An Effective Preparation of Sulfonyl‐ or Sulfinyl‐Substituted Fluorinated Alkenes and their Stereoselective Addition–Elimination Reactions with Organocuprates

Treatment of trifluorovinyl‐ or pentafluoropropen‐1‐yl sulfone or sulfoxide, which are easily prepared from commercially available 1,2‐dibromofluoroalkanes, with various organocuprates affords substitution or β‐reduction products in good to excellent yields through an addition–elimination reaction sequence.     

Electropolymerization of 9,9-difluorofluorene in BF3-OEt2 toward a photostable n-type material

Electropolymerization of 9,9-difluorofluorene was successfully carried out in boron trifluoride-ethylether complex (BF₃-OEt₂, BFEE). The obtained polymer, poly(9,9-difluorofluorene) (PFF) showed a good n-type character by cyclic voltammetric analysis owing to the existence of an electronegative difluoromethylene bridge. In addition, PFF exhibited better photostability than its hydrogenated analogue, poly(fluorene) (PF), in photoluminescence measurement.     

Evaluation of docking calculations on X-ray structures using CONSENSUS-DOCK

We are participating in the challenge of identifying active compounds for target proteins using structure-based virtual screening (SBVS). We use an in-house customized docking program, CONSENSUS-DOCK, which is a customized version of the DOCK4 program in which three scoring functions (DOCK4, FlexX and PMF) and consensus scoring have been implemented. This paper compares the docking calculation results obtained using CONSENSUS-DOCK and DOCK4, and demonstrates that CONSENSUS-DOCK produces better results than DOCK4 for major X-ray structures obtained from the Protein Data Bank (PDB).     

TiO2 nanotube, nanowire, and rhomboid-shaped particle thin films fixed on a titanium metal plate

Titanium dioxide thin films having various nanostructures could be formed by various treatments on sodium titanate nanotube thin films approximately 5 μm thick fixed on titanium metal plates. Using an aqueous solution with a lower hydrochloric acid concentration (0.01 mol/L) and a higher reaction temperature (90 °C) than those previously employed, we obtained a hydrogen titanate nanotube thin film fixed onto a titanium metal plate by H⁺ ion-exchange treatment of the sodium titanate nanotube thin film. Calcination of hydrogen titanate nanotube thin films yielded porous thin films consisting of anatase nanotubes, anatase nanowires, and anatase nanoparticles grown directly from the titanium metal plate. H⁺ ion-exchange treatment of sodium titanate nanotube thin films at 140 °C resulted in porous thin films consisting of rhomboid-shaped anatase nanoparticles.     

A bouncing droplet on an inclined hydrophobic surface

Abstract  

A trajectory of a water droplet of volume 0.4 μL impacting and bouncing on the hydrophobic surface (143°) inclined with 12° is presented. The photograph was taken with a 35 mm format digital SLR camera in a long-time exposure of 2.5 s illuminated with a couple of continuous point lighting. Also, a selected comparison is shown for snapshots of a bouncing millimetric droplet, having volume of 10 μL, inclined angle of 15° and contact angle of 147°, during the first impact between the experimental results which were recorded with a high-speed camera at 1,222 frames/s and the 3D computation (using a Volume-of-Fluid method on 330 × 70 × 35 computational grids with dt = 1.0 × 10⁻⁴ s) which was carried out with FLUENT software. At the impact the droplet is found to deform and then dissipate the energy due to the surface tension.     

The Rossby wave extra invariant in the physical space

It was found out in 1991 that the Fourier space dynamics of Rossby waves possesses an extra positive-definite quadratic invariant, in addition to the energy and enstrophy. This invariant is similar to the adiabatic invariants in the theory of dynamical systems. For many years, it was unclear if this invariant—known only in the Fourier representation—is physically meaningful at all, and if it is, in what sense it is conserved. Does the extra conservation hold only for a class of solutions satisfying certain constraints (like the conservation in the Kadomtsev-Petviashvili equation)? The extra invariant is especially important because this invariant (provided it is meaningful) has been connected to the formation of zonal jets (like Jupiter’s stripes).In the present paper, we find an explicit expression of the extra invariant in the physical (or coordinate) space and show that the invariant is indeed physically meaningful for any fluid flow. In particular, no constraints are needed. The explicit form also enables us to note several properties of the extra invariant.     

Improvement of depth resolution in XPS analysis of fluorinated layer using C60 ion sputtering

Depth profile of C₆₀ ion-used X-ray photoelectron spectroscopy (XPS) was studied on fluorinated organic layers with different thicknesses. We found that the depth resolution decreased, the sputtering rate went down and the surface turned rough as the layer thickness increased. This is because carbon-rich layer was formed on the surface by cross-linking reaction of the polymer and/or accumulation of degraded C₆₀ through continuous sputtering. Surprisingly, the high sputtering rate drastically improved the resolution of the analysis. The rate over 48.7 nm/min did not show any deterioration on the depth resolution, the sputtering rate and surface smoothness.     

Novel oxidation reaction of prochlorperazine with bromate in the presence of synergistic activators and its application to trace determination by flow injection/spectrophotometric method

Valve-based comprehensive two-dimensional gas chromatography (GC × GC) is one of the most compact, robust, and inexpensive GC × GC instrument designs. The major drawback of a valve-based modulation configuration lies in diminished detection sensitivity. This loss in sensitivity is because under typical operating conditions the fraction of the first column (i.e., column 1) effluent transferred to the second column (i.e., column 2) is likely to be ∼5-10%. To address this loss in sensitivity, we report the development of a unique total-transfer (i.e., 100%) valve-based GC × GC, without adding complexity to the instrumentation. The new instrument design relies upon simply blocking one of the appropriate ports of the high-speed six-port diaphragm valve that is used as the modulator between columns 1 and 2. The modulation period and difference in head pressure between columns 1 and 2 are found to be the two primary variables that are controlled to provide good detection sensitivity and 100% mass transfer from column 1 to column 2. The detection sensitivity is better with a longer the modulation period. A limit of detection of 0.03 ng/μl was obtained for octane. This sensitive GC × GC configuration is also shown to provide acceptable separation peak capacity, with good separations achieved for real complex samples: gasoline and Eucalyptus oil, where compounds were spread out over much of the two-dimensional separation space. In principle, this total-transfer, valve-based GC × GC is more portable and less expensive than currently available GC × GC instrumentation.     

Monoterpene constituents from Cistanche tubulosa--chemical structures of kankanosides A-E and kankanol-

Four new iridoid glycosides, kankanosides A (1), B (2), C (3), and D (4), a chlorinated iridoid, kankanol (5), and an acyclic monoterpene glycoside, kankanoside E (6), were isolated from the methanolic extract of dried stems of Cistanche tubulosa (SCHRENK) R. WIGHT (Orobanchaceae) together with 16 known compounds. The structures of these new compounds (1-6) were determined on the basis of the chemical and physicochemical evidence.     

Differences between the internal energy depositions induced by collisional activation and by electron transfer of W(CO)6(2+) ions on collision with Ar and K targets

Doubly charged tungsten hexacarbonyl W(CO)(6) (2+) ions were made to collide with Ar and K targets to give singly and doubly charged positive ions by collision-induced dissociation (CID). The resulting ions were analyzed and detected by using a spherical electrostatic analyzer. Whereas the doubly charged fragment ions resulting from collisional activation (CA) were dominant with the Ar target, singly charged fragment ions resulting from electron transfer were dominant with the K target. The internal energy deposition in collisionally activated dissociation (CAD) evaluated with the Ar target was broad and decreased with increasing internal energy. The predominant peaks observed with the K target were associated with singly charged W(CO)(2) (+) and W(CO)(3) (+) ions: these ions were not the result of CA, but arose from dissociation induced by electron transfer (DIET). The internal energy deposition resulting from the electron transfer was very narrow and centered at a particular energy, 7.8 eV below the energy level of the W(CO)(6) (2+) ion. This narrow internal energy distribution was explained in terms of electron transfer by Landau-Zener potential crossing at a separation of 5.9 x 10(-8) cm between a W(CO)(6) (2+) ion and a K atom, and the coulombic repulsion between singly charged ions in the exit channel. A large cross section of 1.1 x 10(-14) cm(2) was estimated for electron capture of the doubly charged W(CO)(6) (2+) ion from the alkali metal target, whose ionization energy is very low. The term "collision-induced dissociation," taken literally, includes all dissociation processes induced by collision, and therefore encompasses both CAD and DIET processes in the present work. Although the terms CID and CAD have been defined similarly, we would like to propose that they should not be used interchangeably, on the basis that there are differences in the observed ions and in their intensities with Ar and K targets.