Inverse semigroup actions as groupoid actions

To an inverse semigroup, we associate an étale groupoid such that its actions on topological spaces are equivalent to actions of the inverse semigroup. Both the object and the arrow space of this groupoid are non-Hausdorff. We show that this construction provides an adjoint functor to the functor that maps a groupoid to its inverse semigroup of bisections, where we turn étale groupoids into a category using algebraic morphisms. We also discuss how to recover a groupoid from this inverse semigroup.     

A copper(II)-catalyzed,sequential Michael–aldol reaction for the preparation of 1,2-dihydroquinolines

A copper(II)-catalyzed, sequential Michael addition-aldol condensation reaction of N-carboxybenzyl-protected aminobenzaldehyde with various α,β-unsaturated N-acyl pyrroles is described. Substrate scope was found to include both aryl and aliphatic N-acyl pyrroles as the Michael acceptors, and isolated product yields as high as 93% were observed. The use of acetonitrile as the reaction solvent proved to be crucial for catalysis, both to function as a labile ligand for copper, as well as an agent to minimize hydrolytic catalyst poisoning.     

Asynchronous glimpsing of speech: Spread of masking and task set-size

Howard-Jones and Rosen [(1993). J. Acoust. Soc. Am. 93, 2915-2922] investigated the ability to integrate glimpses of speech that are separated in time and frequency using a "checkerboard" masker, with asynchronous amplitude modulation (AM) across frequency. Asynchronous glimpsing was demonstrated only for spectrally wide frequency bands. It is possible that the reduced evidence of spectro-temporal integration with narrower bands was due to spread of masking at the periphery. The present study tested this hypothesis with a dichotic condition, in which the even- and odd-numbered bands of the target speech and asynchronous AM masker were presented to opposite ears, minimizing the deleterious effects of masking spread. For closed-set consonant recognition, thresholds were 5.1-8.5?dB better for dichotic than for monotic asynchronous AM conditions. Results were similar for closed-set word recognition, but for open-set word recognition the benefit of dichotic presentation was more modest and level dependent, consistent with the effects of spread of masking being level dependent. There was greater evidence of asynchronous glimpsing in the open-set than closed-set tasks. Presenting stimuli dichotically supported asynchronous glimpsing with narrower frequency bands than previously shown, though the magnitude of glimpsing was reduced for narrower bandwidths even in some dichotic conditions.     

UV/Vis Spectral Study of the Self-aggregation of Pinacyanol Chloride in Ethanol–Water Solutions

The concentration dependent self-aggregation of 1,1′-diethyl-2,2′-carbocyanine chloride (pinacyanol chloride dye) in 7.5% (v/v) ethanol + 92.5% water solution in the range of 10⁻⁶–10⁻³ mol⋅dm⁻³ has been investigated by quantitative UV/vis and derivative spectroscopy. Bands with maxima at 601, 546, 522, and 507 nm could be attributed, respectively, to the monomer, a sandwich-type dimer, a vibronic overtone of the dimer, and a higher aggregate, most probably a stacked trimeric form of the dye. Using the PeakFit program, the overlapping bands were separated and analyzed for all concentrations studied. From the spectral fitting routine, extinction coefficients of 192,000, 156,000, and 282,000 cm⁻¹⋅mol⁻¹⋅dm³ were determined for the monomer, dimer and trimer respectively.     

Pseudo-distances on symplectomorphism groups and applications to flux theory

Starting from a given norm on the vector space of exact 1-forms of a compact symplectic manifold, we produce pseudo-distances on its symplectomorphism group by generalizing an idea due to Banyaga. We prove that in some cases (which include Banyaga’s construction), their restriction to the Hamiltonian diffeomorphism group is equivalent to the distance induced by the initial norm on exact 1-forms. We also define genuine “distances to the Hamiltonian diffeomorphism group” which we use to derive several consequences, mainly in terms of flux groups.     

Excited State Isomerization of Small Polyeneiminium Ions - The Influence of Initial Torsion and Methyl Substitution on Md-Calculated Reaction Dynamics

Ultrafast photochemical reactions are assumed to progress via a direct crossing of the potential energy surfaces of the ground and excited state. Simulations on an adiabatically corrected Born-Oppenheimer surface of the first excited state of the 3- cis -penta-3,5-dieniminium cation and its 2-methyl derivative form have been performed with high level CASSCF methodology and a modified MD routine to study the cis-trans isomerization of the central double bond. The calculations show that the dynamics depend not only on the slope of the potential energy surface with its two dominant degrees of freedom, double bond stretching and rotation. For fast isomerization an effective coupling of these modes is also necessary. Methyl substitution and an additional initial twist can significantly accelerate this process. The interrelationship between the stretching and torsional modes is discussed in detail.     

Masked detection and discrimination of tone sequences under conditions of monaural and binaural masking release

Experiment 1 examined detection and discrimination of monaural four-tone sequences composed of 400-, 500-, and 625-Hz sinusoids. In the baseline conditions, the masker was monaural composed of 25-Hz-wide bands of random noise centered on 320, 400, 500, 625, and 781 Hz. In the binaural masking release conditions, the noise was presented diotically. In the monaural masking release conditions, the noise was presented to the same ear as the signal, but it was comodulated. Tones had half-amplitude durations of 30, 60, or 150 ms. There was no delay between successive tones, so the rate of frequency change depended on tone duration. Listeners discriminated between sequences composed of 500-400-625-500 Hz and 500-625-400-500 Hz. Discrimination results were poor for rapid sequences in both monaural and binaural masking release conditions relative to baseline conditions. Results from experiment 2 indicated that poor discrimination for rapid sequences could also occur in the baseline conditions, provided that the frequency separation among tonal components was small. Sluggish processing in the present paradigm was not restricted to conditions relying on binaural cues. It is argued that sluggishness may reflect a long temporal window in monaural and binaural masking release conditions or an interaction between poor cue quality and task difficulty.     

Effect of soluble polymer binder on particle distribution in a drying particulate coating

Soluble polymer is frequently added to inorganic particle suspensions to provide mechanical strength and adhesiveness to particulate coatings. To engineer coating microstructure, it is essential to understand how drying conditions and dispersion composition influence particle and polymer distribution in a drying coating. Here, a 1D model revealing the transient concentration profiles of particles and soluble polymer in a drying suspension is proposed. Sedimentation, evaporation and diffusion govern particle movement with the presence of soluble polymer influencing the evaporation rate and solution viscosity. Results are summarized in drying regime maps that predict particle accumulation at the free surface or near the substrate as conditions vary. Calculations and experiments based on a model system of poly(vinyl alcohol) (PVA), silica particles and water reveal that the addition of PVA slows the sedimentation and diffusion of the particles during drying such that accumulation of particles at the free surface is more likely.     

Novel octaketide macrolides related to 6-deoxyerythronolide B provide evidence for iterative operation of the erythromycin polyketide synthase

BACKGROUND: The macrolide antibiotic erythromycin A, like other complex aliphatic polyketides, is synthesised by a bacterial modular polyketide synthase (PKS). Such PKSs, in contrast to other fatty acid and polyketide synthases which work iteratively, contain a separate set or module of enzyme activities for each successive cycle of polyketide chain extension, and the number and type of modules together determine the structure of the polyketide product. Thus, the six extension modules of the erythromycin PKS (DEBS) together catalyse the production of the specific heptaketide 6-deoxyerythronolide B. RESULTS: A mutant strain of the erythromycin producer Saccharopolyspora erythraea, which accumulates the aglycone intermediate erythronolide B, was found unexpectedly to produce two novel octaketides, both 16-membered macrolides. These compounds were detectable in fermentation broths of wild-type S. erythraea, but not in a strain from which the DEBS genes had been specifically deleted. From their structures, both of these octaketides appear to be aberrant products of DEBS in which module 4 has 'stuttered', that is, has catalysed two successive cycles of chain extension. CONCLUSIONS: The isolation of novel DEBS-derived octaketides provides the first evidence that an extension module in a modular PKS has the potential to catalyse iterative rounds of chain elongation like other type I FAS and PKS systems. The factors governing the extent of such 'stuttering' remain to be determined.     

Circular dichroism and theoretical calculations of pinacyanol dimer inclusion in γ-cyclodextrin

Aggregation of pinacyanol chloride is strongly enhanced through inclusion into γ-cyclodextrin, which was studied using both UV/Visible, derivative and Circular Dichroism (CD) spectroscopy. The intensities at 546 and at 507 nm were increased with the growing ratio of γ-cyclodextrin to dye. Both aggregates were shown to be optically active. CD spectra with two and three oppositely signed excitonic bands were shown. The structures of the aggregates have been analysed and discussed in terms of qualitative H-type aggregation and quantitative based on OSCI program. Applying eight different parameter sets aggregates of pinacyanol chloride ranging in size from 2 to 20 dye molecules were considered. The calculated energy splitting was adjusted, via the transition dipole length, to the experimentally observed band shift. Rotational strengths associated with the CD absorptions were calculated and used to obtain an estimate of the inherent twist of the dimer aggregate inside the γ-cyclodextrin cavity.