Light and heat control over secondary structure and amyloid-like fiber formation in an overcrowded-alkene-modified Trp zipper

The external photocontrol over peptide folding, by the incorporation of molecular photoswitches into their structure, provides a powerful tool to study biological processes. However, it is limited so far to switches that exhibit only a rather limited geometrical change upon photoisomerization and that show thermal instability of the photoisomer. Here we describe the use of an overcrowded alkene photoswitch to control a model β-hairpin peptide. This photoresponsive unit undergoes a large conformational change and has two thermally stable isomers which has major influence on the secondary structure and the aggregation of the peptide, permitting the phototriggered formation of amyloid-like fibrils.     

The rational design of modified Cinchona alkaloid catalysts. Application to a new asymmetric synthesis of chiral chromanes

A new asymmetric synthesis of 2-substituted chiral chromanes has been achieved. The key step is the intramolecular conjugate addition of a phenolic nucleophile on a α,β-unsaturated ester catalyzed by Cinchona alkaloids. The high ee’s obtained with cinchonine and its derivatives have been rationalized by ab initio quantum chemistry calculations of transition state structures.     

Some remarks concerning C-spaces

We comment on the definition of C-spaces in [D.F. Addis, J.H. Gresham, A class of infinite-dimensional spaces. Part I: Dimension theory and Alexandroff's Problem, Fund. Math. 101 (1978) 195-205] and [W.E. Haver, A covering property for metric spaces, in: Topology Conference at Virginia Polytechnic Institute 1973, in: Lecture Notes in Math., vol. 375, 1974, pp. 108-113]. Furthermore we introduce two types of ‘finite’ C-spaces one of which gives an internal characterization of all spaces having a metrizable compactification satisfying property C. We also introduce a transfinite dimension function for those finite C-spaces. Several questions arise that are related to Alexandrov's problem.     

The valuations of the near hexagons related to the Witt designs S(5,6,12) and S(5,8,24)

Valuations of dense near polygons were introduced in 16 . In the present paper, we classify all valuations of the near hexagons ??₁ and ??₂, which are related to the respective Witt designs S(5,6,12) and S(5,8,24). Using these classifications, we prove that if a dense near polygon S contains a hex H isomorphic to ??₁ or ??₂, then H is classical in S. We will use this result to determine all dense near octagons that contain a hex isomorphic to ??₁ or ??₂. As a by‐product, we obtain a purely geometrical proof for the nonexistence of regular near 2d‐gons, d ≥ 4, whose parameters s, t, t_i (0 ≤ i ≤ d) satisfy (s, t₂, t₃) = (2, 1, 11) or (2, 2, 14). The nonexistence of these regular near polygons can also be shown with the aid of eigenvalue techniques. © 2005 Wiley Periodicals, Inc. J Combin Designs 14: 214–228, 2006     

On the covariance of the level sizes in random recursive trees

In this paper we study the covariance structure of the number of nodes k and l steps away from the root in random recursive trees. We give an analytic expression valid for all k, l and tree sizes N. The fraction of nodes k steps away from the root is a random probability distribution in k. The expression for the covariances allows us to show that the total variation distance between this (random) probability distribution and its mean converges in probability to zero. © 2002 Wiley Periodicals, Inc. Random Struct. Alg., 20: 519–539, 2002     

Synthesis of enantiomeric-pure cyclohexenyl nucleoside building blocks for oligonucleotide synthesis

Lipases were used for the resolution of (±) (4aR, 7R, 8aS)-2-phenyl-4a,7,8,8a-tetrahydro-4H-1,3-benzodioxine. This separation was carried out on preparative scale and used for the synthesis of eight phosphoramidites of cyclohexenyl nucleosides (d- and l-series).     

Ultrafiltration of a polymer-electrolyte mixture

We present a mathematical model to describe the ultrafiltration behaviour of polymer-electrolyte mixtures. The model combines the proper thermodynamic forces (pressure, chemical potential and electrical potential differences) with multicomponent diffusion theory. The model is verified with experimental data on the ultrafiltration of aqueous solutions of PEG-4000 and potassium phosphate. The single solute rejection of PEG-4000 goes through a maximum as also found by others. The single solute rejection of potassium phosphate depends on the ionic strength of the solution. At low ionic strength rejections are found of 50%. Solutions containing a high concentration of PEG-4000 and potassium phosphate show a negative rejection for potassium phosphate. This is caused by the strongly non-ideal behaviour of these aqueous solutions. The model predicts the behaviour of single solute experiments quite well, but some deviations are found with the mixed solute experiments. However, negative rejections found in the mixed solute experiments are predicted by the model.     

Efficient synthesis of an imidazole-substituted delta-amino acid by the integration of chiral technologies

Two methods to produce (2S)-5-amino-2-(1-n-propyl-1H-imidazol-4-ylmethyl)-pentanoic acid were investigated. Diastereoisomeric salt resolution, using the quinidine salt, gave the desired intermediate in 98% ee and 33% yield. Asymmetric hydrogenation of various substrates gave high conversions, with up to 83% ee. Integration of these two approaches via asymmetric hydrogenation of a quinidine salt substrate followed by crystallization provided the desired intermediate in 94% ee and 76% yield.