A memory function model for the velocity autocorrelation function and the self-diffusion coefficient in simple dense fluids

A memory-function model is used to compute the velocity autocorrelation function and the self-diffusion coefficient of a dense Lennard-Jones fluid from the zero-time correlation functions of the molecular velocity and its first two time derivatives. It is shown that these zero-time correlation functions can be evaluated in terms of the radial distribution function and the pair potential only, i.e. without considering higher order correlation functions. Since molecular dynamics results are available for the radial distribution function as well as the velocity autocorrelation function and the self-diffusion coefficient, a rigorous test of the chosen memory function is possible. The agreement is reasonable, although generally not within the error bands of the molecular dynamics results.     

Phenanthrene‐Fused‐Quinoxaline as a Key Building Block for Highly Efficient and Stable Sensitizers in Copper‐Electrolyte‐Based Dye‐Sensitized Solar Cells

Dye‐sensitized solar cells (DSSCs) based on Cu^II/I bipyridyl or phenanthroline complexes as redox shuttles have achieved very high open‐circuit voltages (V_OC, more than 1 V). However, their short‐circuit photocurrent density (J_SC) has remained modest. Increasing the J_SC is expected to extend the spectral response of sensitizers to the red or NIR region while maintaining efficient electron injection in the mesoscopic TiO₂ film and fast regeneration by the Cu^I complex. Herein, we report two new D‐A‐π‐A‐featured sensitizers termed HY63 and HY64 , which employ benzothiadiazole (BT) or phenanthrene‐fused‐quinoxaline (PFQ), respectively, as the auxiliary electron‐withdrawing acceptor moiety. Despite their very similar energy levels and absorption onsets, HY64 ‐based DSSCs outperform their HY63 counterparts, achieving a power conversion efficiency (PCE) of 12.5 %. PFQ is superior to BT in reducing charge recombination resulting in the near‐quantitative collection of photogenerated charge carriers.     

Annealing of electron irradiated GaP studied by positron lifetime technique

GaP single crystals were irradiated by 3 MeV electrons at 20 K to a dose of 4 × 10¹⁸ e/cm². An isochronal annealing in temperature region 77 ÷ 650 K followed the irradiation. Positron lifetime measurement indicated the presence of irradiation-induced vacancies in Ga sublattice. The vacancies disappeared at two stages observed at temperatures 200 ÷ 300 K and 450 ÷ 550 K.     

Halophilic reactions of a stable silylene with chloro and bromocarbons

A number of disilanes have been synthesized from a stable silylene, 1 (N,N'-di-tert-butyl-1,3-diaza-2-silacyclopent-4-en-2-ylidene), and a variety of halocarbons. It is proposed that disilane formation is a result of an initial halophilic interaction between the silylene and halocarbon. Formation of disilanes from 1 and CCl4, 2a, CHCl3, 2b, CH2Cl2, 2c, benzyl chloride, 2d, and bromobenzene, 5, are described here. An X-ray crystal structure of 2b was determined.     

Intersubband transport in quantum wells in strong magnetic fields mediated by single- and two-electron scattering

We show theoretically that in quantum wells subjected to a strong magnetic field the intersubband current peaks at magnetic field values, which reveal the underlying specific intersubband scattering mechanism. We have designed and grown a superlattice structure in which such current oscillations are clearly visible, and in which the transition from the purely single-electron to the mixed single- and two-electron scattering regimes can be observed by tuning the applied voltage bias. The measurements were conducted in ultrahigh magnetic fields (up to 45 T) to obtain the full spectrum of the current oscillations.     

Comparison of multi-echo spiral and echo planar imaging in functional MRI

Multi-echo spiral and echo-planar (EPI) imaging sequences were compared in functional imaging experiments at 3 Tesla. Both sequence types allow calculation of the effective transversal relaxation time T(2)* and the initial signal intensity I(0). These parameters can be used in evaluation of the functional signal with respect to inflow effects and other vascular sources. Prior to functional magnetic resonance imaging (fMRI) experiments T(2)* measurements in the human brain were performed with single- and multi-echo FLASH (fast low angle shot) and compared with EPI und spiral imaging sequences. These experiments resulted in T(2)* values ranging from 42.9 to 53.8 ms in a ROI including white and gray matter and CSF in a prefrontal brain region, and allowed validation of the quantitative results of the fast single-shot techniques. In functional experiments with motor stimulation mean absolute T(2)* increases during stimulation of 1.1 +/- 0.6 ms and 1.4 +/- 0.9 ms were found with multi-echo EPI and spiral imaging, respectively, averaged over the activated pixels. In addition, absolute T(2)* values and the size of activated areas obtained with both sequences are comparable. In these investigations spiral imaging allowed higher spatial resolution due to more efficient use of available gradient performance.     

The influence of hyperoxia on regional cerebral blood flow (rCBF), regional cerebral blood volume (rCBV) and cerebral blood flow velocity in the middle cerebral artery (CBFVMCA) in human volunteers

Conflicting results reported on the effects of hyperoxia on cerebral hemodynamics have been attributed mainly to methodical and species differences. In the present study contrast-enhanced magnetic resonance imaging (MRI) perfusion measurement was used to analyze the influence of hyperoxia (fraction of inspired oxygen (FiO2) = 1.0) on regional cerebral blood flow (rCBF) and regional cerebral blood volume (rCBV) in awake, normoventilating volunteers (n = 19). Furthermore, the experiment was repeated in 20 volunteers for transcranial Doppler sonography (TCD) measurement of cerebral blood flow velocity in the middle cerebral artery (CBFV(MCA)). When compared to normoxia (FiO2 = 0.21), hyperoxia heterogeneously influenced rCBV (4.95 +/- 0.02 to 12.87 +/- 0.08 mL/100g (FiO2 = 0.21) vs. 4.50 +/- 0.02 to 13.09 +/- 0.09 mL/100g (FiO2 = 1.0). In contrast, hyperoxia diminished rCBF in all regions (68.08 +/- 0.38 to 199.58 +/- 1.58 mL/100g/min (FiO2 = 0.21) vs. 58.63 +/- 0.32 to 175.16 +/- 1.51 mL/100g/min (FiO2 = 1.0)) except in parietal and left frontal gray matter. CBFV(MCA) remained unchanged regardless of the inspired oxygen fraction (62 +/- 9 cm/s (FiO2 = 0.21) vs. 64 +/- 8 cm/s (FiO2 = 1.0)). Finding CBFV(MCA) unchanged during hyperoxia is consistent with the present study's unchanged rCBF in parietal and left frontal gray matter. In these fronto-parietal regions predominantly fed by the middle cerebral artery, the vasoconstrictor effect of oxygen was probably counteracted by increased perfusion of foci of neuronal activity controlling general behavior and arousal.     

Photobinding of carprofen to protein

Carprofen is a non-steroidal antiinflammatory drug with marked photosensitising properties. In order to elucidate the mechanisms underlying the phenomenon of drug-protein photobinding, mixtures of the drug and human serum albumin were irradiated under different experimental conditions. After irradiation and subsequent gel-filtration chromatography of the photomixture, the eluting protein fraction was analysed by means of fluorescence spectroscopy. The formation of drug-protein photoadducts could be evidenced by the characteristic emission properties of the carbazole chromophore. The photobinding of the drug to human serum albumin appears to involve the formation of aryl radicals resulting from carbon-halogen photocleavage. This mechanistic interpretation is supported by the observed variations in the intensity of the fluorescence spectra, which can be correlated with the lower quantum yield emission of chlorocarbazoles as compared to non-halogenated analogues. The results from laser flash photolysis studies are also in agreement with this proposal.