Molecular Heterojunctions of Oligo(phenylene ethynylene)s with Linear to Cruciform Framework

Electrical transport properties of molecular junctions are fundamentally affected by the energy alignment between molecular frontier orbitals (highest occupied molecular orbital (HOMO) or lowest unoccupied molecular orbital (LUMO)) and Fermi level (or work function) of electrode metals. Dithiafulvene (DTF) is used as substituent group to the oligo(phenylene ethynylene) (OPE) molecular wires and different molecular structures based on OPE3 backbone (with linear to cruciform framework) are achieved, with viable molecular orbitals and HOMO–LUMO energy gaps. OPE3, OPE3–DTF, and OPE3–tetrathiafulvalene (TTF) can form good self‐assembled monolayers (SAMs) on Au substrates. Molecular heterojunctions based on these SAMs are investigated using conducting probe–atomic force microscopy with different tips (Ag, Au, and Pt) and Fermi levels. The calibrated conductance values follow the sequence OPE3–TTF > OPE3–DTF > OPE3 irrespective of the tip metal. Rectification properties (or diode behavior) are observed in case of the Ag tip for which the work function is furthest from the HOMO levels of the OPE3s. Quantum chemical calculations of the transmission qualitatively agree with the experimental data and reproduce the substituent effect of DTF. Zero‐bias conductance, and symmetric or asymmetric couplings to the electrodes are investigated. The results indicate that improved fidelity of molecular transport measurements may be achieved by systematic studies of homologues series of molecular wires applying several different metal electrodes.     

3- Instead of 4-helix formation in a de novo designed protein in solution revealed by small-angle X-ray scattering

De novo design and chemical synthesis of proteins and their mimics are central approaches for understanding protein folding and accessing proteins with novel functions. We have previously described carbohydrates as templates for the assembly of artificial proteins, so-called carboproteins. Here, we describe the preparation and structural studies of three alpha-helical bundle carboproteins, which were assembled from three different carbohydrate templates and one amphiphilic hexadecapeptide sequence. This heptad repeat peptide sequence has been reported to lead to 4-alpha-helix formation. The low resolution solution structures of the three carboproteins were analyzed by means of small-angle X-ray scattering (SAXS) and synchrotron radiation circular dichroism (SRCD). The ab initio SAXS data analysis revealed that all three carboproteins adopted an unexpected 3+1-helix folding topology in solution, while the free peptide formed a 3-helix bundle. This finding is consistent with the calculated alpha-helicities based on the SRCD data, which are 72 and 68 % for two of the carboproteins. The choice of template did not affect the overall folding topology (that is for the 3+1 helix bundle) the template did have a noticeable impact on the solution structure. This was particularly evident when comparing 4-helix carboprotein monomers with the 2x2-helix carboprotein dimer as the latter adopted a more compact conformation. Furthermore, the clear conformational differences observed between the two 4-helix (3+1) carboproteins based on D-altropyranoside and D-galactopyranoside support the notion that folding is affected by the template, and subtle variations in template distance-geometry design may be exploited to control the solution fold. In addition, the SRCD data show that template assembly significantly increases thermostability.     

Numerical Simulation of Metal Melt Flow in a One-Strand Tundish Regarding Active Filtration and Reactive Cleaning

Metallurgical and Materials Transactions B - In the paper, two different cleaning strategies for nonmetallic inclusions in steel melts, active filtration and reactive cleaning, are examined in a...     

Synthesis and thermal decomposition of potassium tetraamidoboranealuminate,K[Al(NH2BH3)4]

A new potassium tetraamidoboranealuminate, K[Al(NH₂BH₃)₄], has been synthesized by a mechanochemical reaction between KAlH₄ and NH₃BH₃. The compound, K[Al(NH₂BH₃)₄], crystallizes in a triclinic unit cell with space group symmetry P?1. The crystal structure consists of [K(NH₂BH₃)₆]^5? octahedra which facilitate the bridging between K⁺ in 1D chains, while also bridging K⁺ to Al³⁺ to connect the 1D chains in a 3D network. Thermal analysis reveals that K[Al(NH₂BH₃)₄] decomposes in two exothermic steps at T ～ 94 and 138 °C and releases primarily hydrogen. The total gas release amounts to ～6.0 wt% H₂. The decomposition products are investigated ex situ by powder X-ray diffraction, infrared spectroscopy, and ¹¹B and ²⁷Al NMR and identified as KBH₄ and amorphous phases, possibly BN₃, N₂BH, and/or NBH₂ whereas aluminum is found in four-, five-, and six-fold coordination. Unfortunately, the decomposed sample shows no hydrogen absorption at T = 260 °C and p(H₂) = 110 bar.     

Chronic obstructive pulmonary disease in patients with end‐stage kidney disease on hemodialysis

The objectives of this study were to assess the prevalence of chronic obstructive pulmonary disease (COPD) in hemodialysis patients with spirometry and to examine the effects of fluid removal by hemodialysis on lung volumes. Patients ≥18 years at two Danish hemodialysis centers were included. Forced expiratory volume in one second (FEV₁), forced vital capacity (FVC), and FEV₁/FVC ratio were measured with spirometry before and after hemodialysis. The diagnosis of COPD was based on both the GOLD criteria and the lower limit of normal criteria. There were 372 patients in treatment at the two centers, 255 patients (69%) completed spirometry before dialysis and 242 of these (65%) repeated the test after. In the initial test, 117 subjects (46%) had airflow limitation indicative of COPD with GOLD criteria and 103 subjects (40.4%) with lower limit of normal criteria; COPD was previously diagnosed in 24 patients (9%). Mean FVC and FEV₁ decreased mildly after dialysis (FVC: 2.84 to 2.79 L, P < 0.01. FEV₁: 1.97 to 1.93 L, P < 0.01) Hemodialysis did not affect the FEV₁/FVC ratio or number of subjects with airflow limitation indicative of COPD (113 vs. 120, P = 0.324; n = 242). COPD is a frequent and underdiagnosed comorbidity in patients on chronic hemodialysis. Spirometry should be considered in all patients on dialysis in order to address dyspnea adequately. Hemodialysis induced a small fall in mean FEV₁ and FVC, which was more pronounced in patients with little or no fluid removal, but the FEV₁/FVC ratio and the number of subjects with airflow limitation indicative of COPD were not affected by dialysis.     

Structure and density of deposits formed on filter fibers by inertial particle deposition and bounce

The morphology and packing density of particle deposits formed by accumulation on thin steel fibers suspended in an aerosol stream were studied by confocal microscopy. Measurements were made with electrically neutral polystyrene spheres (d_P=1.3, 2.0, 2.6 and 5.2 μm) as a function of flow velocity (v=0.7–5 m/s) and fiber diameters (d_F=8 and 30 μm). Deposition under these conditions was dominated by inertia (Stokes number St=0.3–9), interception (interception parameter R=0.04–0.35) and particle bounce, with a negligible contribution from diffusion.The experiments show a systematic transition of deposit morphologies with a newly introduced particle bounce parameter β～St/R, where St and R are based on the diameter d_F of the bare fiber. Compact, forward facing deposit structures dominate in case of significant particle bounce (i.e. for β>β?, where β* represents the critical conditions for the onset of bounce on the bare fiber). Dendritic structures with pronounced sideways branching are formed at β<β*. R is of relatively little influence as an independent parameter, probably because interception occurs mostly on preexisting deposit structures with dimensions in the order of d_P.The mean porosity ε of the deposit structures was determined on the basis of contour measurements by confocal microscopy, in combination with data on the accumulated particle volume per unit fiber length (known accurately from a previous paper by Kasper, Schollmeier, Meyer, and Hoferer (2009). Once noticeable deposits had formed, ε was found to attain stable values between 0.80 at d_P=1.3 μm and 0.55 at d_p=5.2 μm.     

Primes and targets in rapid chases: Tracing sequential waves of motor activation.

Single-cell recordings have indicated that visual stimuli elicit rapid waves of neuronal activation that propagate so fast that they might be free of intracortical feedback. Here, the time course of feedforward activation was traced by measuring pointing responses to color targets preceded by color primes initiating either the same or opposite response. The early time course of priming effects was strictly time locked to prime onset and depended only on properties of the primes, but was independent of the onset times of the actual targets as well as the perceptual effects of targets on primes. Results indicated that nonoverlapping feedforward signals by primes and targets traverse the visuomotor system in a rapid chase, controlling associated motor responses in strict sequence. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Patent foramen ovale is an important predictor of adverse outcome in patients with major pulmonary embolism

BACKGROUND: Right-to-left shunt through a patent foramen ovale is frequently diagnosed by contrast echocardiography and can be particularly prominent in the presence of elevated pressures in the right side of the heart. Its prognostic significance in patients with pulmonary thromboembolism, however, is unknown. METHODS AND RESULTS: The present prospective study included 139 consecutive patients with major pulmonary embolism diagnosed on the basis of clinical, echocardiographic, and cardiac catheterization criteria. All patients underwent contrast echocardiography at presentation. The end points of the study were overall mortality and complicated clinical course during the hospital stay defined as death, cerebral or peripheral arterial thromboembolism, major bleeding, or need for endotracheal intubation or cardiopulmonary resuscitation. Patent foramen ovale was diagnosed in 48 patients (35%). These patients had a death rate of 33% as opposed to 14% in patients with a negative echo-contrast examination (P=.015). Logistic regression analysis demonstrated that the only independent predictors of mortality in the study population were a patent foramen ovale (odds ratio [OR], 11.4; P<.001) and arterial hypotension at presentation (OR, 26.3; P<.001). Patients with a patent foramen ovale also had a significantly higher incidence of ischemic stroke (13% versus 2.2%; P=.02) and peripheral arterial embolism (15 versus 0%; P<.001). Overall, the risk of a complicated in-hospital course was 5.2 times higher in this patient group (P<.001). CONCLUSIONS: In patients with major pulmonary embolism, echocardiographic detection of a patent foramen ovale signifies a particularly high risk of death and arterial thromboembolic complications.     

Nonlinear optical susceptibility of HgGa2S4

The second harmonic coefficient d36of HgGa2S4has been measured to be 5 times larger than d36(LiNbO3). The birefringence is usefully large.