A novel class of organo- (hydro-) gelators based on ascorbic acid

A library of novel, lipid-modified derivatives of ascorbic acid was shown to exhibit highly attractive properties as surfactants, emulsifiers, oil soluble antioxidants, and highly effective gelators in organic solvents and especially water. In these systems, intermolecular hydrogen bonding and van der Waals forces act synergistically to induce gelation as confirmed by spectroscopic studies. The morphology of the formed gel has been characterized by scanning electron microscopy.     

On the sequences of the Weyl semi-radii associated with matricial Carathéodory and Schur sequences in both nondegenerate and degenerate cases

In this paper we discuss Weyl matrix balls in the context of the matricial versions of the classical interpolation problems named after Carathéodory and Schur. Our particular focus will be on studying the monotonicity of suitably normalized semi-radii of the corresponding Weyl matrix balls. We, furthermore, devote a fair bit of attention to characterizing the case in which equality holds for particular matricial inequalities. Solving these problems will provide us with a new perspective on the role of the central functions for the classes of Carathéodory and Schur.     

A probabilistic comparison of the strength of split, triangle, and quadrilateral cuts

We consider mixed integer linear sets defined by two equations involving two integer variables and any number of non-negative continuous variables. We analyze the benefit from adding a non-split inequality on top of the split closure. Applying a probabilistic model, we show that the importance of a type 2 triangle inequality decreases with decreasing lattice width, on average. Our results suggest that this is also true for type 3 triangle and quadrilateral inequalities.     

Isoperimetric inequalities for special classes of curves

In this paper the classical Banchoff-Pohl inequality, an isoperimetric inequality for nonsimple closed curves in the Euclidean plane, involving the square of the winding number, is sharpened for homothetic or Abresch-Langer solutions of curve shortening. For a larger class of curves and for rotationally symmetric curves, further isoperimetric inequalities containing the rotation number and the winding number, are presented.     

N-terminal protein modification using simple aminoacyl transferase substrates

Methods for synthetically manipulating protein structure enable greater flexibility in the study of protein function. Previous characterization of the Escherichia coli aminoacyl tRNA transferase (AaT) has shown that it can modify the N-terminus of a protein with an amino acid from a tRNA or a synthetic oligonucleotide donor. Here, we demonstrate that AaT can efficiently use a minimal adenosine substrate, which can be synthesized in one to two steps from readily available starting materials. We have characterized the enzymatic activity of AaT with aminoacyl adenosyl donors and found that reaction products do not inhibit AaT. The use of adenosyl donors removes the substrate limitations imposed by the use of synthetases for tRNA charging and avoids the complex synthesis of an oligonucleotide donor. Thus, our AaT donors increase the potential substrate scope and reaction scale for N-terminal protein modification under conditions that maintain folding.     

Towards nanoscale composite particles of dual complexity

The fabrication of heteroaggregates comprising inorganic and organic nanoparticles of different sizes is reported. Control over the assembly of nanoscale functional building units is of great significance to many practical applications. Joining together different spherical nanoparticles in a defined manner allows control over the shape of the composites. If two types of constituents are chosen that differ in size, the surfaces of the composites exhibit two specific radii of curvature, yielding aggregates of dual surface roughness. Moreover, if the constituents consist of different materials, the resulting heteroaggregates feature both compositional and interfacial anisotropy, offering unprecedented perspectives for custom-tailored colloids. This study describes a two-step approach towards such designer particles. At first, amine-modified polystyrene particles with 154 nm diameter were assembled into clusters of well-defined configurations. Onto these, oppositely charged inorganic particles with diameters of only a few nanometres were deposited by direct uptake from solution, resulting in numerous functional entities all over the surface of the polymer clusters. Despite the fact that oppositely charged constituents are brought together, charge reversal by uptake of nanoparticles allows for stable suspensions of heterocomposites. Hence, the possibility to assemble particles into nanoscale heterocomposites with full control over shape, composition, and surface roughness is demonstrated.     

Synthesis and reactions of pyrido[3,2,1‐jk]carbazole‐4,6‐diones

Pyrido[3,2,1‐jk]carbazoles 1 , synthesized from carbazoles and alkyl‐ or arylmalonates, gave regioselective electrophilic substitution reactions at position 5 such as chlorination to 5‐chloro derivatives 2 , nitration to 5‐nitro compounds 3 , or hydroxylation to 5‐hydroxy derivatives 4 . 5‐Hydroxy compounds 4 gave on treatment with strong bases ring contraction to 5 , 6 or the ring opening product 7 . Exchange of the chloro group in 2 with azide or amines gave the corresponding azides 8 and the 5‐amino derivatives 9 and 10 . Alkylation of 1 with benzyl chloride or allyl bromide resulted in the formation of 5‐C‐alkylated products 11 together with 4‐alkyloxy derivatives 12 . J. Heterocyclic Chem., 48, 1039 (2011).     

LC-MS based quantification of 2'-ribosylated nucleosides Ar(p) and Gr(p) in tRNA

RNA nucleosides are often naturally modified into complex non-canonical structures with key biological functions. Here we report LC-MS quantification of the Ar(p) and Gr(p) 2'-ribosylated nucleosides in tRNA using deuterium labelled standards, and the first detection of Gr(p) in complex fungi.     

9-H-9-Borafluorene dimethyl sulfide adduct: a product of a unique ring-contraction reaction and a useful hydroboration reagent

The dimethyl sulfide adduct 2(DMS) is a crystalline storage form of the unstable hydroboration reagent 9-H-9-borafluorene (2); 2(DMS) is available by the addition of DMS to either in situ generated [2](2) or 1,2-(2,2'-biphenylylene)diborane(6) (7).