Temperature, composition, and hydrogen isotope effect in the hydrogenation of CO on amorphous ice surface at 10-20 K

An experiment on the addition reaction of a D atom (deuteration) to CO on a cold ice surface is performed by deuterium atom exposure of three types of samples (pure solid CO, CO-capped H2O ice, and CO-H2O mixed ice) at 10-20 K. The variation of IR absorption spectra for the samples was measured by a Fourier transform infrared spectrometer during exposure to deuterium atoms. Reactions on pure solid CO were observed only at 10 K, while reactions on CO-capped H2O ice and CO-H2O mixed ice were observed to proceed even at 20 K. This indicates that the coexistence of H2O at the surface raises the reactive temperature. In addition, the experiment on H atom exposure was also carried out at 15 K to compare the reaction rate constant between the H and D atoms. The ratio of reaction rate constant kD/kH obtained is about 0.08 at 15 K. The authors provide information on the potential energy for the H+CO reaction at the surface by using the ratio kD/kH and by a model calculation of the potential tunneling with the asymmetric Eckart potential.     

Experimental and analytical investigation of liquid sheet breakup characteristics

The main objective of this research is to study analytically and experimentally the liquid sheet breakup of a flat fan jet nozzle resulting from pressure-swirling. In this study the effects of nozzle shape and spray pressure on the liquid sheet characteristics were investigated for four nozzles with different exit widths (1.0, 1.5, 2.0 and 2.5 mm). The length of liquid sheet breakup, liquid sheet velocity and the size of formed droplets were measured by a digital high speed camera. The breakup characteristics of plane liquid sheets in atmosphere are analytically investigated by means of linear and nonlinear hydrodynamic instability analyses. The liquid sheet breakup process was studied for initial sinuous and also varicose modes of disturbance. The results presented the effect of the nozzle width and the spray pressure on the breakup length and also on the size of the formed droplets. Comparing the experimental results with the theoretical ones for all the four types of nozzles, gives a good agreement with difference ranges from 4% to 12%. Also, the comparison between the obtained results and the results due to others shows a good agreement with difference ranged from 5% to 16%. Empirical correlations have been deduced describing the relation between the liquid sheet breakup characteristics and affecting parameters; liquid sheet Reynolds number, Weber number and the nozzle width.     

Programmed placement of gold nanoparticles onto a slit-type DNA origami scaffold

A novel DNA scaffold, called a DNA slit, was designed for the programmed positioning of Au nanoparticles (AuNPs), and various patterns of thiolated DNA slits were constructed. AuNPs were correctly placed at the predesigned positions in the thiolated DNA slits, indicating that the thiolated staples and the slit cavities guide the correct assembly of AuNPs.     

Two-dimensional DNA origami assemblies using a four-way connector

Two-dimensional self-assembly of DNA origami structures was carried out using a connector that has connection sites at all four edges. By utilizing this four-way connector, five and eight origami monomers were assembled to form a cruciate and a hollow square structure, respectively.     

Z-Selective Preparation of β-Monosubstituted α,β-Unsaturated Amides Using Diphenylphosphonoacetamides

The Horner-Wadsworth-Emmons reaction of diphenylphosphonoacetamides [(PhO) 2 P(O)CH 2 CONRR'] ( 2a : R, R' = CH 2 Ph; 2b : R = CH 2 Ph, R' = H; 2c : R = Me, R' = OMe) was examined. The reaction of 2a was found to be Z -selective for benzaldehyde with selectivities up to 94:6. Reagent 2b led to reasonable selectivity for both benzaldehyde (85:15) and 3-phenylpropionaldehyde (87:13), while 2c was somewhat effective only for the latter aldehyde (83:17).     

Helical DNA Origami Tubular Structures with Various Sizes and Arrangements

We developed a novel method to design various helical tubular structures using the DNA origami method. The size‐controlled tubular structures which have 192, 256, and 320 base pairs for one turn of the tube were designed and prepared. We observed the formation of the expected short tubes and unexpected long ones. Detailed analyses of the surface patterns of the tubes showed that the short tubes had mainly a left‐handed helical structure. The long tubes mainly formed a right‐handed helical structure and extended to the directions of the double helical axes as structural isomers of the short tubes. The folding pathways of the tubes were estimated by analyzing the proportions of short and long tubes obtained at different annealing conditions. Depending on the number of base pairs involved in one turn of the tube, the population of left‐/right‐handed and short/long tubes changed. The bending stress caused by the stiffness of the bundled double helices and the non‐natural helical pitch determine the structural variety of the tubes.     

Light-induced transformation of alkylurea derivatives in aqueous TiO2 dispersion

The light-induced degradation of alkylurea derivatives under simulated solar irradiation has been investigated in aqueous solutions containing TiO(2) as a photocatalyst. Herein, we will focus on how the presence of one or more methyl (or ethyl) groups on urea modifies the kinetics of disappearance and influences both the ratio and the extent of the inorganic nitrogen formation caused by different degradation pathways. In the present work, we have elucidated a mechanism for the formation of transformation products of the alkyl derivatives by combining several analytical and spectroscopic procedures and the theoretical simulation of ab initio calculations. In all cases, N-demethylation represents only a secondary pathway, while the main transformation proceeds through an unexpected cyclization, involving (m)ethyl- and di(m)ethylureas with the formation of (methyl)amino-2,3-dihydro-1,2,4-oxadiazol-3-one as the principal intermediate of the reaction (with a yield of 60 %). This behaviour is rather unexpected and in contrast with the typical photocatalyzed transformation pathways, which proceed through the formation of more simple structures.     

Synthesis of β‐monosubstituted α,β‐unsaturated amides with Z‐selectivity using diphenylphosphonoacetamides

The utility of diphenylphosphonoacetamides [(PhO)₂P(O)CH₂CONRR′] as Horner–Wadsworth–Emmons reagents was examined with five different patterns of substitution upon the amide nitrogen atom ( 2a : R, R′ = CH₂Ph; 2b : R = CH₂Ph, R′ = H; 2c : R = Me, R′ = OMe; 2d : R, R′ = Ph; 2e : R, R′ = (CH₂)₄). The reaction of 2a was found to be Z‐selective for aromatic aldehydes with selectivities up to 95:5. Reagent 2b led to reasonable selectivity for both benzaldehyde (85:15) and 3‐phenylpropionaldehyde (87:13), while 2c was somewhat effective for only the latter alkyl aldehyde (83:17). Compounds 2d and 2e exhibited slightly lower selectivities compared with 2a . © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:515–523, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20054