A nanoscale dendrimer-based Fe24 cluster: synthesis and molecular self-assembly

We report the synthesis, characterisation and self-assembly of a nanoscopic Fe24 cluster using an organic dendrimer as a molecular substrate for building up well-defined molecular nanostructures.     

Elasticity of stiff polymer networks

We study the elasticity of a two-dimensional random network of rigid rods ("Mikado model"). The essential features incorporated into the model are the anisotropic elasticity of the rods and the random geometry of the network. We show that there are three distinct scaling regimes, characterized by two distinct length scales on the elastic backbone. In addition to a critical rigidity percolation region and a homogeneously elastic regime we find a novel intermediate scaling regime, where the elasticity is dominated by bending deformations.     

N-(17-Acyloxy-acyl)-glutamines: novel surfactants from oral secretions of lepidopteran larvae

N-(17-Acyloxy-acyl)-glutamine conjugates such as N-(17-linolenoyloxy-linolenoyl)-glutamine (6), N-(17-linolenoyloxy-linoleoyl)-glutamine (7), N-(17-linoleoyloxy-linolenoyl)-glutamine (8), and N-(17-linoleoyloxy-linoleoyl)-glutamine (9) were identified as novel surfactants in the oral secretion of several lepidopteran larvae (S. exigua, S. littoralis, S. frugiperda, and H. virescens) by LC-MS/MS and chemical degradation. Authentic reference compounds were synthesized via a dissymmetric bis-Wittig approach and confirmed the assigned structures.     

Multifunctional gold nanoparticle-peptide complexes for nuclear targeting

The ability of peptide-modified gold nanoparticles to target the nucleus of HepG2 cells was explored. Five peptide/nanoparticle complexes were investigated, particles modified with (1) the nuclear localization signal (NLS) from the SV 40 virus; (2) the adenovirus NLS; (3) the adenovirus receptor-mediated endocytosis (RME) peptide; (4) one long peptide containing the adenovirus RME and NLS; and (5) the adenovirus RME and NLS peptides attached to the nanoparticle as separate pieces. Gold nanoparticles were used because they are easy to identify using video-enhanced color differential interference contrast microscopy, and they are excellent scaffolds from which to build multifunctional nuclear targeting vectors. For example, particles modified solely with NLS peptides were not able to target the nucleus of HepG2 cells from outside the plasma membrane, because they either could not enter the cell or were trapped in endosomes. The combination of NLS/RME particles (4) and (5) did reach the nucleus; however, nuclear targeting was more efficient when the two signals were attached to nanoparticles as separate short pieces versus one long peptide. These studies highlight the challenges associated with nuclear targeting and the potential advantages of designing multifunctional nanostructured materials as tools for intracellular diagnostics and therapeutic delivery.     

First Cr(III)-SNS complexes and their use as highly efficient catalysts for the trimerization of ethylene to 1-hexene

Cr(III) complexes of tridentate SNS ligands have been prepared and evaluated as catalysts for ethylene trimerization, with several giving very high activity and excellent selectivity toward 1-hexene when activated with methylaluminoxane. The new complexes illustrate the potential of sulfur-based ligands on early transition metals for catalysis.     

Cavity cluster approach for quantification of cavitational intensity in sonochemical reactors

The mechanism involved in the spectacular effects from cavitation phenomenon is very complex and there have been several proposed theories to explain the observed results. The experimental as well as the visual observations indicate that a single collapsing cavity is also influenced by the dynamics of the surrounding cavities, which are very near to the collapsing cavity. The observed effects and erosion patterns cannot be explained properly on the basis of a single cavity collapse and hence in this study a cavity cluster (group of cavities) has been considered to understand the mechanism of cavitational effects. The effect of intensity, frequency of ultrasound, initial size of the cluster and the fraction of energy transferred from the collapsing cavities to the surrounding cavities on the cavitational intensity quantified in terms of the pressure pulse generated at the collapse of cavities as well as the active zone of cavitation has been investigated using bubble/cavity dynamics equations, numerically. On the basis of the trends obtained, empirical correlations estimating the collapse pressure and active volume of cavitation, have been developed.     

In vivo 31P echo-planar spectroscopic imaging of human calf muscle

Localized phosphorus-31 NMR spectra of human calf muscle in vivo were obtained by means of echo-planar spectroscopic imaging (EPSI) with a 1.5-T whole-body scanner. The technique permits the measurement of two-dimensional 31P SI data at a minimum acquisition time of 2.4 s (8x8 voxels, TR=300 ms). With 9.4 min measurement time (TR=1100 ms, 64 averages) and 25x25x40 mm spatial resolution in vivo the 31P NMR signal-to-noise ratio (S/N) of the phosphocreatine (PCr) resonance was about 45; the multiplets of nucleoside 5'-triphosphates were resolved. Spectral quality permits quantitative assessment of the PCr signal in a measurement time that is shorter by a factor of 2 or more than the minimum measurement time feasible with chemical-shift imaging. In a functional EPSI study with a time resolution of 20.5 s on the calf muscle of volunteers, spectra showed a 40% decrease of the PCr signal intensity (at rest: S/N congruent with12) upon exertion of the muscle.     

Old and new from SOR

From the long history of Successive Over Relaxation (SOR) between the end of second world war and today three points are considered: (1) Classical results of Young and Varga are described. (2) It is shown how results on semiiterative methods can be used to derive these classical results in a unifying way and to compare SOR with other iterative methods. (3) In the last 15 years the application of SOR to compute the stationary distribution of a homogeneous Markov chain has been discussed. These results are reported, considering especially the term extended convergence introduced by Kontovasilis, Plemmons and Stewart.     

Layer-resolved magnetic moments in Ni/Pt multilayers

The magnetic moments in Ni/Pt multilayers are thoroughly studied by combining experimental and ab initio theoretical techniques. SQUID magnetometry probes the samples' magnetizations. X-ray magnetic circular dichroism separates the contribution of Ni and Pt and provides a layer-resolved magnetic moment profile for the whole system. The results are compared to band-structure calculations. Induced Pt magnetic moments localized mostly at the interface are revealed. No magnetically "dead" Ni layers are found. The magnetization per Ni volume is slightly enhanced compared to bulk NiPt alloys.     

Synthesis and structural study of 2′‐ and 2′,6′‐positioned methyl‐ and nitro‐substituted 3‐(arylhydrazono)pentane‐2,4‐diones

A systematic series of ortho‐methyl‐ and nitro‐substituted arylhydrazones 2–6 formed by Japp–Klingemann reaction between pentane‐2,4‐dione and the respective aryldiazonium salts have been synthesized and studied by X‐ray crystal structure analysis, with added quantum chemical calculations. The optimized molecular geometries based on DFT calculations, enabling determination of relevant rotational barriers, and the calculated bond and ring critical points, using the method of ‘atoms in molecules’, were found to correspond with the experimental data, involving specific molecular conformations and hydrogen‐bonded ring structure dependent on the ortho‐substitution, thus making possible reliable structural prediction of this compound class. Copyright © 2007 John Wiley & Sons, Ltd.