Andirolides H–P from the flower of andiroba (Carapa guianensis,Meliaceae)

Three new gedunins, an andirobin, three mexicanolides, and two phragmalin-type limonoids named andirolides H (1), I (2), J (3), K (4), L (5), M (6), N (7), O (8), and P (9) were isolated from an oil of the flower of Carapa guianensis Aublet (Meliaceae). Their structures including the absolute configurations were determined by means of the NMR and CD spectra as well as FABMS. Andirolide H (1) showed antimalarial activity against Plasmodium falciparum in vitro.     

Synthesis of unsymmetrically disubstituted ethynes by the palladium/copper(I)-cocatalyzed sila-Sonogashira–Hagihara coupling reactions of alkynylsilanes with aryl iodides,bromides, and chlorides through a direct activation of a carbon–silicon bond

In this paper, we explore the copper/palladium-cocatalyzed cross-coupling reactions of 1-aryl-2-trimethylsilylethynes with aryl iodides, bromides, and chlorides as coupling partners, to furnish unsymmetrically disubstituted ethynes in moderate to excellent yields. Various aryl iodides were subjected to reaction under the optimized conditions with 5 mol % of Pd(PPh₃)₂ and 50 mol % of CuCl. The steric properties of the aryl iodide proved more influential to the outcome of the cross-coupling reaction than electronic factors. In addition, we succeeded in synthesizing unsymmetrical diarylethynes using two different aryl iodides in one-pot. Furthermore, under the same reaction conditions with 10 mol % of PdCl₂, 40 mol % of P(4-FC₆H₄)₃, and 50 mol % of CuCl as catalyst, we succeeded in synthesizing unsymmetrical diarylethynes from various aryl bromides. Finally, we explored reactions with aryl chlorides and duly discovered that unsymmetrical diarylethynes were obtainable in moderate to good yields when 10 mol % of Pd(OAc)₂, 10 mol % of (?)-DIOP, and 10 mol % of CuCl were used. These reactions proceed through a direct activation of a carbon–silicon bond in alkynylsilanes by CuCl to generate the corresponding alkynylcopper species via transmetalation from silicon to copper. Mechanistic investigations on the reaction of alkynylsilanes with aryl bromides confirmed that the trimethylsilyl bromide generated in situ retarded both transmetalation steps between CuCl and alkynylsilane, and between palladium(II) species formed by oxidative addition and alkynylcopper species.     

Instantaneous vibrational frequencies of diffusing and desorbing adsorbates: CO/Pt(111)

Electronic excitation of metal by intense laser pulses stimulates nuclear motions of adsorbates through nonadiabatic coupling, resulting in diffusion and desorption of adsorbates. These processes take place via precursor states: adsorbates whose vibrational modes with respect to substrate are highly excited. This paper reports the dynamics of precursor states of CO on Pt(111) probed by use of infrared-visible sum frequency generation with phase-sensitive detection, which allows us to obtain the second-order nonlinear susceptibility and thus the vibrational response function. Without pump pulses at 400 nm, the inverse Fourier transformation of the vibrational response function reveals a free induction decay of vibrational polarization of C-O stretching created by a short infrared pulse. The free induction decay is perturbed when an intense 400-nm pump pulse following the infrared pulse is irradiated, because diffusion and desorption of CO are induced by the pump pulse. The time evolution of instantaneous C-O stretching frequency retrieved from the perturbed free induction decay shows a redshift followed by a rapid reverse shift when the fluence of pump pulse is high enough to desorb CO. This indicates that the frustrated modes of CO is first substantially excited and then the parallel momentum of CO is converted to the normal one through mutual collisions, leading to substantial excitation of the external stretching mode of CO.     

Crystalline morphology in polymer blends via competition with spinodal decomposition

Miscible polymer blends containing one crystallizable component and exhibiting liquid-liquid phase separation at elevated temperatures [lower critical solution temperature (LCST) behavior] offer an excellent possibility of controlling morphology and thus mechanical properties. For instance, if a homogeneous mixture of dissimilar polymers is allowed to undergo a rapid temperature jump from below LCST to above LCST, spinodal decomposition takes place and a highly interconnected two-phase morphology with uniform domain size (so-called modulated structure) develops. By quenching the phase-separated system below the glass transition temperature after an appropriate time of phase separation, one is able to fix this characteristic morphology [1]. By quenching the phase-separated blend below the melting point of the crystallizable component to different supercooling depths, it is possible to control the number of nuclei and thus the spherulite's size, creating more or less ordered structures.     

Nuclear spin maser and experimental search for 129 Xe atomic EDM

The present status of an active spin maser which is being developed for an experimental search for ¹²⁹Xe atomic electric dipole moment (EDM) is presented. In order to realize the long term stability of maser frequency, systematic effects for the spin maser operation were investigated. The correlations in the maser frequency with the solenoid current, the environmental field and the cell temperature were found. With the solenoid current and environmental field being stabilized and the cell temperature lowered, a frequency precision of 7.9 nHz has been achieved for the maser operation.     

Highly Conductive TCNQ Salts of Cu Chelates

Abstract

Cu(II) chelates with ethylenediamine, 2,2′-bipyridine, 1,10-phenanthroline and their analogues form highly conductive TCNQ salts CuL_n(TCNQ)₂. The powder conductivity at room temperature amounts to 7 × 10^?4-1.9 Ω_?1cm^?1, depending on the coordinating ligands. The ESR and magnetic susceptibility studies indicate that the Cu atoms of the complexes have incomplete oxidation states.     

Proton activity of Nafion 117 membrane measured from potential difference of hydrogen electrodes

The proton activity of the Nafion membrane was estimated from the potential difference between a normal hydrogen electrode (NHE) in 0.5 mol dm^?3 H₂SO₄ and a dynamic hydrogen electrode (DHE) constructed on a Nafion 117 membrane. The potential difference between the DHE and the NHE was directly measured at the same temperature in a box chamber filled with N₂ gas. As a result, the potential difference of E _NHE???E _DHE changes from 0.006 to ?0.024 V with the increasing temperature from 289 to 313 K; however, the potential difference remains at around ?0.024 V when the temperature is between 313 and 343 K. Based on these data in combination with the Nernst equation, the proton activity of the Nafion 117 membrane at 289 K is estimated to be 0.8, which increases up to ca. 2.4 with the increasing temperature.     

Prediction of Fractional Brownian Motion-Type Processes

Abstract

We introduce a class of continuous-time Gaussian processes with stationary increments via moving-average representation with good MA coefficient. The class includes fractional Brownian motion with Hurst index less than 1/2 as a typical example. It also includes processes which have different indices corresponding to the local and long-time properties, repsectively. We derive some basic properties of the processes, and, using the results, we establish a prediction formula for them. The prediction kernel in the formula is given explicitly in terms of MA and AR coefficients.     

Guest-to-host transmission of structural changes for stimuli-responsive adsorption property

We show that structural changes of a guest molecule can trigger structural transformations of a crystalline host framework. Azobenzene was introduced into a flexible porous coordination polymer (PCP), and cis/trans isomerizations of the guest azobenzene by light or heat successfully induced structural transformations of the host PCP in a reversible fashion. This guest-to-host structural transmission resulted in drastic changes in the gas adsorption property of the host-guest composite, displaying a new strategy for creating stimuli-responsive porous materials.     

Electrochemical synthesis of mesoporous Pt-Au binary alloys with tunable compositions for enhancement of electrochemical performance

Mesoporous Pt-Au binary alloys were electrochemically synthesized from lyotropic liquid crystals (LLCs) containing corresponding metal species. Two-dimensional exagonally ordered LLC templates were prepared on conductive substrates from diluted surfactant solutions including water, a nonionic surfactant, ethanol, and metal species by drop-coating. Electrochemical synthesis using such LLC templates enabled the preparation of ordered mesoporous Pt-Au binary alloys without phase segregation. The framework composition in the mesoporous Pt-Au alloy was controlled simply by changing the compositional ratios in the precursor solution. Mesoporous Pt-Au alloys with low Au content exhibited well-ordered 2D hexagonal mesostructures, reflecting those of the original templates. With increasing Au content, however, the mesostructural order gradually decreased, thereby reducing the electrochemically active surface area. Wide-angle X-ray diffraction profiles, X-ray photoelectron spectra, and elemental mapping showed that both Pt and Au were atomically distributed in the frameworks. The electrochemical stability of mesoporous Pt-Au alloys toward methanol oxidation was highly improved relative to that of nonporous Pt and mesoporous Pt films, suggesting that mesoporous Pt-Au alloy films are potentially applicable as electrocatalysts for direct methanol fuel cells. Also, mesoporous Pt-Au alloy electrodes showed a highly sensitive amperometric response for glucose molecules, which will be useful in next-generation enzyme-free glucose sensors.