The Role of Depth and 1/f Dynamics in Perceiving Reversible Figures

When confronted with a reversible figure, such as the Necker Cube, viewers experience a spontaneously changing percept. We assess the dynamic of how the human visual system resolves perceptual ambiguity in stimuli that offer multiple interpretations. Subjects observed the Necker cube for one of three viewing durations during which they pressed a key each time they perceived a change in the orientation of the cube. Manipulations of binocular disparity served as a parameter to control perceptual stability. Low-depth conditions yielded more perceptual reversals than high-depth conditions. A Fourier analysis performed on the time series of reversals show 1/f (pink) noise was evident in their power spectra. These results together with theoretical models of complex systems (e.g., Bak, Tang, & Wiesenfeld, 1987) suggest that depth information may guide our perceptual system into a self-organized state to assist us in resolving ambiguous information. Moreover, slopes of the spectra were steeper in high-depth and brief viewing conditions, suggesting that the visual system relies more on previous perceptual states and filters more white noise in these conditions.     

C-C bond formation via C-H bond activation: catalytic arylation and alkenylation of alkane segments

A new system for catalytic arylation and alkenylation of alkane segments has been developed. The ortho-tert-butylaniline substrates and 2-pivaloylpyridine may be arylated and alkenylated at the tert-butyl group, while no functionalization occurred at more reactive C-H and other bonds. Arylation and alkenylation of these substrates are achieved in the presence of Ph2Si(OH)Me and Ph-CH=CH-Si(OH)Me2, respectively, and the catalytic amount of Pd(OAc)2 and stoichiometric oxidant (Cu(OAc)2, 2 equiv) in DMF. In contrast, the ortho-i-propylaniline substrate underwent cyclopalladation, but no arylation product was obtained. Complex compound 14 was synthesized via tandem arylation-alkenylation of tert-butylaniline 11. We hypothesize that the high selectivity of this system stems from the confluence of directing effect of the Schiff base or pyridine moiety and unique reactivity properties of a phenyl-palladium acetate species (Ph-Pd-OAc.Ln).     

Manganese(III) acetate promoted acetoxylation of various α,β-unsaturated cyclopentanones

We describe the results of manganese(III) acetate based regioselective oxidation of various α,β-unsaturated cyclopentanones leading to α′-acetoxy α,β-unsaturated cyclopentanones in good yields. Products due to monophenyl and diphenyl substituted dimerization have been identified as byproducts of the reaction.     

Oxidative C-arylation of free (NH)-heterocycles via direct (sp3) C-H bond functionalization

The development of a new chemical transformation, namely oxidative C-arylation of saturated (NH)-heterocycles, is described. This reaction combines dehydrogenation and arylation in one process, leading to cross-coupling of (NH)-heterocycles and haloarenes. Typical reaction conditions involve heating the reaction partners in anhydrous dioxane at 120-150 degrees C in the presence of RhCl(CO)[P(Fur)3]2 as the catalyst and Cs2CO3 as the base. Addition of tert-butylethylene as the hydrogen acceptor increases the chemical yield by diminishing the dehalogenation pathway. This method demonstrated a good substrate scope, allowing for cross-coupling of a variety of (NH)-heterocycles (e.g., pyrrolidine, piperidine, piperazine, morpholine) and halo(hetero)arenes to afford valuable heterocyclic products in one step. The preliminary mechanistic studies provided some insight regarding the key events in the proposed catalytic cycle, including beta-hydride elimination of an amido rhodium complex and carbometalation of the resulting imine. A large kinetic isotope effect [KIE (kC-H/kC-D) = 4.3] suggests that one or both beta-hydride elimination steps are rate determining. The central role for the phosphine ligand was established in controlling the partitioning between the oxidative C-arylation and N-arylation pathways.     

Automatic tuned MRI RF coil for multinuclear imaging of small animals at 3T

We have developed an MRI RF coil whose tuning can be adjusted automatically between 120 and 128 MHz for sequential spectroscopic imaging of hydrogen and fluorine nuclei at field strength 3 T. Variable capacitance (varactor) diodes were placed on each rung of an eight-leg low-pass birdcage coil to change the tuning frequency of the coil. The diode junction capacitance can be controlled by the amount of applied reverse bias voltage. Impedance matching was also done automatically by another pair of varactor diodes to obtain the maximum SNR at each frequency. The same bias voltage was applied to the tuning varactors on all rungs to avoid perturbations in the coil. A network analyzer was used to monitor matching and tuning of the coil. A Pentium PC controlled the analyzer through the GPIB bus. A code written in LABVIEW was used to communicate with the network analyzer and adjust the bias voltages of the varactors via D/A converters. Serially programmed D/A converter devices were used to apply the bias voltages to the varactors. Isolation amplifiers were used together with RF choke inductors to provide isolation between the RF coil and the DC bias lines. We acquired proton and fluorine images sequentially from a multicompartment phantom using the designed coil. Good matching and tuning were obtained at both resonance frequencies. The tuning and matching of the coil were changed from one resonance frequency to the other within 60 s.     

Memory Across Eye-Movements: 1/f Dynamic in Visual Search

The ubiquity of apparently random behavior in visual search (e.g., Horowitz & Wolfe, 1998) has led to our proposal that the human oculomotor system has subtle deterministic properties that underlie its complex behavior. We report the results of one subject's performance in a challenging search task in which 10,215 fixations were accumulated. A number of statistical and spectral tests revealed both fractal and 1/f structure. First, scaling properties emerged in differences across eye positions and their relative dispersion (SD/M)—both decreasing over time. Fractal microstructure also emerged in an iterated function systems test and delay plot. Power spectra obtained from the Fourier analysis of fixations produced brown (1/f ²) noise and the spectra of differences across eye positions showed 1/f (pink) noise. Thus, while the sequence of absolute eye positions resembles a random walk, the differences in fixations reflect a longer-term dynamic of 1/f pink noise. These results suggest that memory across eye-movements may serve to facilitate our ability to select out useful information from the environment. The 1/f patterns in relative eye positions together with models of complex systems (e.g., Bak, Tang & Wiesenfeld, 1987) suggest that our oculomotor system may produce a complex and self-organizing search pattern providing maximum coverage with minimal effort.     

Rhodium catalyzed reaction of internal alkynes with organoborons under CO atmosphere: a product tunable reaction

Alkynes react with organoborons under a CO atmosphere in the presence of a rhodium(I) catalyst to afford mainly 5-aryl-2(5H)-furanones, α,β-unsaturated ketones, and indanones. The product selectivity can be tuned by modifying the reaction conditions.     

Laurenyne,a new acetylene from Laurencia obtusa: crystal structure and absolute configuration

Laurenyne, a new chloroacetylene from the red form of the alga Laurencia obtusa has been identified and its crystal structure determined.