Metal coordination to the formal P=N bond of an iminophosphorane and charge-density evidence against hypervalent phosphorus(V)

The iminophosphorane Ph(2)P(CH(2)Py)(NSiMe(3)) (1) was treated with deprotonating alkali metal reagents to give [(Et(2)O)Li[Ph(2)P(CHPy)(NSiMe(3))]] (2), [[Ph(2)P(CH(2)Py)(NSiMe(3))]Li[Ph(2)P(CHPy)(NSiMe(3))]] (3) and [[Ph(2)P(CH(2)Py)(NSiMe(3))]Na[Ph(2)P(CHPy)(NSiMe(3))]] (4). We report their coordination behaviour in solid-state structures and NMR spectroscopic features in solution. Furthermore, we furnish experimental evidence against hypervalency of the phosphorus atom in iminophosphoranes from experimental charge-density studies and subsequent topological analysis. The topological properties, correlated to the results from NMR spectroscopic investigations, illustrate that the formal P=N double bond is better written as a polar P(+)--N(-) single bond. Additionally, the effects of metal coordination on the bonding parameters of the iminophosphorane and the related anion are discussed.     

Multicomponent redox gradients on photoactive electrode surfaces

Redox gradients have been used to tailor the arrangement of photoactive ITO-electrodes at the molecular level.     

Selective synthesis of U-shaped terpyridines. Versatile ligands for the preparation of platinum complexes

The development of a simple and highly selective method for the preparation of substituted U-shaped terpyridines is described. The treatment of imine 5 with ternary iminium salts 2 leads to the terpyridines 4. A possible mechanism is discussed. The terpyridine derivatives are used for the preparation of several platinum(II) complexes 14. Complex 14e is characterized by single-crystal X-ray analysis.     

Capillary electrochromatography of peptides and proteins

This review surveys the accomplishments in the separation of peptides and proteins by capillary electrochromatography (CEC) over the last decade. A significant number of research articles have been published on this topic since the last review. Peptide and proteins separations have been carried out in all three formats of CEC, i.e., packed bed, continuous bed and open-tubular (OT) format. In addition to electrophoresis, different chromatographic modes have been successfully exploited with the most prevalent being reversed-phase mode followed by ion-exchange. Although many researchers continue to use model proteins and peptides primarily to evaluate the performance of novel stationary phases some researchers have also applied CEC to the analysis of real-life samples. The potential of CEC to yield complementary information and sometimes a superior separation with respect to established techniques, i.e., microbore HPLC and capillary electrophoresis has been demonstrated. Instrumental modifications in order to facilitate coupling of CEC to mass spectrometry have further upgraded the value of CEC for proteomic analysis. Capillaries are still the separation vehicle of choice for most researchers yet the microfluidic platform is gaining momentum, propelled particularly by its potential for multitasking, e.g., performing different chromatographic modes in series.     

Coherence of acoustic modes propagating through shallow water internal waves

The 1995 Shallow Water Acoustics in a Random Medium (SWARM) experiment [Apel et al., IEEE J. Ocean. Eng. 22, 445-464 (1997)] was conducted off the New Jersey coast. The experiment featured two well-populated vertical receiving arrays, which permitted the measured acoustic field to be decomposed into its normal modes. The decomposition was repeated for successive transmissions allowing the amplitude of each mode to be tracked. The modal amplitudes were observed to decorrelate with time scales on the order of 100 s [Headrick et al., J. Acoust. Soc. Am. 107(1), 201-220 (2000)]. In the present work, a theoretical model is proposed to explain the observed decorrelation. Packets of intense internal waves are modeled as coherent structures moving along the acoustic propagation path without changing shape. The packets cause mode coupling and their motion results in a changing acoustic interference pattern. The model is consistent with the rapid decorrelation observed in SWARM. The model also predicts the observed partial recorrelation of the field at longer time scales. The model is first tested in simple continuous-wave simulations using canonical representations for the internal waves. More detailed time-domain simulations are presented mimicking the situation in SWARM. Modeling results are compared to experimental data.     

Dynamics of the electric field-assisted charge carrier photogeneration in ladder-type poly(para-phenylene) at a low excitation intensity

Electric field-assisted charge carrier photogeneration in a ladder-type methyl-substituted poly(paraphenylene) was investigated by ultrafast absorption spectroscopy at low excitation intensity. The dissociation of excitons into electron-hole pairs occurs from the vibrationally relaxed excited state throughout its lifetime and is caused by the applied electric field, rather than by existence of special "dissociation sites." These findings are of importance for material choice in device applications.     

Charge-transfer states in strongly coupled phthalocyanine fullerene ensembles

Fluorescence and transient absorption measurements show that in strongly coupled ZnPc-C60 and H2Pc-C60 dyads charge-separated states are formed; large -delta GCR degree and small lambda assist in stabilising ZnPc(.+)-C60.-/H2Pc(.+)-C60.-.