Theory of asymmetric organocatalysis of Aldol and related reactions: rationalizations and predictions

Computational studies have led to models to understand some classic and contemporary asymmetric reactions involving organocatalysts. The Hajos-Parrish-Eder-Sauer-Wiechert reaction and intermolecular aldol reactions as well as Mannich reactions and oxyaminations catalyzed by proline and other amino acids, and Diels-Alder reactions catalyzed by MacMillan's chiral amine organocatalysts have been studied with density functional theory. Quantitative predictions for several new catalysts and reactions are provided.     

Effect of diffusional mass transfer on the performance of horizontal subsurface flow constructed wetlands in tropical climate conditions

The effect of mass transfer on the removal rate constants of BOD5, NH3, NO3 and TKN has been investigated in a Horizontal Subsurface Flow Constructed Wetland (HSSFCW) planted with Phragmites mauritianus. The plug flow model was assumed and the inlet and outlet concentrations were used to determine the observed removal rate constants. Mass transfer effects were studied by assessing the influence of interstitial velocity on pollutant removal rates in CW cells of different widths. The flow velocities varied between 3-46 m/d. Results indicate that the observed removal rate constants are highly influenced by the flow velocity. Correlation of dimensionless groups namely Reynolds Number (Re), Sherwood Number (Sh) and Schmidt Number (Sc) were applied and log-log plots of rate constants against velocity yielded straight lines with values beta = 0.87 for BOD5, 1.88 for NH3, 1.20 for NO3 and 0.94 for TKN. The correlation matched the expected for packed beds although the constant beta was higher than expected for low Reynolds numbers. These results indicate that the design values of rate constants used to size wetlands are influenced by flow velocity. This paper suggests the incorporation of mass transfer into CW design procedures in order to improve the performance of CW systems and reduce land requirements.     

Geometric-optics-integral-equation method for light scattering by nonspherical ice crystals

A new geometric-optics model has been developed for the calculation of the single-scattering and polarization properties for arbitrarily oriented hexagonal ice crystals. The model uses the ray-tracing technique to solve the near field on the ice crystal surface, which is then transformed to the far field on the basis of the electromagnetic equivalence theorem. From comparisons with the results computed by the finite-difference time domain method, we show that the novel geometric-optics method can be applied to the computation of the extinction cross section and single-scattering albedo for ice crystals with size parameters along the minimum dimension as small as ~6. Overall agreement has also been obtained for the phase function when size parameters along the minimum dimension are larger than ~20. We demonstrate that the present model converges to the conventional ray-tracing method for large size parameters and produces single-scattering results close to those computed by the finite-difference time domain method for size parameters along the minimum dimension smaller than ~20. The present geometric-optics method can therefore bridge the gap between the conventional ray-tracing and the exact numerical methods that are applicable to large and small size parameters, respectively.     

Modeling basal ganglia for understanding Parkinsonian reaching movements

We present a computational model that highlights the role of basal ganglia (BG) in generating simple reaching movements. The model is cast within the reinforcement learning (RL) framework with correspondence between RL components and neuroanatomy as follows: dopamine signal of substantia nigra pars compacta as the temporal difference error, striatum as the substrate for the critic, and the motor cortex as the actor. A key feature of this neurobiological interpretation is our hypothesis that the indirect pathway is the explorer. Chaotic activity, originating from the indirect pathway part of the model, drives the wandering, exploratory movements of the arm. Thus, the direct pathway subserves exploitation, while the indirect pathway subserves exploration. The motor cortex becomes more and more independent of the corrective influence of BG as training progresses. Reaching trajectories show diminishing variability with training. Reaching movements associated with Parkinson's disease (PD) are simulated by reducing dopamine and degrading the complexity of indirect pathway dynamics by switching it from chaotic to periodic behavior. Under the simulated PD conditions, the arm exhibits PD motor symptoms like tremor, bradykinesia and undershooting. The model echoes the notion that PD is a dynamical disease.     

Light-efficient photography

In this paper, we consider the problem of imaging a scene with a given depth of field at a given exposure level in the shortest amount of time possible. We show that by 1) collecting a sequence of photos and 2) controlling the aperture, focus, and exposure time of each photo individually, we can span the given depth of field in less total time than it takes to expose a single narrower-aperture photo. Using this as a starting point, we obtain two key results. First, for lenses with continuously variable apertures, we derive a closed-form solution for the globally optimal capture sequence, i.e., that collects light from the specified depth of field in the most efficient way possible. Second, for lenses with discrete apertures, we derive an integer programming problem whose solution is the optimal sequence. Our results are applicable to off-the-shelf cameras and typical photography conditions, and advocate the use of dense, wide-aperture photo sequences as a light-efficient alternative to single-shot, narrow-aperture photography.     

Envelope pulsed ultrasonic distance measurement system based upon amplitude modulation and phase modulation

A novel microcomputer-based ultrasonic distance measurement system is presented. This study proposes an efficient algorithm which combines both the amplitude modulation (AM) and the phase modulation (PM) of the pulse-echo technique. The proposed system can reduce error caused by inertia delay and amplitude attenuation effect when using the AM and PM envelope square wave form (APESW). The APESW ultrasonic driving wave form causes a phase inversion phenomenon in the relative wave form of the receiver. The phase inversion phenomenon sufficiently identifies the "measurement pulse" in the received wave forms, which can be used for accurate time-of-flight (TOF) measurement. In addition, combining a countertechnique to compute the phase shifts of the last cycle for TOF, the presented system can obtain distance resolution of 0.1% of the wavelength corresponding to the 40 kHz frequency of the ultrasonic wave. The standard uncertainty of the proposed distance measurement system is found to be 0.2 mm at a range of 50-500 mm. The APESW signal generator and phase detector of this measuring system are designed on a complex programmable logic device, which is used to govern the TOF measurement and send the data to a personal computer for distance calibration and examination. The main advantages of this APESW system are high resolution, low cost, narrow bandwidth requirement, and ease of implementation.     

Magnetic multipole line-cusp plasma generator for neutral beam injectors

The magnetic multipole line-cusp device developed by MacKenzie and associates has been adapted for use as a neutral beam ion source. It has produced high-density, large volume, quiescent, uniform hydrogen plasmas, which makes it a potential candidate for use as a plasma generator for neutral beam injectors. The device is a water-cooled cylindrical copper discharge chamber (25 cm in diameter by 36 cm long) with one end enclosed by a set of extraction grids with a 15-cm-diam multi-aperture pattern. The chamber wall serves as an anode and is surrounded by an external system of rare-earth cobalt magnets arranged in a line-cusp geometry of 12 cusps; plasma is produced by electron emission from a hot cathode assembly. This source has achieved extracted beam currents of 12 A at 18.5 kV, radial plasma density uniformities of +/-5% over a 15-cm diameter, noise levels of less than +/-0.5%, and arc efficiencies (beam current/arc power) of 0.6 A/kW.     

Gossypol disrupts embryo development in heifers

Our objectives were to determine the effects of dietary free gossypol (FG) intake on plasma and uterine gossypol concentrations and embryo development and viability before and after culture with gossypol. Fifty postpubertal Holstein heifers weighing (±SD) 406 ± 34.5 kg at 11.5 mo of age were blocked by age and body weight (BW) and randomly assigned to 1 of 3 isocaloric and isonitrogenous diets differing in their FG content: control (0 mg of FG/kg of BW), moderate (17.8 mg of FG/kg of BW), and high (36.8 mg of FG/kg of BW). Heifers were fed the diets for 70 d before superovulation and embryo collection. Superovulated heifers were flushed on d 5 after induction of ovulation, and early morulae were either stained, to determine the number and proportion of live and dead cells, or randomly assigned to an in vitro culture for 96 h in media containing either 0 or 10 μg/mL of gossypol acetic acid. Plasma and uterine gossypol concentrations increased with increasing gossypol intake. The number of low-quality embryos-ova was greater for the high than for the moderate and control diets. Embryos collected from the high diet had the least number of cells because of fewer live cells, and were smaller in diameter. Greater dietary gossypol reduced blastocyst development and extended the time to reach the blastocyst stage. Similarly, gossypol concentration at 10 μg/mL compromised in vitro development and increased the proportion of degenerated embryos at 96 h in culture. These findings provide in vivo and in vitro evidence that intake of 36.8 mg of FG/kg of BW per d and gossypol concentrations >7 μg/mL in plasma, in uterine flush, or in vitro compromise early embryo development, which might explain some of the negative effects of gossypol on the fertility of dairy cows.