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1.
Glaus S Calzaferri G Hoffmann R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(8):1785-1794
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. 相似文献
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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. 相似文献
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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. 相似文献
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Reto Glaus Ralf Kaegi Frank Krumeich Detlef Günther 《Spectrochimica Acta Part B: Atomic Spectroscopy》2010,65(9-10):812-822
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. 相似文献
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Dr. Didier Zurwerra M. Sc. Chem. Florian Glaus M. Sc. Chem. Leo Betschart Julia Schuster Prof. Dr. Jürg Gertsch Dr. Walter Ganci Prof. Dr. Karl‐Heinz Altmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(52):16868-16883
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 . 相似文献
6.
It has been demonstrated that the triplet lifetime of nonemitting molecules in the dilute vapor phase - even for complex triplet decays - can be accurately determined by means of time-resolved triplet-triplet (T-T) energy transfer to a strong emitter molecule. Besides the test molecules 1-butyne-3-one and benzaldehyde the lifetime of the vibrationally relaxed nonemitting T1(nπ*) state of cycloheptanone, τ=63 ± 5 µs at ~?0.5 Torr, together with its energy transfer rate constant to biacetyl, kET=(1.80±0.08) x 106 s?1 Torr?1, have been measured. 相似文献
7.
M. Sc. Florian Glaus Prof. Karl‐Heinz Altmann 《Angewandte Chemie (International ed. in English)》2015,54(6):1937-1940
Tiacumicin B (lipiarmycin A3, fidaxomicin) is an atypical macrolide antibiotic which is used for the treatment of Clostridium difficile infections. Tiacumicin B is also a potent inhibitor of Mycobacterium tuberculosis, but due to its limited oral bioavailability is unsuitable for systemic therapy. To provide a basis for structure–activity studies that might eventually lead to improved variants of tiacumicin B, we have developed an efficient approach to the synthesis of the tiacumicin B aglycone. The synthesis features a high‐yielding intramolecular Suzuki cross‐coupling reaction to effect macrocyclic ring closure. Key steps in the synthesis of the macrocyclization precursor were a highly selective, one‐pot Corey–Peterson olefination and an ene–diene cross‐metathesis reaction. Depending on the reaction conditions, the final deprotection delivered either the fully deprotected tiacumicin B aglycone or partially protected versions thereof. 相似文献
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Tobias Lünskens Constantin A. Walenta Philipp Heister Aras Kartouzian Ueli Heiz 《Journal of Cluster Science》2017,28(5):2401-2408
We use surface second harmonic generation spectroscopy to study the oxidation of supported, size-selected silver clusters under ultra-high vacuum conditions. The oxidation reaction of small silver clusters between \(Ag_{9}\) and \(Ag_{55}\) is monitored by means of their localized surface plasmon resonance. We observe a rapid decline of the SH-intensity, as soon as cluster samples are exposed to an oxygen partial pressure of \(5 \cdot 10^{-6}\) mbar, which is attributed to the formation of silver–oxygen-bonds. The evolution of the SH-intensity under exposure to oxygen shows a double-exponential character for all investigated cluster sizes. Since the oxidation of single crystalline silver surfaces follow single-exponential Langmuir-kinetics, the two independent pathways of SH-intensity loss are attributed to a surface- and an interface-oxidation of supported clusters, respectiveley. For small cluster sizes, a complete loss of the SH intensity is obtained, which suggests the complete oxidation of the clusters. For larger clusters a plasmonic resonance is still observed after oxidation, indicating a residual free-electron density. 相似文献