Energy loss rate and inelastic mean free path of low-energy electrons and positrons in condensed matter

An “optical-data model” is employed to evaluate energy loss per unit pathlength and inelastic mean free path for low-energy electrons and positrons ( 10 keV) from optical data on the medium of interest. Exchange between the incident electron and electrons in the medium is included. Results from the optical-data model are given for Al, Au, Ag, Cu, C, and polyethylene, and some comparisons are made with previous theoretical results.     

On the Distinguishability of Random Quantum States

We develop two analytic lower bounds on the probability of success p of identifying a state picked from a known ensemble of pure states: a bound based on the pairwise inner products of the states, and a bound based on the eigenvalues of their Gram matrix. We use the latter, and results from random matrix theory, to lower bound the asymptotic distinguishability of ensembles of n random quantum states in d dimensions, where n/d approaches a constant. In particular, for almost all ensembles of n states in n dimensions, p > 0.72. An application to distinguishing Boolean functions (the “oracle identification problem”) in quantum computation is given.     

The effect of head position on glottic closure in patients with unilateral vocal fold paralysis

The present study was designed to assess the effect of head position on glottic closure as reflected in airflow rates (open quotient and maximum flow declination rate), in patients with unilateral vocal fold paralysis. Ten patients, 2 males and 8 females ranging in age from 40 to 75, with a mean age of 57.3, served as subjects. Airflow measures were taken during sustained phonation of two vowels (/i/ and /a/) in 3 head positions (center, right, left). Vowels /i/ and /a/ were produced at subject's comfortable pitch and loudness, with random ordering of both vowel order and head orientation. Subjects were trained to focus eye gaze on right and left markers (70-degree angle) and a central marker at eye level directly in front of the subject. Theoretically, if turning the head during phonation alters the laryngeal anatomic relationship by bringing the vocal folds in closer proximity to one another, then airflow rate should lessen. Our results indicate that head position does not improve glottic closure in these patients, which is in contrast to previously published research.(1) Our results question the utility and underlying theoretical construct for the use of head turning as a therapeutic technique for improvement of voice in patients with unilateral vocal fold paralysis.     

Critical behavior in the relaminarization of localized turbulence in pipe flow

The statistics of the relaminarization of localized turbulence in a pipe are examined by direct numerical simulation. As in recent experimental data [J. Peixinho and T. Mullin, Phys. Rev. Lett. 96, 094501 (2006)10.1103/PhysRevLett.96.094501], the half-life for the decaying turbulence is consistent with the scaling (Rec-Re) -1, indicating a boundary crisis of the localized turbulent state familiar in low-dimensional dynamical systems. The crisis Reynolds number is estimated as Rec=1870, a value within 7% of the experimental value 1750. We argue that the frequently asked question, of which initial disturbances at a given Re trigger sustained turbulence in a pipe, is really two separate questions: the "local phase space" question (local to the laminar state) of what threshold disturbance at a given Re is needed to initially trigger turbulence, followed by the "global phase space" question of whether Re exceeds Rec at which point the turbulent state becomes an attractor.     

Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex

The HAsAsH molecule has hitherto only been proposed tentatively as a short‐lived species generated in electrochemical or microwave‐plasma experiments. After two centuries of inconclusive or disproven claims of HAsAsH formation in the condensed phase, we report the isolation and structural authentication of HAsAsH in the diuranium(IV) complex [{U(Tren^TIPS)}₂(μ‐η²:η²‐As₂H₂)] ( 3 , Tren^TIPS=N(CH₂CH₂NSiPrⁱ₃)₃; Prⁱ=CH(CH₃)₂). Complex 3 was prepared by deprotonation and oxidative homocoupling of an arsenide precursor. Characterization and computational data are consistent with back‐bonding‐type interactions from uranium to the HAsAsH π*‐orbital. This experimentally confirms the theoretically predicted excellent π‐acceptor character of HAsAsH, and is tantamount to full reduction to the diarsane‐1,2‐diide form.     

Predictive model for ice formation on superhydrophobic surfaces

The prevention and control of ice accumulation has important applications in aviation, building construction, and energy conversion devices. One area of active research concerns the use of superhydrophobic surfaces for preventing ice formation. The present work develops a physics-based modeling framework to predict ice formation on cooled superhydrophobic surfaces resulting from the impact of supercooled water droplets. This modeling approach analyzes the multiple phenomena influencing ice formation on superhydrophobic surfaces through the development of submodels describing droplet impact dynamics, heat transfer, and heterogeneous ice nucleation. These models are then integrated together to achieve a comprehensive understanding of ice formation upon impact of liquid droplets at freezing conditions. The accuracy of this model is validated by its successful prediction of the experimental findings that demonstrate that superhydrophobic surfaces can fully prevent the freezing of impacting water droplets down to surface temperatures of as low as -20 to -25 °C. The model can be used to study the influence of surface morphology, surface chemistry, and fluid and thermal properties on dynamic ice formation and identify parameters critical to achieving icephobic surfaces. The framework of the present work is the first detailed modeling tool developed for the design and analysis of surfaces for various ice prevention/reduction strategies.     

Cationic iridium complexes of the Xantphos ligand. Flexible coordination modes and the isolation of the hydride insertion product with an alkene

Reaction of the Ir(I)-Xantphos complex [Ir(κ²-Xantphos)(COD)][BAr^F₄] (Xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, Ar^F = C₆H₃(CF₃)₂) with H₂ in acetone or CH₂Cl₂/MeCN affords the Ir(III)-hydrido complexes [Ir(κ³-Xantphos)(H)₂(L)][BAr^F₄], L = acetone or MeCN, whereas in non-coordinating CH₂Cl₂ solvent dimeric [Ir(κ³-Xantphos)(H)(μ-H)]₂[BAr^F₄]₂ is formed. A common intermediate in these reactions that invokes a (σ, η²-C₈H₁₃) ligand is reported. Addition of excess tert-butylethene (tbe) to [Ir(κ³-Xantphos)(H)₂(MeCN)][BAr^F₄] results in insertion of a hydride into the alkene to form [Ir(κ³-Xantphos)(MeCN)(CH₂CH₂C(CH₃)₃)(H)][BAr^F₄], an Ir(III) alkyl-hydrido-Xantphos complex. This reaction is reversible, and heating (80 °C) results in the reformation of [Ir(κ³-Xantphos)(H)₂(MeCN)][BAr^F₄] and tbe. These complexes have been characterised by NMR spectroscopy, ESI-MS and single-crystal X-ray diffraction. They show variable coordination modes of the Xantphos ligand: cis-κ²-P,P, fac-κ³-P,O,P and mer-κ³-P,O,P with the later coordination mode like that found in related PNP-pincer complexes.     

Assessment of the electronic structure of 2,2'-pyridylpyrrolides as ligands

The ligand class 2,2'-pyridylpyrrolide is surveyed, both for its structural features and its electronic structure, when attached to monovalent K, Cu, Ag, Au, and Rh. The influence of pyrrolide ring substituents is studied, as well as the question of push/pull interaction between the pyridyl and pyrrolide halves. The π donor ability of the pyrrolide is found to be less than that of an analogous phenyl. However, in contrast to the phenyl analog, the HOMO is pyrrolide π in character for pyridylpyrrolide complexes of copper and rhodium, while it is conventionally metal localized for planar, d(8) rhodium pyridylphenyl. Monovalent three-coordinate copper complexes show great deviations from Y-shaped toward T-shaped structures, including cases where the pyridyl ligand bonds only weakly.     

Isomeric trimethylene and ethylene pendant-armed cross-bridged tetraazamacrocycles and in vitro/in vivo comparisions of their copper(II) complexes

Ethylene cross-bridged tetraamine macrocycles are useful chelators in coordination, catalytic, medicinal, and radiopharmaceutical chemistry. Springborg and co-workers developed trimethylene cross-bridged analogues, although their pendant-armed derivatives received little attention. We report here the synthesis of a bis-carboxymethyl pendant-armed cyclen with a trimethylene cross-bridge (C3B-DO2A) and its isomeric ethylene-cross-bridged homocyclen ligand (CB-TR2A) as well as their copper(II) complexes. The in vitro and in vivo properties of these complexes are compared with respect to their potential application as (64)Cu-radiopharmaceuticals in positron emission tomography (PET imaging). The inertness of Cu-C3B-DO2A to decomplexation is remarkable, exceeding that of Cu-CB-TE2A. Electrochemical reduction of Cu-CB-TR2A is quasi-reversible, whereas that of Cu-C3B-DO2A is irreversible. The reaction conditions for preparing (64)Cu-C3B-DO2A (microwaving at high temperature) are relatively harsh compared to (64)Cu-CB-TR2A (basic ethanol). The in vivo behavior of the (64)Cu complexes was evaluated in normal rats. Rapid and continual clearance of (64)Cu-CB-TR2A through the blood, liver, and kidneys suggests relatively good in vivo stability, albeit inferior to (64)Cu-CB-TE2A. Although (64)Cu-C3B-DO2A clears continually, the initial uptake is high and only about half is excreted within 22 h, suggesting poor stability and transchelation of (64)Cu to proteins in the blood and/or liver. These data suggest that in vitro inertness of a chelator complex may not always be a good indicator of in vivo stability.