Inclusion complexing by water-soluble β-cyclodextrin polymers

Cross-linked -cyclodextrin with a molecular weight of less than 10000 has good solubility in water, and it is a better inclusion complexing agent than the parent -cyclodextrin. By including lipophilic guest molecules into the apolar cyclodextrin cavity, their apparent lipophilicity is reduced because the outer surface of the molecular wrapping (the crosslinked -CD) is highly hydrophilic. The relative stability of the inclusion complexes can be rapidly determined by reversed-phase thin-layer chromatography. The reversed-phase TLC behaviour of 25 triphenylmethane derivatives and analogues were studied in the presence of -cyclodextrin polymers containing neutral and carboxyl groups. Increasing the molecular weight results in an increased complex-forming capacity. The carboxyl group modifies the accessibility of the CD cavity which in turn results in increased or decreased complex stability, depending on the guest molecule. The presence of organic solvents diminishes the stability of the CD complexes.     

Alkali-stable high-pI isoelectric membranes for isoelectric trapping separations

Alkali-stable, high-pI isoelectric membranes have been synthesized from quaternary ammonium derivatives of cyclodextrins and poly(vinyl alcohol), and bifunctional cross-linkers, such as glycerol-1,3-diglycidyl ether. The new, high-pI isoelectric membranes were successfully applied as cathodic membranes in isoelectric trapping separations in place of the hydrolytically more labile, polyacrylamide-based cathodic isoelectric membranes, and permitted the use of catholytes as alkaline as 1 M NaOH. The new high-pI isoelectric membranes have shown excellent mechanical stability, low electric resistance and long life times, even when subjected to electrophoresis with current densities as high as 80 mA/cm2.     

Petrov Types of Slowly Rotating Fluid Balls

Circularly rotating axisymmetric perfect fluid space-times are investigated to second order in the small angular velocity. The conditions of various special Petrov types are solved in a comoving tetrad formalism. A number of theorems are stated on the possible Petrov types of various fluid models. It is shown that Petrov type II solutions must reduce to the de Sitter spacetime in the static limit. Two space-times with a physically satisfactory energy-momentum tensor are investigated in detail. For the rotating incompressible fluid, it is proven that the Petrov type cannot be D. The equation of the rotation function can be solved for the Tolman type IV fluid in terms of quadratures. It is also shown that the rotating version of the Tolman IV space-time cannot be Petrov type D.     

Synthesis of three regioisomers of the pentasaccharide part of the Skp1 glycoprotein of Dictyostelium discoideum

Three regioisomers of the linear pentasaccharide part of the Skp1 glycoprotein, found in Dictyostelium discoideum, were prepared in the form of (2-trimethylsilyl)ethyl glycosides by means of 2+3 block syntheses using the disaccharide donor at the non-reducing end, and three different trisaccharide acceptors at the reducing end. Fucosylation of (2-trimethylsilyl)ethyl 3,4,6-tri-O-benzyl-β-d-galactopyranosyl-(1→3)-4,6-O-benzylidene-2-deoxy-2-NPhth-β-d-glucopyranoside with different fucosyl donors carrying an O-(2-naphthyl)methyl ether as a temporary-protecting group at positions C2, C3 or C4 gave rise to the protected core trisaccharides. After selective removal of the (2-naphthyl)methyl group, the resulting acceptors were glycosylated with the α(1→6) linked digalactosyl donor to yield the respective three regioisomeric pentasaccharides. Transformation of the phthalimido moiety into an N-acetyl group, followed by catalytic hydrogenation of the reducible-protecting groups furnished the free target pentasaccharides, which should be able to assist during the elucidation of the exact structure of the natural pentasaccharide.     

High-accuracy theoretical study on the thermochemistry of several formaldehyde derivatives

In the case of several formaldehyde derivatives, with importance in atmospheric and combustion chemistry, the currently available thermochemical values suffer from considerably large uncertainties. In this study a high-accuracy theoretical model chemistry has been used to provide accurate thermochemical data including heats of formation at 0 and 298 K and standard molar entropies at 298 K for CF(2)O, FCO, HFCO, HClCO, FClCO, HOCO, and NH(2)CO. For most of the thermochemical quantities studied here, this investigation delivers the best available estimate.     

Faceting and branching in 2D crystal growth

Using atomic scale time-dependent density functional calculations we confirm that both diffusion-controlled and diffusionless crystallization modes exist in simple 2D systems. We provide theoretical evidence that a faceted to nonfaceted transition is coupled to these crystallization modes, and faceting is governed by the local supersaturation at the fluid-crystalline interface. We also show that competing modes of crystallization have a major influence on mesopattern formation. Irregularly branched and porous structures are emerging at the crossover of the crystallization modes. The proposed branching mechanism differs essentially from dendritic fingering driven by diffusive instability.     

Tree metrics and edge-disjoint S-paths

Given an undirected graph \(G=(V,E)\) with a terminal set \(S \subseteq V\) , a weight function on terminal pairs, and an edge-cost \(a: E \rightarrow \mathbf{Z}_+\) , the \(\mu \) -weighted minimum-cost edge-disjoint \(S\) -paths problem ( \(\mu \) -CEDP) is to maximize \(\sum \nolimits _{P \in \mathcal{P}} \mu (s_P,t_P) - a(P)\) over all edge-disjoint sets \(\mathcal{P}\) of \(S\) -paths, where \(s_P,t_P\) denote the ends of \(P\) and \(a(P)\) is the sum of edge-cost \(a(e)\) over edges \(e\) in \(P\) . Our main result is a complete characterization of terminal weights \(\mu \) for which \(\mu \) -CEDP is tractable and admits a combinatorial min–max theorem. We prove that if \(\mu \) is a tree metric, then \(\mu \) -CEDP is solvable in polynomial time and has a combinatorial min–max formula, which extends Mader’s edge-disjoint \(S\) -paths theorem and its minimum-cost generalization by Karzanov. Our min–max theorem includes the dual half-integrality, which was earlier conjectured by Karzanov for a special case. We also prove that \(\mu \) -EDP, which is \(\mu \) -CEDP with \(a = 0\) , is NP-hard if \(\mu \) is not a truncated tree metric, where a truncated tree metric is a weight function represented as pairwise distances between balls in a tree. On the other hand, \(\mu \) -CEDP for a truncated tree metric \(\mu \) reduces to \(\mu '\) -CEDP for a tree metric \(\mu '\) . Thus our result is best possible unless P = NP. As an application, we obtain a good approximation algorithm for \(\mu \) -EDP with “near” tree metric \(\mu \) by utilizing results from the theory of low-distortion embedding.