Evolving P450pyr hydroxylase for highly enantioselective hydroxylation at non-activated carbon atom

Directed evolution of a monooxygenase to achieve very high enantioselectivity for hydroxylation at non-activated carbon atoms is demonstrated for the first time, where a triple mutant of P450pyr hydroxylase is obtained via determination of enzyme structure, iterative saturation mutagenesis, and high-throughput screening with a MS-based ee assay to increase the product ee from 53% to 98% for the hydroxylation of N-benzyl pyrrolidine to (S)-N-benzyl 3-hydroxypyrrolidine.     

Simple Synthesis of Modafinil Derivatives and Their Anti-inflammatory Activity

Simple synthesis of modafinil derivatives and their biological activity are described. The key synthetic strategies involve substitution and coupling reactions. We determined the anti-inflammatory effects of modafinil derivatives in cultured BV2 cells by measuring the inhibition of nitrite production and expression of iNOS and COX-2 after LPS stimulation. It was found that for sulfide analogues introduction of aliphatic groups on the amide part (compounds 11a-d) resulted in lower anti-inflammatory activity compared with cyclic or aromatic moieties (compounds 11e-k). However, for the sulfoxide analogues, introduction of aliphatic moieties (compounds 12a-d) showed higher anti-inflammatory activity than cyclic or aromatic fragments (compounds 12e-k) in BV-2 microglia cells.     

Spreading of inkjet droplet of non-Newtonian fluid on solid surface with controlled contact angle at low Weber and Reynolds numbers

The dynamics of inkjet droplet of non-Newtonian fluid on glass substrates was investigated experimentally and compared with that of Newtonian fluid. The non-Newtonian fluids used here were 100 ppm solutions of polyethylene oxide (300k, 600k and 900k) dissolved in the 1:1 mixture of water and glycerin. Weber number (We) was 2–35 and Ohnesorge number was fixed at 0.057 ± 0.003. The wettability of solid substrate was also varied. The diameter of inkjet droplets in the present study was about 50 μm and was much smaller than the size of the previous studies on drop impact. Due to the development of a thin and long thread at the rear of the main drop the jetting window of polymer solution was much narrower than that of Newtonian fluid, and hence the experimental range of Weber number was restricted. The impact scenarios of non-Newtonian inkjet droplets were found to be qualitatively different from those of Newtonian droplets during the receding phase while they were almost the same as the Newtonian fluid case during the kinematic phase. The spreading diameter at the equilibrium was well correlated with the modified Weber number (We′ = We/(1 − cos θ_eq)) as in the case of Newtonian fluid, where θ_eq is the equilibrium contact angle. The similarity or disparity between the Newtonian and non-Newtonian cases was discussed considering the conformation of polymer chains during each stage of drop deformation.     

Hyperbranched polymers from propargyloxysilanes: New types of acetylenic resins

New hyperbranched polymers ( 1P – 3P ) from propargyloxysilanes ( 1 – 3 ) are described. The propargyloxysilanes were prepared from readily available reagents in 53–61% yields. The polymerizations were clean, one‐pot hydrosilylation processes catalyzed by Pt/C that were typically complete within 3 h. The polymers contained pendant acetylenic groups that underwent thermally induced crosslinking reactions. Heating the polymers to 1300 °C in flowing nitrogen resulted in weight losses ranging from 33 to 66%. Methyl substitution resulted in lower thermal stability. Further modification of the polymers was demonstrated by the reaction of 1P and 2P with phenylethynyldimethylsilane in the presence of a Pt catalyst. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3383–3391, 2001     

Synthesis of lariat ether carboxylic acids based on dibenzo‐16‐crown‐5

Synthetic routes to forty‐seven dibenzo‐16‐crown‐5 compounds with pendant carboxylic acid groups are reported. When taken together with previously described lariat ether carboxylic acids, these new compounds provide several series with systematic structural variations including changes in the identity and attachment site(s) of one or more lipophilic groups and the length of the spacer that connects the carboxylic acid group to the polyether framework.     

Application of the multiensemble sampling to the hydration free energy

We demonstrate the feasibility of using multiensemble sampling method (MESM) to determine the free energy difference between two far states for which the configurational distributions do not overlap at all. The MESM is a recently developed non‐Boltzmann sampling technique. The free energy of charging a sodium ion in water is accurately calculated in a single simulation, introducing nine intermediate ionic states. This is due to the ability of the method to explore the relevant parts of configuration space equally for every state, and this ability comes from the universality of weighting function W and the simplicity in adjusting its parameters. Detailed procedures of adjusting the parameters are presented. The comparison with a free energy perturbation method (FEPM) shows that the MESM is more reliable and efficient. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1004–1009, 2001     

Fission Mode Description of Mass Distributions for Fissioning Systems Ranging from Mass 230 to 262

Data on fragment mass yields in spontaneous and thermal neutron induced fission of wide range of nuclides from light actinides through heavy actinides were analyzed and completely described as mass distribution parameters, based on the concept of multimodal fission. The evidence that supports the existence of multi-components in the mass distribution of fission fragments, bimodal asymmetric mode in light actinide fission, bimodal symmetric mode in heavy actinide fission, and the existence of the boundaries of fission asymmetry has been obtained.     

Study on Reduction of Energy Consumption in Pulsed Corona Discharge Process for NOx Removal

We investigated the reduction of electrical energy consumption in thepulsed corona discharge process for the removal of nitrogenoxides. Hydrocarbon chemical additives used in the laboratory-scaleexperiment are responsible for the enhancement of the NO conversionthrough the chain reactions of free radicals, such as, R, RCO, RO,and others. Electrical energy consumption per converted NO moleculehas a minimum value of 17 eV when pentanol is injected. When ethyleneand propylene are injected, 30 and 22 eV of electrical energy consumptionare required for the conversion of a NO molecule, respectively. The ratioof the pulse-forming capacitance (C_e) to the reactor capacitance (C_R)plays an important role in the energy transfer efficiency to thereactor. The maximum energy transfer efficiency of approximately 72%could be obtained by the pulse-forming capacitance, which is 3.4 timeslarger than the reactor capacitance; the maximum NO conversionefficiency was also observed with the same condition.     

Numerical approximation of the Smagorinsky model by a two-level method

A two-level method for discretizing the Smagorinsky model for the numerical simulation of turbulent flows is proposed. In the two-level algorithm, the solution to the fully nonlinear coarse mesh problem is utilized in a single-step linear fine mesh problem. When modeling parameters are chosen appropriately, the error in the two-level algorithm is comparable to the error in solving the fully nonlinear problem on the fine mesh. We provide an a priori error estimate for the two-level method, which yields appropriate scalings between the coarse and fine mesh-sizes (H and h, respectively), and the radius of the spatial filter used in the Smagorinsky model (δ). In addition, we provide an algorithm in which a coarse mesh correction is performed to further enhance the accuracy. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Evaluation of transient turbulent flow fields using digital cinematographic particle image velocimetry

This paper describes an experimental development for temporal and spatial reconstruction of continuously varying flow fields by means of digital cinematographic particle image velocimetry (PIV). The system uses a copper-vapor laser illumination synchronized with a high-speed camera, and continuously samples at 250 fps to measure transient and non-periodic turbulent flows with relatively low frequencies, i.e., the surf zone turbulence produced by depth-limited wave break in a long laboratory flume. The use of the developed PIV system comprehensively records the temporal development of both phase-averaged and instantaneous turbulent vortex flows descended from the breaking waves to the bottom. Also, the measured power spectra show harmonic frequencies, ranging from the orbital frequency of 0.5 Hz up to the order of 5 Hz, and the well-known −5/3 dependence upon the turbulence fluctuation frequencies thereafter. Received: 2 December 1999/Accepted: 6 September 2000