Mechanism of BPh3-Catalyzed N-Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane

BPh₃ catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO₂ and PhSiH₃; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C₆F₅)₃ shows little or no activity. ¹¹B NMR spectra suggested the generation of [HBPh₃]⁻. The detailed mechanism of the BPh₃-catalyzed N-methylation of N-methylaniline ( 1 ) with CO₂ and PhSiH₃ was studied by using DFT calculations. BPh₃ promotes the conversion of two substrates (N-methylaniline and CO₂) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N⁺CO₂⁻⋅⋅⋅BPh₃]. The carbamate and BPh₃ act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH₃ to generate [HBPh₃]⁻, which is used to produce key CO₂-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh₃]⁻ species.     

pH-Sensitive Oscillatory Motion of a Urease Motor on the Urea Aqueous Phase

A self-propelled object coupled with an enzyme reaction between urease and urea was investigated at the air/aqueous interface. A plastic object that was fixed to a urease-immobilized filter paper was used as a self-propelled object, termed a urease motor, placed on an aqueous urea solution. The driving force of the urease motor is the difference in the surface tension around the object. Oscillatory motion or no motion was triggered depending on the initial pH of the urea solution. Both the frequency and maximum speed of the oscillatory motion varied depending on the initial pH of the water phase. The mechanisms underlying the oscillatory motion and no motion were discussed in relation to the bell-shaped enzyme activity of urease in the enzyme reaction and the surface tension around the urease motor.     

Roles of SiH4 and SiF4 in growth and structural changes of poly-Si films

The structural properties of polycrystalline silicon films, prepared by plasma enhanced chemical vapor deposition system, with different flow rates of SiH₄/SiF₄ mixtures at 300 °C were investigated. This study indicates that the low hydrogen coverage on the growing surface, under optimum fluorine radicals, will be leaded to an improvement of crystallized area as compared with case of high hydrogen coverage surface. Moreover, the studies of the role of SiH₄ and SiF₄ radicals show that the SiH₄ radicals are important in the nucleation and growth of grains. However, SiF₄ radicals are effective in the structural change of grain boundaries regions and by this way, in the present system, establish the growth of grains under the dominant 〈1 1 0〉 direction. The stress investigation indicates that addition of high flow rate of SiF₄ in amorphous film, results in the nearly stress free films. Finally, we found that the changes in g-value reflect the changes in the intrinsic compressive and tensile stress in the both polycrystalline and amorphous silicon films.     

Stable all-optical formation of Bose–Einstein condensate using pointing-stabilized optical trapping beams

By stabilizing the beam pointing of optical trapping beams, we have succeeded in stable formation of Bose–Einstein condensate (BEC) of ⁸⁷Rb with all-optical method. The thermal effect of acousto-optic modulator (AOM) is usually one of the most serious problems to induce beam-pointing instability, especially for high power CO₂ laser. By passing the beam through AOM twice, we have improved the beam pointing from about 4.8 mrad to less than 0.4 mrad, which has been experimentally confirmed to be small enough to stably form BEC at the crossed region of CO₂ lasers as well as to perform experiments using an optical lattice which might have been affected by beam-pointing instability. PACS 32.80.Pj; 42.79.Jq; 03.75.Mn     

Classification for dimethylarsenate-decomposing bacteria using a restrict fragment length polymorphism analysis of 16S rRNA genes.

A new monitoring system for bacterial communities involving dimethylarsinic acid (DMAA) decomposition was provided by combining the MPN (Most Probable Number) method and RFLP (restriction-fragment-length polymorphism analysis). The abundance of DMAA decomposing bacteria was estimated by the MPN method using a bacterial culture medium, which included DMAA as the sole carbon source, indicating bacterial cell densities of 1700 cells/ml in Lake Kahokugata and 330 cells/ml in Lake Kibagata. After isolating the dominant bacteria using agar plates, the isolates were classified into some genotype groups by RFLP analysis using 16S rDNA sequences. Classification of the RFLP analysis indicated that 14 isolates of Lake Kahokugata were classified into 6 types, which included 2 dominant types related to genus Pseudomonas, while 8 isolates of Lake Kibagata displayed 6 types including one or two isolates. Moreover, the RFLP types were unique for each lake, suggesting that DMAA decomposing bacteria were specific for the aquatic environment related to the arsenic cycle. The activities of DMAA decomposition mostly matched with the RFLP type category of the isolates. Accordingly, combining the MPN method with the RFLP analysis will play an important role in elucidating the distributions and dynamics of the DMAA-decomposing bacterial community.     

High-throughput characterization of local conductivity of Nd0.9Ca0.1Ba2Cu3O7−δ thin film by the low-temperature scanning microwave microscope

We developed a scanning microwave microscope (SμM) designed for high-throughput electric-property screening as well as for rapid construction of electronic phase diagrams at low temperatures. As a sensor probe, we used a high-Qλ/4 coaxial cavity resonator to which a thin needle with ball-tip end was attached. The sensor module was mounted on the low-temperature XYZ stage, which allowed us to map out the change of resonance frequency and quality factor due to the local tip-sample interaction at low temperatures. From the measurements of combinatorial thin films, such as Ti_1−xCo_xO_2−δ and Nd_0.9Ca_0.1Ba₂Cu₃O_7−δ (NCBCO), it was demonstrated that this SμM system has enough performance for the high-throughput characterization of sample conductance under variable temperature conditions.     

Collection of iron(III) from homogeneous aqueous solutions on membrane filters using Chromazurol B with Triton X-100.

A membrane filtration method was examined concerning the effective collection of iron(III) from a homogeneous aqueous solution with Chromazurol B (CAB), one of the triphenylmethane dyes, as a precipitating reagent in the presence of a non-ionic surfactant, polyethylene glycol mono[4-(1,1,3,3-tetramethylbutyl)phenyl]ether (Triton X-100). A formed blue Fe(III)-CAB complex was collected as a precipitate on a membrane filter by filtration under suction from a homogeneous aqueous solution in the pH range over about 2. The original solution was prepared at a concentration ratio of CAB to Fe(III) of to 10, and that of Triton X-100 to CAB of 10 to 100. It was then adjusted to a pH value of between 1.0 and 6.5. A linear relationship (r = 0.999) was obtained between the initial concentration and the found one of Fe(III) in the range of 2.0 x 10(-5) to 4.0 x 10(-4) mol dm(-3) at a fixed concentration ratio of CAB to Fe(III) of 3 and that of Triton X-100 to CAB of 20. This membrane filtration with CAB and Triton X-100 may be utilized for the separation of Fe(III) as a background species.     

An experiment to measure collisionless radial transport ofenergetic electrons confined by a dipole magnetic field

A new laboratory terrella has been constructed in order to study collisionless radial diffusion of particles trapped within a dipole magnetic field. Columbia's collisionless terrella experiment (CTX) aims to reproduce the process of wave-induced radial transport and does not try to simulate magnetospheric structure. The first experiment planned for CTX is the direct measurement of stochastic radial diffusion induced from wave-particle drift resonances. The motivation for the CTX experiment is described, and the procedures to be used to measure the intensity and spectrum of fluctuations generating chaos, the rate of radial transport, and the evolution of the density and pressure profiles are illustrated. Because of the success of similar experiments conducted earlier in a long thin magnetic mirror, these dipole experiments can be performed with a high degree of confidence. An example from these earlier experiments is presented     

Application of total reflection X-ray fluorescence spectrometry to small glass fragments.

Total reflection X-ray fluorescence spectrometry (TXRF) has been applied for trace elemental analysis of small glass fragments. A small glass sample (a fragment with weight less than 0.5 mg) was decomposed by 100 microg of HF/HNO3 acid; the material was condensed to 10 microl and was dried on a Si wafer. Since the size of the dried residue on the Si wafer was less than 1 cm in diameter, an incident X-ray beam with about 1 cm in width could effectively excite elemental components in such a small glass fragment. The precision of the present technique was checked by analyzing the glass fragments (<0.5 mg) from NIST SRM612; the relative standard deviations (RSD) of less than 8.1% were achieved for elemental ratios that were normalized by Sr. Fragments (<0.5 mg) obtained from 23 figured sheet glasses were used as samples for estimating the utility of this technique to forensic discrimination. Comparison of five elemental ratios of Ti/Sr, Mn/Sr, Zn/Sr, Rb/Sr, and Pb/Sr calculated from X-ray fluorescence spectra was effective in distinguishing glass fragments that could not be differentiated by their refractive indexes (RI).