Tandem Isomerization/α,ß-Site-Selective and Enantioselective Addition Reactions of N-(3-Butynoyl)-3,5-dimethylpyrazole Induced by Chiral π-Cu(II) Catalysts.

Allenes are important building blocks, and derivatization of products via cycloadditions of allenes could become a powerful strategy for constructing carbocyclic and heterocyclic rings. However, the development of catalytic site-selective and enantioselective cycloaddition reactions of allenes still presents significant challenges. Here, we report chiral π-Cu(II)-complex-catalyzed isomerization of N-(3-butynoyl)-3,5-dimethyl-1H-pyrazole to generate N-allenoylpyrazole in situ and subsequent α,ß-site-selective and enantioselective [3 + 2], [4 + 2], or [2 + 2] cycloaddition or conjugate addition reactions. The asymmetric environment created by the intramolecular π-Cu(II) interactions provides the corresponding adducts in moderate to high yield with excellent enantioselectivity. To the best of our knowledge, this is the first successful method for chiral-Lewis-acid-catalyzed tandem isomerization/α,ß-site-selective and enantioselective cycloaddition or conjugate addition reactions of latent non-γ-substituted allenoyl derivative.

Highly stable Fe/CeO2 catalyst for the reverse water gas shift reaction in the presence of H2S.

This study focused on evaluating the catalytic properties for the reverse water gas shift reaction (RWGS: CO2 + H2 → CO + H2O ΔH 0 = 42.1 kJ mol-1) in the presence of hydrogen sulfide (H2S) over a Fe/CeO2 catalyst, commercial Cu-Zn catalyst for the WGS reaction (MDC-7), and Co-Mo catalyst for hydrocarbon desulfurization. The Fe/CeO2 catalyst exhibited a relatively high catalytic activity to RWGS, compared to the commercial MDC-7 and Co-Mo catalysts. In addition, the Fe/CeO2 catalyst showed stable performance in the RWGS environment that contained high concentrations of H2S. The role of co-feeding H2S was investigated over the Fe/CeO2 catalyst by the temperature programmed reaction (TPR) of CO2 and H2 in the presence of H2S. The result of TPR indicated that the co-feeding H2S might enhance RWGS performance due to H2S acting as the hydrogen source to reduce CO2.

Electron aspirator using electron-electron scattering in nanoscale silicon.

Current enhancement without increasing the input power is a critical issue to be pursued for electronic circuits. However, drivability of metal-oxide-semiconductor (MOS) transistors is limited by the source-injection current, and electrons that have passed through the source unavoidably waste their momentum to the phonon bath. Here, we propose the Si electron-aspirator, a nanometer-scaled MOS device with a T-shaped branch, to go beyond this limit. The device utilizes the hydrodynamic nature of electrons due to the electron-electron scattering, by which the injected hot electrons transfer their momentum to cold electrons before they relax with the phonon bath. This momentum transfer induces an electron flow from the grounded side terminal without additional power sources. The operation is demonstrated by observing the output-current enhancement by a factor of about 3 at 8 K, which reveals that the electron-electron scattering can govern the electron transport in nanometer-scaled MOS devices, and increase their effective drivability.

Fast yet accurate computation of radiances in shortwave infrared satellite remote sensing channels.

Accurate radiative transfer simulations of signals received by sensors deployed on satellite platforms for remote sensing purposes can be computationally demanding depending on channel width and the spectral variation of atmospheric and surface optical properties. Therefore, methods that can speed up such simulations are desirable. While it is common practice to use atmospheric "window" channels to minimize the influence of gaseous absorption, the impact of the underlying surface as well as clouds and aerosols has received less attention. To reduce the number of monochromatic computations required to obtain a desired accuracy, one may average the inherent optical properties (IOPs) over a spectral band to generate effective or mean IOP values to be used in "quasi-monochromatic" radiative transfer computations. Comparison of radiances produced by computations based on mean (quasi-monochromatic) IOPs with benchmark results in typical shortwave infrared window channels, revealed that while this approach may be sufficient for gaseous absorption, it led to significant errors in the presence spectrally varying surface IOPs, in general, and snow/ice surfaces, in particular. To solve this problem, a new method was developed in which a satellite channel is represented by a few subbands. This new method significantly reduces the error resulting from IOP averaging to be typically less than 1%. An additional correction was also developed to further reduce the error incurred by use of mean gas IOPs for large solar zenith angles to be less than 0.01%.

Band transport across a chain of dopant sites in silicon over micron distances and high temperatures.

Macroscopic manifestations of quantum mechanics are among the most spectacular effects of physics. In most of them, novel collective properties emerge from the quantum mechanical behaviour of their microscopic constituents. Others, like superconductivity, extend a property typical of the atomic scale to macroscopic length scale. Similarly, features of quantum transport in Hubbard systems which are only observed at nanometric distances in natural and artificial atoms embedded in quantum devices, could be in principle extended to macroscopic distances in microelectronic devices. By employing an atomic chain consists of an array of 20 atoms implanted along the channel of a silicon transistor with length of 1 µm, we extend to such unprecedented distance both the single electron quantum transport via sequential tunneling, and to room temperature the features of the Hubbard bands. Their observation provides a new example of scaling of quantum mechanical properties, previously observed only at the nanoscale, up to lengths typical of microelectronics, by opening new perspectives towards passage of quantum states and band engineering in silicon devices.

Retrieval of snow physical parameters by neural networks and optimal estimation: case study for ground-based spectral radiometer system.

A new retrieval algorithm for estimation of snow grain size and impurity concentration from spectral radiation data is developed for remote sensing applications. A radiative transfer (RT) model for the coupled atmosphere-snow system is used as a forward model. This model simulates spectral radiant quantities for visible and near-infrared channels. The forward RT calculation is, however, the most time-consuming part of the forward-inverse modeling. Therefore, we replaced it with a neural network (NN) function for fast computation of radiances and Jacobians. The retrieval scheme is based on an optimal estimation method with a priori constraints. The NN function was also employed to obtain an accurate first guess in the retrieval scheme. Validation with simulation data shows that a combination of NN techniques and optimal estimation method can provide more accurate retrievals than by using only NN techniques. In addition, validation with in-situ measurements conducted by using ground-based spectral radiometer system shows that comparison between retrieved snow parameters with in-situ measurements is acceptable with satisfactory accuracy. The algorithm provides simultaneous, accurate and fast retrieval of the snow properties. The algorithm presented here is useful for airborne/satellite remote sensing.

Synthesis and Applications of Hajos-Parrish Ketone Isomers.

Numerous natural products possess ring systems and functionality for which Hajos-Parrish ketone isomers with a transposed methyl group (termed "iso-Hajos-Parrish ketones") would be of value. However, such building blocks have not been exploited to the same degree as the more typical Hajos-Parrish hydrindane. An efficient three-step synthesis of such materials was fueled by a simple method for the rapid preparation of highly functionalized cyclopentenones, several of which are new chemical entities that would be challenging to access through other approaches. Furthermore, one iso-Hajos-Parrish ketone was converted into two distinct natural product analogues and one natural product. As one indication of the value of these new building blocks, that latter target was obtained in 10 steps, having previously been accessed in 18 steps using the Hajos-Parrish ketone.

Enantioselective 1,3-dipolar cycloaddition of azomethine imines with propioloylpyrazoles induced by chiral π-cation catalysts.

We developed 1,3-dipolar cycloadditions of azomethine imines with propioloylpyrazoles catalyzed by a chiral copper(II) complex of 3-(2-naphthyl)-l-alanine amide. The asymmetric environment created by intramolecular π-cation interaction and the N-alkyl group of the chiral ligand gives the corresponding adducts in high yields with excellent enantioselectivity. This is the first successful method for the catalytic enantioselective 1,3-dipolar cycloaddition of azomethine imines with internal alkyne derivatives to give fully substituted pyrazolines.

Modeling angular-dependent spectral emissivity of snow and ice in the thermal infrared atmospheric window.

A model of angular-dependent emissivity spectra of snow and ice in the 8-14 µm atmospheric window is constructed. Past field research revealed that snow emissivity varies depending on snow grain size and the exitance angle. Thermography images acquired in this study further revealed that not only welded snow particles such as sun crust, but also disaggregated particles such as granular snow and dendrite crystals exhibit high reflectivity on their crystal facets, even when the bulk snow surface exhibits blackbody-like behavior as a whole. The observed thermal emissive behaviors of snow particles suggest that emissivity of the bulk snow surface can be expressed by a weighted sum of two emissivity components: those of the specular and blackbody surfaces. Based on this assumption, a semi-empirical emissivity model was constructed; it is expressed by a linear combination of specular and blackbody surfaces' emissivities with a weighting parameter characterizing the specularity of the bulk surface. Emissivity spectra calculated using the model succeeded in reproducing the past in situ measured directional spectra of various snow types by employing a specific weighting parameter for each snow type.

Anderson-Mott transition in arrays of a few dopant atoms in a silicon transistor.

Dopant atoms are used to control the properties of semiconductors in most electronic devices. Recent advances such as single-ion implantation have allowed the precise positioning of single dopants in semiconductors as well as the fabrication of single-atom transistors, representing steps forward in the realization of quantum circuits. However, the interactions between dopant atoms have only been studied in systems containing large numbers of dopants, so it has not been possible to explore fundamental phenomena such as the Anderson-Mott transition between conduction by sequential tunnelling through isolated dopant atoms, and conduction through thermally activated impurity Hubbard bands. Here, we observe the Anderson-Mott transition at low temperatures in silicon transistors containing arrays of two, four or six arsenic dopant atoms that have been deterministically implanted along the channel of the device. The transition is induced by controlling the spacing between dopant atoms. Furthermore, at the critical density between tunnelling and band transport regimes, we are able to change the phase of the electron system from a frozen Wigner-like phase to a Fermi glass by increasing the temperature. Our results open up new approaches for the investigation of coherent transport, band engineering and strongly correlated systems in condensed-matter physics.

Catalytic enantioselective 1,3-dipolar cycloadditions of nitrones with propioloylpyrazoles and acryloylpyrazoles induced by chiral π-cation catalysts.

A chiral copper(II) complex of 3-(2-naphthyl)-l-alanine amide successfully catalyzes the enantioselective 1,3-dipolar cycloaddition reaction of nitrones with propioloylpyrazole and acryloylpyrazole derivatives. The asymmetric environment created by intramolecular π-cation interaction gives the corresponding adducts in high yields with excellent enantioselectivity. This is the first successful method for the catalytic enantioselective 1,3-dipolar cycloaddition of nitrones with acetylene derivatives. The 1,3-dipolar cycloadducts can be stereoselectively converted to ß-lactams via reductive cleavage of the N-O bond using SmI(2).

Characterization, in vitro cytotoxicity and cellular accumulation of paclitaxel-loaded lipid nano-emulsions.

Lipid nano-emulsions (LNEs) having a mean droplet size of approximately 50 nm were investigated as drug carriers for paclitaxel (TXL) to achieve its satisfactory loadings and to develop a pharmaceutically acceptable alternative to the current formulation, Taxol. TXL was incorporated into the LNEs at 2.0 mg/ml without changes in particle size or drug precipitation. In the cytotoxicity study, TXL-loaded LNEs had cytotoxicity to HeLa cells equivalent to that of TXL alone; the 50% growth inhibitory concentrations (IC(50)) of TXL-loaded LNEs and TXL alone were 1.53 +/- 0.23 nM and 1.76 +/- 0.08 nM, respectively. However, a cellular accumulation study using 1,6-diphenyl-1,3,5-hexatriene (DPH) as a fluorescent probe showed that the accumulation of DPH-loaded LNEs in HeLa cells was remarkably lower than that of DPH alone. These results indicated that LNEs were a useful vehicle for TXL, even though LNEs themselves could not be efficiently accumulated in HeLa cells.

Determination of nonylphenol ethoxylates and octylphenol ethoxylates in environmental samples using 13C-labeled surrogate compounds.

Alkylphenol polyethoxylates (APEOs) have been widely used as nonionic surfactants in a variety of industrial and commercial products. Typical compounds are nonylphenol polyethoxylates (NPEOs) and octylphenol polyethoxylates (OPEOs), which serve as precursors to nonylphenol (NP) and octylphenol (OP), respectively. NP and 4-t-OP are known to have endocrine disrupting effects on fish (medaka, Oryzias latipes), so it is important to know the concentrations of APEOs in the environment. Because the analytical characteristics of these compounds depend on the length of the ethoxy chain, it is necessary to use appropriate compounds as internal standards or surrogates. We synthesized two 13C-labeled surrogate compounds and used these compounds as internal standards to determine NPEOs and OPEOs by high-performance liquid chromatography (LC)-mass spectrometry. Method detection limits were 0.015 microg/L for NP (2)EO to 0.037 microg/L for NP(12)EO, and 0.011 microg/L for OP(3,6)EO to 0.024 microg/L for OP (4)EO. NPEO concentrations in water from a sewage treatment plant were less than 0.05-0.52 microg/L for final effluent and 1.2-15 microg/L for influent. OPEO concentrations were less than 0.05-0.15 microg/L for the final effluent and less than 0.05-1.1 microg/L for influent.

Monte Carlo simulations of spectral albedo for artificial snowpacks composed of spherical and nonspherical particles.

The optical properties of snowpacks composed of spherical and nonspherical particles artificially prepared in a cold laboratory are investigated by measuring spectral albedos. The measured spectral albedo in the spectral region lambda=0.35-2.5 microm is compared with the theoretically calculated albedo, for which a Monte Carlo radiative transfer model is employed for multiple scattering combined with the Mie theory and the ray-tracing technique for single scattering by snow particles. Since the spherical particles are a little aggregate, the effects of a cluster of the spheres on snow albedo are examined using a generalized multiparticle Mie-solution model [Appl. Opt. 34, 4573 (1995); J. Quant. Spectrosc. Radiat. Transf. 79-80, 1121 (2003)]. The snow albedo of a cluster of the spheres can be represented with that of the singe sphere slightly larger than its component of the cluster in case of small grains. The observed albedos for the spherical snow particles agree with the theoretically calculated ones for the snow grain size measured in the snow pit work. The snow albedos for the nonspherical particles, which were dendrites, are influenced by the branch width and the branch length, based on a comparison of the theoretically calculated albedo by using circular cylindrical snow particles and the observed albedo. The snow albedo in the near-infrared region depends on the branch width only when the branch length is sufficiently greater than the branch width. The comparison between the spherical and nonspherical snow particles indicates that the spectral albedo of the nonspherical particles can be represented by using an equal volume-area ratio sphere.

Efficient use of an improved radiative transfer code to simulate near-global distributions of satellite-measured radiances.

Two new extension modules that give the water-leaving radiance from the ocean and the snow bidirectional reflectance distribution function were implemented in the latest radiative transfer code. In addition, to simulate the near-global distributions of satellite-measured radiances by using the improved radiative transfer code, we tested and applied the look-up table method together with the process-separation technique of the radiative transfer calculation. The computing time was reduced from 1 year to 20 s to simulate one channel, one scene of the Global Imager image by use of an Alpha 21164A-2 (600-MHz) machine. The error analyses showed that the radiances were simulated with less than 1% error for the nonabsorbing visible channels and approximately 2% error for absorbing channels by use of this method.