The application of MAS recoupling methods in the intermediate motional regime

We present investigations concerning the effect of molecular motions on the experimental timescale upon the recoupling of anisotropic interactions under magic-angle spinning conditions. An approach for the efficient simulation of spin dynamics occurring during complex pulse sequences, based on a linearization of the general solution of the stochastic Liouville-von Neumann equation, was developed. Using (13)C CSA recoupling of the methyl carbon in dimethylsulfon as a sample interaction, we observed a characteristic signal decay under recoupling upon entering the intermediate motional regime, which can be well described by an apparent transverse relaxation time, T(2)(rcpl). This quantity does not depend on the spinning frequency to a first approximation. Specific recoupling experiments, namely the measurement of tensor parameters by spinning sideband analysis, and the determination of rate constants with the CODEX experiment, are discussed with respect to possibilities and limits of their application in the intermediate motional regime. Important conclusions are drawn with regards to the limited applicability of popular recoupling methods like REDOR to samples exhibiting intermediate mobility.     

Orthogonale Polynome,die inn=0, 1, 2,...,N definiert sind und linearen homogenen Randbedingungen genügen

Ohne Zusammenfassung     

A combinatorial approach toward the generation of ambiphilic peptide-based inhibitors of protein:geranylgeranyl transferase-1

A combinatorial synthesis of oligopeptide analogues and their evaluation as protein:geranylgeranyl transferase inhibitors is presented. The combinatorial strategy is based on the random mutation, in each new generation, of one of any of the four amino acid building blocks of which the most effective compounds of the previous generation are assembled. In this way, a progressive improvement of the average inhibitory activity was observed until the fifth generation. The most active inhibitors were found to inhibit PGGT-1 in the low micromolar range (IC(50): 3.8-8.1 microM).     

Pairs of Dual Wavelet Frames from Any Two Refinable Functions

Starting from any two compactly supported refinable functions in L₂(R) with dilation factor d,we show that it is always possible to construct 2d wavelet functions with compact support such that they generate a pair of dual d-wavelet frames in L₂(R). Moreover, the number of vanishing moments of each of these wavelet frames is equal to the approximation order of the dual MRA; this is the highest possible. In particular, when we consider symmetric refinable functions, the constructed dual wavelets are also symmetric or antisymmetric. As a consequence, for any compactly supported refinable function in L₂(R), it is possible to construct, explicitly and easily, wavelets that are finite linear combinations of translates (d · – k), and that generate a wavelet frame with an arbitrarily preassigned number of vanishing moments.We illustrate the general theory by examples of such pairs of dual wavelet frames derived from B-spline functions.     

A nonmusical paradigm for identifying absolute pitch possessors

The ability to identify and reproduce sounds of specific frequencies is remarkable and uncommon. The etiology and defining characteristics of this skill, absolute pitch (AP), have been very controversial. One theory suggests that AP requires a specific type of early musical training and that the ability to encode and remember tones depends on these learned musical associations. An alternate theory argues that AP may be strongly dependent on hereditary factors and relatively independent of musical experience. To date, it has been difficult to test these hypotheses because all previous paradigms for identifying AP have required subjects to employ knowledge of musical nomenclature. As such, these tests are insensitive to the possibility of discovering AP in either nonmusicians or musicians of non-Western training. Based on previous literature in pitch memory, a paradigm is presented that is intended to distinguish between AP possessors and nonpossessors independent of the subjects' musical experience. The efficacy of this method is then tested with 20 classically defined AP possessors and 22 nonpossessors. Data from these groups strongly support the validity of the paradigm. The use of a nonmusical paradigm to identify AP may facilitate research into many aspects of this phenomenon.     

Peak dispersion and contributions to plate height in nonaqueous capillary electrophoresis at high electric field strengths: propanol as background electrolyte solvent

Peak dispersion effects in nonaqueous capillary electrophoretic separations of aromatic anionic analytes were investigated in a propanolic background electrolyte solution. Poly(glycidylmethacrylate-co-N-vinylpyrrolidone) coating was applied to the capillary to suppress the electroosmotic flow and to improve the repeatability of the migration times. Electrical field strengths up to 2000 Vcm(-1) were applied in separations and the separation efficiencies were compared with theoretical values calculated on the basis of plate height theory. The contributions to the total plate height were calculated for injection plug length, diffusion, Joule heating, electromigration dispersion, analyte adsorption to the capillary wall, and detector slit aperture length. Analyte diffusion coefficients were measured by Taylor dispersion method, while distribution constants were measured chromatographically. Agreement between the calculated and empirical results was fairly good even though some approximations were required. In most cases the longitudinal diffusion contribution governed the total plate height, while the contribution of Joule heating was insignificant even at exceptionally high field strengths used. The relatively long detection slit aperture was found to influence the separation efficiency strongly, while the other dispersion sources that were investigated were of minor importance, except for adsorption in the case of one analyte. With all analytes, the dispersive effect of longitudinal diffusion was reduced as the field strength was increased, leading to enhanced migration velocities and faster separations.     

Off‐diagonal and asymptotic results on the Ramsey number r(K2,m,K2,n)

An upper bound on the Ramsey number r(K_2,n‐s,K_2,n) where s ≥ 2 is presented. Considering certain r(K_2,n‐s,K_2,n)‐colorings obtained from strongly regular graphs, we additionally prove that this bound matches the exact value of r(K_2,n‐s,K_2,n) in infinitely many cases if holds. Moreover, the asymptotic behavior of r(K_2,m,K_2,n) is studied for n being sufficiently large depending on m. We conclude with a table of all known Ramsey numbers r(K_2,m,K_2,n) where m,n ≤ 10. © 2003 Wiley Periodicals, Inc. J Graph Theory 43: 252–268, 2003     

Novel polyesteramide-based di- and triblock copolymers: From thermo-mechanical properties to hydrolytic degradation

Two types of biodegradable poly(ε-caprolactone (CLo))-co-poly(ε-caprolactam (CLa)) copolymers were prepared by catalyzed hydrolytic ring-opening polymerization. For the first type of materials, the respective cyclic comonomers were added simultaneously in the reaction medium leading to the formation of copolymers having a random distribution of co-units within the polyesteramide sequence, as evidenced by ¹H and ¹³C NMR. For the second type of copolymers, the cyclic comonomers were added sequentially in the reaction medium yielding diblock polyesteramides, again evidenced by NMR. The thermal and thermo-mechanical properties of the copolymers were investigated by DSC and DMA and correlated with the copolymer topology and composition. The copolymers were characterized by a storage modulus and α transition temperature intermediate to the modulus and T_g of the corresponding homopolymers. The chemical composition and molecular weight of the copolymers proved to have only a limited effect on the thermo-mechanical properties of the materials. The hydrolytic degradation of random copolymers was studied in a phosphate buffer at 60 °C and discussed in terms of chemical composition and molecular weight of the copolymers.