Ni-catalyzed [3+2+2] cycloaddition of ethyl cyclopropylideneacetate and 1,3-diynes. Application to the three-component cycloaddition

The Ni-catalyzed [3+2+2] cocyclization between ethyl cyclopropylideneacetate (1) and 1,3-diynes afforded cycloheptadiene derivatives. The three-component reaction of 1, 1,3-diynes, and alkynes proceeded with good yield and high selectivity. Scope of the substrates was studied, and the origin of chemo- and regioselectivity of the reaction is discussed.     

Effect of thermal treatment on the photocatalytic degradation of ethylene,trichloroethylene, and chloroform

The thermal treatment of TiO₂ pellets prepared by the sol–gel method decreased the photocatalytic activity. The activity divided by the specific surface area of the pellets for the complete mineralization of ethylene or chloroform was maximized at the firing temperature of 400°C. For the photocatalytic degradation of trichloroethylene (TCE), most of them were converted to chlorinated by-products, such as dichloroacetic acid, chloroform, and phosgene, and the stoichiometric ratio of [CO₂]_formed/[TCE]_degraded showed a maximal value at 400°C. The electron spin resonance (ESR) spin-trapping with 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) in the flow injection system indicated that firing at 400°C gave the highest signal intensity of DMPO–OH adducts. These findings indicated that the OH radical was produced most effectively on the TiO₂ fired at 400°C, which would be related to the content of anatase and rutile. Concerning the formation of chlorinated by-products from TCE, more dichloroacetic acid (DCAA) were detected and less CHCl₃ and COCl₂ were formed at lower firing temperatures, suggesting that the branching ratio of chloroethoxy radicals to the formation of DCAA or CHCl₃ and COCl₂ by C–C bond scission depended on the firing temperature.     

Isotope effects in the dissociation of the B 1A1 state of SiH2, SiHD, and SiD2 using three-dimensional wave packet propagation

Dissociations after the A 1B1-->B 1A1 photoexcitation of SiH2, SiHD, and SiD2 were studied to investigate excited-state dynamics and effects of the initial vibrational state. The cross section (sigma) for the photodissociation relative to SiH2(B)-->Si(1D)+H2 and the rovibrational population of the H2 fragment were computed using the wave packet propagation technique based on the three-dimensional potential energy surfaces (PESs) of the A and B electronic states and the transition dipole surfaces, which were reported in our previous paper [J. Chem. Phys. 122, 144307 (2005)]. The photodissociation spectrum consists of a broadband and a number of sharp peaks. For SiH2 and SiD2, the sharp peaks correspond to the resonance structure of the vibrational levels of the B state and the broadbands are nearly independent of the photon energy. The broadband for SiHD increases steeply with the photon energy above 30,000 cm(-1). The flux leaving the computational grid for SiH2 and SiD2 consists of at least two components, whereas that for SiHD consists of only a faster component. These large isotope effects were discussed based on the valley to the dissociation channel on PES and the difference in the position of the initial wave packet for three isotopomers.     

Mass spectrometric strategy for the characterization of lipooligosaccharides from Neisseria gonorrhoeae 302 using FTICR

The lipooligosaccharides (LOS) of Neisseria gonorrhoeae 302 were profiled using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Using techniques developed in this laboratory, the topology and some of the linkages of the LOS were determined. Mass spectrometric analysis in the negative ion mode yielded a glycoform of the composition: Hex3 Hep2 Hxn1 PEA1 KDO2 DPLA. The composition was confirmed through exact mass measurements, which showed only a 2 ppm error between the exact mass and theoretical mass. Although the core structure has been postulated previously, the positioning of the three hexose moieties were in question for this particular strain of N. gonorrhoeae. Topology assignment was performed through collision-induced dissociation analysis of the O-deacylated glycoform in the negative ion mode followed by submission to the saccharide topology analysis tool (STAT) computer program, which confirmed the topology assignment. It was found that the three hexoses were added to the Hep[I] of the conserved core of N. gonorrhoeae in a linear fashion, while Hep[II] remains unbranched. Linkage position analysis was performed through application of a mild acid hydrolysis technique followed by collision-induced dissociation of the sodiated precursor ions, yielding a 1 --> 4 linkage between the terminating and penultimate hexoses.     

A carbaboranylmercuric salt catalyzed reaction; highly regioselective cycloisomerization of 1,3-dienes

The combination of carbaboranylmercuric chloride (new type of bulky Lewis acid) and silver triflate efficiently catalyzes cycloisomerization of 1,3-dienes at room temperature. The catalytic system gives allyl-substituted azacycles and cycloalkanes in excellent yields with high to complete regioselectivity.     

Prospects for tertiary structure prediction of RNA based on secondary structure information

We developed a method, called RNA Assembler using Secondary Structure Information Effectively (RASSIE), for predicting RNA tertiary structures using known secondary structure information. We attempted a fragment assembly-based method that uses a secondary structure-based fragment library. For several typical target structures such as stem-loops, bulge-loops, and 2-way junctions, our method provided numerous good quality candidate structures in less computational time than previously proposed methods. By using a high-resolution potential energy function, we were able to select good predicted structures from candidate structures. This method of efficient conformational search and detailed structure evaluation using high-resolution potential is potentially useful for the tertiary structure prediction of RNA.     

Bottom-up Synthesis and Thread-in-Bead Structures of Finite (n,0)-Zigzag Single-Wall Carbon Nanotubes

The last remaining synthetic target of finite single-wall carbon nanotube models, the zigzag nanotube, has been accomplished through bottom-up chemical synthesis. The zigzag nanotube was synthetically accessible without constructing long-sought yet elusive cyclacene structures but with a cycloarylene structure by devising its cutout positions. The persistent tubular shape was also perfected in this last model by cyclization of zigzag-shaped aromatic molecules with a synchronous topological arrangement. The crystal structure of this nanotube further revealed an entangled supramolecular assembly, which showed a novel way to align nanotube molecules by utilizing their open-end functional groups in a thread-in-bead molecular assembly.     

Method validation by interlaboratory studies of improved hydrophilic oxygen radical absorbance capacity methods for the determination of antioxidant capacities of antioxidant solutions and food extracts

Hydrophilic oxygen radical absorbance capacity (H-ORAC) is a method for evaluating antioxidant capacities of solutions of hydrophilic compounds. In this study, we improved the original method for H-ORAC determination, and evaluated the precision of the two improved methods (methods A and B) by interlaboratory studies using 5 antioxidant solutions and 5 food extracts as test samples. An interlaboratory study of method A, in accordance with the harmonized protocol, demonstrated satisfactory performance (intermediate precision relative standard deviations (RSD(int)) ranging from 4.6 to 18.8%; the reproducibility relative standard deviations (RSD(R)) ranging from 7.0 to 21.1%, and the HorRat values ranging from 0.40 to 1.93). However, methodological problems remained, and a further improved method, method B, was thus developed. An interlaboratory study of method B by 5 participating laboratories showed better intermediate precision and reproducibility (RSD(int) and RSD(R) ranging from 1.8 to 9.4%, and from 4.4 to 13.8%, respectively), and all HorRat values for the test samples were less than 1.3, suggesting good performance for the H-ORAC measurement.     

A color-coded backlighted defocusing digital particle image velocimetry system

Defocusing digital particle image velocimetry (DDPIV), as a true three-dimensional (3D) measurement technique, allows for the measurement of 3D velocities within a volume. Initially designed using a single CCD and 3-pinhole mask (Willert and Gharib in Exp Fluids 12:353–358, 1992), it has evolved into a multi-camera system in order to overcome the limitations of image saturation due to multiple exposures of each particle. In order to still use a single camera and overcome this limitation, we have modified the original single CCD implementation by placing different color filters over each pinhole, thus color-coding each pinhole exposure, and using a 3-CCD color camera for image acquisition. Due to the pinhole mask, there exists the problem of a significant lack of illumination in a conventional lighting setup, which we have solved by backlighting the field-of-view and seeding the flow with black particles. This produces images with a white background superimposed with colored triple exposures of each particle. A color space linear transformation is used to allow for accurate identification of each pinhole exposure when the color filters’ spectrum does not match those of the 3-CCD color camera. Because the imaging is performed with a multi-element lens instead of a single-element lens, an effective pinhole separation, d _e, is defined when using a pinhole mask within a multi-element lens. Calibration results of the system with and without fluid are performed and compared, and a correction of the effective pinhole separation, d _e, due to refraction through multiple surfaces is proposed. Uncertainty analyses are also performed, and the technique is successfully applied to a buoyancy-driven flow, where a 3D velocity field is extracted.     

Can a linearly polarized light beam polarize atomic spin?

Lax et al. [Phys. Rev. 11 (1975) 1365] discovered that a light beam in vacuum is not a transverse wave but does have a longitudinal field component. We investigate atomic and molecular electric dipole transitions induced by such a light beam, in particular, linearly polarized in a transverse plane. We derive the selection rules and the transition rates for various quantization axes using the paraxial approximation up to the first order of 1/kw, where k is the wave number and w is the transverse size of the light beam. The light beam is able to yield atomic spin polarization in the direction perpendicular to both the optical axis and the transverse electric field, and its magnitude is approximately 1/kw times that generated by a circularly polarized light wave with the similar intensity.