Phenomenological studies on structure and elemental composition of nanosecond and femtosecond laser-generated aerosols with implications on laser ablation inductively coupled plasma mass spectrometry

In laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS), the properties of laser-generated aerosols, such as size and composition, are crucial for matrix-independent quantification. In this study, the aerosol particle morphology and elemental composition generated by two state-of-the-art laser systems (ArF excimer nanosecond-UV laser and Ti:sapphire femtosecond-IR laser) were investigated by electron microscopic techniques. Electrostatic sampling of the aerosols directly onto transmission electron microscopy (TEM) grids allowed us to study the morphology and elemental composition of the aerosols using TEM and TEM–EDX (energy dispersive X-ray spectroscopy) analyses, respectively. The results of the electron microscopic studies were finally compared to the LA-ICPMS signals of the main matrix components. The investigations were carried out for non-conducting materials (glass and zircon), metallic samples (steel and brass) and semiconductors (sulfides). The studies confirm that ns-LA-generated aerosols dominantly consist of nanoparticle agglomerates while conducting samples additionally contain larger spherical particles (diameter typically 50 to 500 nm). In contrast to ns-laser ablation, fs-LA-generated aerosols consist of a mixture of spherical particles and nanoparticle agglomerates for all investigated samples. Surprisingly, the differences in elemental composition between nanoparticle agglomerates and spherical particles produced with fs-LA were much more pronounced than in the case of ns-LA, especially for zircon (Si/Zr fractionation) and brass (Cu/Zn fractionation). These observations indicate different ablation and particle formation mechanisms for ns- and fs-LA. The particle growth mechanism for ns-LA is most likely a gas-to-particle conversion followed by agglomeration and additional hydrodynamic sputtering for conducting samples. On the other hand, phase explosion is assumed to be responsible for the mixture of large spherical particles and nanoparticle agglomerates as found for fs-LA-generated aerosols. Based on these mechanisms, the overall temporal elemental fractionation effects in ns-LA-ICPMS seem to occur mainly during the ablation. This effect was not observed for fs-LA-ICPMS despite the element separation into different particle fractions, which, on the other hand, could induce severe ICP-induced fractionation.     

Total Synthesis of (−)‐Zampanolide and Structure–Activity Relationship Studies on (−)‐Dactylolide Derivatives

A new total synthesis of the marine macrolide (?)‐zampanolide ( 1 ) and the structurally and stereochemically related non‐natural levorotatory enantiomer of (+)‐dactylolide ( 2 ), that is, ent‐ 2 , has been developed. The synthesis features a high‐yielding, selective intramolecular Horner–Wadsworth–Emmons (HWE) reaction to close the 20‐membered macrolactone ring of 1 and ent‐ 2 . The β‐keto phosphonate/aldehyde precursor for the ring‐closure reaction was obtained by esterification of a ω‐diethylphosphono carboxylic acid fragment and a secondary alcohol fragment incorporating the THP ring that is embedded in the macrocyclic core structure of 1 and ent‐ 2 . THP ring formation was accomplished through a segment coupling Prins‐type cyclization. Employing the same overall strategy, 13‐desmethylene‐ent‐ 2 as well as the monocyclic desTHP derivatives of 1 and ent‐ 2 were prepared. Synthetic 1 inhibited human cancer cell growth in vitro with nM IC₅₀ values, while ent‐ 2 , which lacks the diene‐containing hemiaminal‐linked side chain of 1 , is 25‐ to 260‐fold less active. 13‐Desmethylene‐ent‐ 2 as well as the reduced versions of ent‐ 2 and 13‐desmethylene‐ent‐ 2 all showed similar cellular activity as ent‐ 2 itself. The same activity level was attained by the monocyclic desTHP derivative of 1 . Oxidation of the aldehyde functionality of ent‐ 2 gave a carboxylic acid that was converted into the corresponding N‐hexyl amide. The latter showed only μM antiproliferative activity, thus being several hundred‐fold less potent than 1 .     

Electronic properties of the silver-silver chloride cluster interface

The objective of this study was to gain insight into the electronic structure of silver-silver chloride cluster composites and especially into the metal-semiconductor interface. For this purpose a theoretical study of (AgCl)(n) (n=4, 32, 108, 192, and 256), of Ag(m) (m=1-9, 30, 115, 276, and 409), and of the cluster composites Ag(115)-(AgCl)(192) and Ag(409)-(AgCl)(192) has been carried out. Density of levels (DOL), local density of levels (l-DOL), and projection of surface states, as well as projection of properties of individual atoms or groups of atoms obtained in molecular orbital calculations, are shown to be powerful tools for gaining deep insight into the properties of these large systems. The Ag(115)-(AgCl)(192) aggregate, consisting of a cubic Ag(115) cluster without corner atoms on top of a cubic (AgCl)(192) cluster, was found to be remarkably stable with a cluster-to-cluster distance of about 280 pm, and a geometry in which the number of bonding interactions between the silver atoms of Ag(115) and the chloride ions of (AgCl)(192) is at its maximum. A sharp jump in charge distribution occurs at the Ag(115)-(AgCl)(192) composite interface. The first AgCl slab picks up negative charge from the two adjacent silver slabs, so that in total the silver cluster is positively charged. In addition, the core of the silver cluster is positively charged with respect to its outermost layer. The main reason for the charge transfer from the silver cluster to the silver chloride is the newly formed MIGS (metal induced gap states) in the energy-gap range of the silver chloride and the MIdS (metal induced d states) in the d-orbital region. Their wave functions mix with orbitals of the silver cluster and with both the orbitals of the silver and the chloride ions of the silver chloride. The MIGS and the MIdS are of a quite localized nature. In them, nearest neighbor interactions dominate, with the exception of close-lying silver chloride surface states-which mix in to a large extent. We conclude that especially the MIGS not only influence the photochemical properties of silver chloride, but that their existence might be probed by appropriate spectroscopic measurements.     

A new Monte Carlo simulation for two models of self-avoiding lattice trees in two dimensions

By means of a new Monte Carlo sampling of a grand canonical ensemble, we verify universality for the critical exponents and of two models of lattice trees constrained to be self-avoiding on sites or on bonds. The attrition constants are also obtained. This algorithm, a generalization of that recently proposed by Berretti and Sokal for random walks, appears to optimize the critical slowing down in the scaling region. Systematic and statistical errors are carefully estimated.     

Size-Selected Clusters on Solid Surfaces

The present critical review examines the status of the research on supported, size-selected clusters with specific emphasis on their size-dependent physical and chemical properties. We describe the most relevant experimental methods with their advantages and drawbacks for the production of size-selected clusters and look critically at the present evidence for soft-landing of the clusters onto solid surfaces. Growth and characterization of cluster support materials are surveyed and the important role of surface defects for the properties of the supported clusters is considered. Recent advances in the characterization of the supported, size-selected clusters with local and non-local surface science analytical tools are presented and a few illustrative examples for size effects are given. Of specific and possibly broad impact on heterogeneous catalysis, we consider the discovery of the size-dependence of chemical reactions on very small supported clusters where recent experimental and theoretical evidence indicates charge transfer from the support to the cluster. This charge transfer turns inactive clusters into active ones, opening new perspectives to tune catalytic processes on the nanoscale.     

Total synthesis of the bacterial RNA polymerase inhibitor ripostatin b

A modular and highly stereoselective synthesis of the title compound was developed. Key steps in the assembly of the carbon framework of ripostatin?B (1; see scheme) were a stereoselective Paterson aldol reaction and a high-yielding ring-closing metathesis mediated by Grubbs first generation catalyst. The C15 hydroxy group was established through Tishchenko-Evans reduction in excellent yield and selectivity.