Comodulation detection differences for fixed-frequency and roved-frequency maskers

This study investigated comodulation detection differences (CDD) for fixed- and roved-frequency maskers. The objective was to determine whether CDD could be accounted for better in terms of energetic masking or in terms of perceptual fusion/segregation related to comodulation. Roved-frequency maskers were used in order to minimize the role of energetic masking, allowing possible effects related to perceptual fusion/segregation to be revealed. The signals and maskers were composed of 30-Hz-wide noise bands. The signal was either comodulated with the masker (A/A condition) or had a temporal envelope that was independent (A/B condition). The masker was either gated synchronously with the signal or had a leading temporal fringe of 200 ms. In the fixed-frequency masker conditions, listeners with low A/A thresholds showed little masking release due to masker temporal fringe and had CDDs that could be accounted for by energetic masking. Listeners with higher A/A thresholds in the fixed-frequency masker conditions showed relatively large CDDs and large masking release due to a masker temporal fringe. The CDDs of these listeners may have arisen, at least in part, from processes related to perceptual segregation. Some listeners in the roved masker conditions also had large CDDs that appeared to be related to perceptual segregation.     

On‐Surface Reactive Planarization of Pt(II) Complexes

A series of Pt(II) complexes with tetradentate luminophores has been designed, synthesized, and deposited on coinage metal surfaces with the aim to produce highly planar self‐assembled monolayers. Low‐temperature scanning tunneling microscopy (STM) and density functional theory (DFT) calculations reveal a significant initial nonplanarity for all complexes. A subsequent metal‐catalyzed separation of the nonplanar moiety at the bridging unit via the scission of a C?N bond is observed, leaving behind a largely planar core complex. The activation barrier of this bond scission process is found to depend strongly on the chemical nature of both bridging group and coordination plane, and to increase from Cu(111) through Ag(111) to Au(111).     

Evidence for the Cyclodextrin Mediated Aggregation of Cyanine Dyes into Oligomers

Based on the analysis of UV/Vis-and CD spectra of several cyanine dyes in - and -cyclodextrin a case is made for the aggregation of the dyes into oligomers. The criteria for this new type of aggregates are: (i) the appearance of a concentration and temperature dependent shoulder on the high energy side of the dimer band in the UV/Vis-spectra; (ii) two oppositely signed high intensity CD absorptions, one centered at the shoulder, the other at about the energy of the monomer absorption. Calculations based on coupled-oscillator theory support the contention that chiral dye aggregates are formed in the presence of cyclodextrins, most probably trimers and tetramers. From UV/Vis- and CD-data a helically twisted sandwich structure is suggested for these aggregates. In contrast to the reported inclusion complexes these aggregates must form — at least partly — outside the chiral host.     

Synthesis and structural studies of <Emphasis Type="Italic">tris</Emphasis>-2-chlorobenzylamine and <Emphasis Type="Italic">tris</Emphasis>-2-bromobenzylamine

The tris-2-chloro and 2-bromotribenzylamines are prepared from aqueous ammonia and 2-chlorobenzyl chloride and 2-bromobenzyl bromide, respectively, in ethanol. Recrystallization yielded colorless cubes of each product. The crystal structures are each solved in space group P , and are isostructural. The tris-2-chloro compound, 1, has a = 7.4226(5) Å, b = 9.0825(7) Å, c = 14.529(1) Å, = 78.279(1), = 82.389(1), = 84.661(1), and V = 948.41(12) ų with Z = 2, and d_calc = 1.368 Mg/m³. The tris-2-bromo analog, 2, has a = 7.6569(11) Å, b = 9.0922(13) Å, c = 14.614(2) Å, = 79.286(2), = 81.777(2), = 85.401(2), and V = 987.9(2) ų with Z = 2, and d_calc = 1.762 Mg/m³. Lithium–halogen exchange experiments conducted in tetrahydrofuran at –78C using n-butyl lithium revealed that no exchange occurred for the tris-2-chloro compound, but did occur for the tris-2-bromo analog to yield tribenzylamine upon quench and work-up.     

Non-Hausdorff symmetries of C*-algebras

Symmetry groups or groupoids of C*-algebras associated to non-Hausdorff spaces are often non-Hausdorff as well. We describe such symmetries using crossed modules of groupoids. We define actions of crossed modules on C*-algebras and crossed products for such actions, and justify these definitions with some basic general results and examples.     

Comparative studies on the reactivity of molecules by atomic valences

SINDO1 calculations were performed to study the reactivity of molecules with a valence number derived from the density matrix. A comparison of valence numbers was made for selected examples of rotation barriers, substituted strained molecules, radical gas phase reactions, and acid-base reactions. Relations between valence, geometry, and energy changes are discussed.     

Ordinal notations and well-orderings in bounded arithmetic

This paper investigates provability and non-provability of well-foundedness of ordinal notations in weak theories of bounded arithmetic. We define a notion of well-foundedness on bounded domains. We show that T₂¹ and S₂² can prove the well-foundedness on bounded domains of the ordinal notations below ₀ and Γ₀. As a corollary, the class of polynomial local search problems, PLS, can be augmented with cost functions that take ordinal values below ₀ and Γ₀ without increasing the class PLS.     

A Low‐Valent Molybdenum Nitride Complex: Reduction Promotes Carbonylation Chemistry

Toward nitrogen functionalization, reactive terminal transition metal nitrides with high d‐electron counts are of interest. A series of terminal Mo^IV nitride complexes were prepared within the context of exploring nitride/carbonyl coupling to cyanate. Reduction affords the first Mo^II nitrido complex, an early metal nitride with four valence d‐electrons. The binding mode of the para‐terphenyl diphosphine ancillary ligand changes to stabilize an electronic configuration with a high electron count and a formal M?N bond order of three. Even with an intact Mo≡N bond, this low‐valent nitrido complex proves to be highly reactive, readily undergoing N‐atom transfer upon addition of CO, releasing cyanate anion.