groups and modules to be of type FP_n over a profinite ring R, analogous to the Bieri–Eckmann criteria for abstract groups. We use these to prove that the class of groups of type FP_n is closed under extensions, quotients by subgroups of type FP_n, proper amalgamated free products and proper HNN-extensions, for each n. We show, as a consequence of this, that elementary amenable profinite groups of finite rank are of type FP_∞ over all profinite R. For any class C of finite groups closed under subgroups, quotients and extensions, we also construct pro-C groups of type FP_n but not of type FP_n+1 over Z_? for each n. Finally, we show that the natural analogue of the usual condition measuring when pro-p groups are of type FP_n fails for general profinite groups, answering in the negative the profinite analogue of a question of Kropholler.     

Neutron resonances in planar waveguides

We report on the results of the experimental investigation of the spectral width of neutron resonances in planar waveguides using the time-of-flight method and recording the microbeam emerging from the waveguide end. Experimental data are compared with the results of theoretical calculations.     

Convergence rates for sparse chaos approximations of elliptic problems with stochastic coefficients

^** Email: todor{at}math.ethz.ch^*** Corresponding author. Email: schwab{at}math.ethz.ch A scalar, elliptic boundary-value problem in divergence formwith stochastic diffusion coefficient a(x, ) in a bounded domainD ^d is reformulated as a deterministic, infinite-dimensional,parametric problem by separation of deterministic (x D) andstochastic ( ) variables in a(x, ) via Karhúnen–Loèveor Legendre expansions of the diffusion coefficient. Deterministic,approximate solvers are obtained by projection of this probleminto a product probability space of finite dimension M and sparsediscretizations of the resulting M-dimensional parametric problem.Both Galerkin and collocation approximations are considered.Under regularity assumptions on the fluctuation of a(x, ) inthe deterministic variable x, the convergence rate of the deterministicsolution algorithm is analysed in terms of the number N of deterministicproblems to be solved as both the chaos dimension M and themultiresolution level of the sparse discretization resp. thepolynomial degree of the chaos expansion increase simultaneously.     

Weighted Estimations from a Conjugate Operator

In this Letter we develop a general procedure leading from a Mourre-type estimation for a given self-adjoint operator H to a Hardy-type weighted inequality. We use this method in order to prove exponential decay for eigenvectors of a large class of perturbations of operators of convolution with bounded analytic functions.