A model iridium hydroformylation system with the large bite angle ligand xantphos: reactivity with parahydrogen and implications for hydroformylation catalysis

Iridium complexes containing the large bite angle bisphosphine ligand xantphos have been synthesized and their reactivity studied. Several of these complexes are the first reported Ir(xantphos) systems to be characterized by X-ray diffraction. Variable-temperature NMR spectroscopic studies of IrI(CO)2(xantphos) (1-I) and Ir(COEt)(CO)2(xantphos) (8) show two separate dynamic processes in which the phosphorus donors and the backbone methyl groups of the xantphos ligand are exchanged. The addition of parahydrogen (p-H2) to 1-I leads to the formation of two dihydride isomers including one in which both hydride ligands are trans to the phosphorus donors, suggestive of an Ir(I) xantphos intermediate with the ligand chelated in a trans-spanning fashion (2b). The bromide and chloride Ir(I) analogues (1-Br and 1-Cl) also form this isomer upon reaction with parahydrogen, with 1-Cl yielding only this dihydride species. The trihydride complex IrH3(CO)(xantphos) (7) has been prepared, and its exchange with free hydrogen at elevated temperature is confirmed by reaction with p-H2. The hydride complexes IrH(CO)2(xantphos) (6) and IrH3(CO)(xantphos) (7), as well as the propionyl complex 8, are modest catalysts for the hydroformylation of 1-hexene and styrene under mild conditions. The addition of p-H2 to 8 permits direct observation of the propionyl dihydride species IrH2(COEt)(CO)(xantphos) (9) under both thermal and photolytic conditions, as well as unusual but weak polarization of the aldehydic proton of the propanal product that forms upon reductive elimination from 9.     

Influence of the precipitation agent in the deposition-precipitation on the formation and properties of Au nanoparticles supported on Al2O3

Au nanoparticles supported on Al2O3 were prepared by deposition-precipitation of HAuCl4 with different precipitation agents NaOH and urea. The samples were investigated by means of different characterization techniques such as X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and transmission electron microscopy (TEM). The results show that depending on the precipitation agent, the Au particles have a different Au-Au coordination number and size after calcination at 523 K. Whereas the use of NaOH leads to the formation of Au nanoparticles with a Au-Au coordination number of 6.7 and a mean diameter below 2 nm, those prepared with urea have a mean size of 3.1 nm. The Au-Au coordination number could be determined as 8.6. At the smaller particles obtained with NaOH, hints for Au-O interactions were found. For these particles TEM results advise a rather flat lenticular morphology. Different deposition mechanisms depending on the precipitation agent are discussed as the reason for the formation of nanoparticles with different shapes, sizes, and valence states.     

Age-related changes in within- and between-channel gap detection using sinusoidal stimuli

Pure tone gap stimuli with identical (within-channel) or dissimilar (between-channel) marker frequencies of 1 and 2 kHz were presented to young and old listeners in a two-interval forced choice gap detection task. To estimate the influence of extraneous duration cues on gap detection, thresholds in the between-channel conditions were obtained for two different sets of reference stimuli: reference stimuli that were matched to the overall duration of the gap stimulus, i.e., two markers plus the gap, and reference stimuli that were fixed at the combined duration of the two markers excluding the gap. Results from within-channel conditions were consistent with previous studies, i.e., there were small but highly reliable age differences, smaller gap thresholds at longer marker durations, and an interaction between the two variables. In between-channel conditions, however, age differences were not as clear cut. Rather, the effect of age varied as a function of duration cue and was more pronounced when stimuli were matched for overall duration than when the duration of the reference tone was fixed.     

Continuity and Schatten-von Neumann p-class membership of Hankel operators with anti-holomorphic symbols on (generalized) Fock spaces

In this paper we investigate Hankel operators with anti-holomorphic symbols ∈L²(C,m|z|), where are general Fock spaces. We will show that is not continuous if the corresponding symbol is not a polynomial . For polynomial symbols we will give necessary and sufficient conditions for continuity and compactness in terms of N and m. For monomials we will give a complete characterization of the Schatten-von Neumann p-class membership for p>0. Namely in case 2k<m the Hankel operators are in the Schatten-von Neumann p-class iff p>2m/(m−2k); and in case 2k?m they are not in the Schatten-von Neumann p-class.     

NIPALSTREE: a new hierarchical clustering approach for large compound libraries and its application to virtual screening

A hierarchical clustering algorithm--NIPALSTREE--was developed that is able to analyze large data sets in high-dimensional space. The result can be displayed as a dendrogram. At each tree level the algorithm projects a data set via principle component analysis onto one dimension. The data set is sorted according to this one dimension and split at the median position. To avoid distortion of clusters at the median position, the algorithm identifies a potentially more suited split point left or right of the median. The procedure is recursively applied on the resulting subsets until the maximal distance between cluster members exceeds a user-defined threshold. The approach was validated in a retrospective screening study for angiotensin converting enzyme (ACE) inhibitors. The resulting clusters were assessed for their purity and enrichment in actives belonging to this ligand class. Enrichment was observed in individual branches of the dendrogram. In further retrospective virtual screening studies employing the MDL Drug Data Report (MDDR), COBRA, and the SPECS catalog, NIPALSTREE was compared with the hierarchical k-means clustering approach. Results show that both algorithms can be used in the context of virtual screening. Intersecting the result lists obtained with both algorithms improved enrichment factors while losing only few chemotypes.     

Spin-flip processes and ultrafast magnetization dynamics in Co: Unifying the microscopic and macroscopic view of femtosecond magnetism

The femtosecond magnetization dynamics of a thin cobalt film excited with ultrashort laser pulses has been studied using two complementary pump-probe techniques, namely, spin-, energy-, and time-resolved photoemission and the time-resolved magneto-optical Kerr effect. Combining the two methods, it is possible to identify the microscopic electron spin-flip mechanisms responsible for the ultrafast macroscopic magnetization dynamics of the cobalt film. In particular, we show that electron-magnon excitation does not affect the overall magnetization even though it is an efficient spin-flip channel on the sub-200 fs time scale. Instead, we find experimental evidence for the relevance of Elliott-Yafet-type spin-flip processes for the ultrafast demagnetization taking place on a time scale of 300 fs.     

Creation of hot radiation environments in laser-driven targets

A hot radiation environment, produced by maximizing laser-energy deposition into a small, high- "can," is a platform being developed for investigations of material properties under extreme conditions. In such small targets, almost doubling the laser energy results in only an incremental increase in the x-radiation flux, and almost no increase in the maximum achieved radiation temperature. That most of this additional laser energy is not deposited within the target is a direct consequence of laser-plasma interactions (LPI) outside of the target, which result in high-angle beams never entering the target late in the laser pulse. Accounting for these processes in the modeling results in quantitative agreement for the first time with experiments using very small cans. These findings have provided the scientific foundation for modifying the target geometry to mitigate the LPI and to achieve higher radiation temperatures.