Total synthesis of broussonetine F: the orthoamide Overman rearrangement of an allylic diol

A first total synthesis of broussonetine F from diethyl L-tartrate was achieved. The cornerstone of our synthesis was an orthoamide Overman rearrangement, which provided an allylic amino alcohol with complete diastereoselectivity.     

Limiting size index distributions for ball-bin models with Zipf-type frequencies

We consider a random ball-bin model where balls are thrown randomly and sequentially into a set of bins. The frequency of choices of bins follows the Zipf-type (power-law) distribution; that is, the probability with which a ball enters the ith most popular bin is asymptotically proportional to 1/i ^α , α > 0. In this model, we derive the limiting size index distributions to which the empirical distributions of size indices converge almost surely, where the size index of degree k at time t represents the number of bins containing exactly k balls at t. While earlier studies have only treated the case where the power α of the Zipf-type distribution is greater than unity, we here consider the case of α ≤ 1 as well as α > 1. We first investigate the limiting size index distributions for the independent throw models and then extend the derived results to a case where bins are chosen dependently. Simulation experiments demonstrate not only that our analysis is valid but also that the derived limiting distributions well approximate the empirical size index distributions in a relatively short period.     

Synthesis and properties of 1,1′-bis(diacetylene-group) connected ferrocene-thiophene derivative: a cooperatively functional behavior of diacetylene-group connected constituents

An extended π-electronic conjugation system of 1,1′-bis(diacetylene-group) connected ferrocene-thiophene derivative has been synthesized, with our integrated reaction between the corresponding TMS-protected acetylenes in one-pot. Its electronic properties have been examined, suggesting a cooperatively functional behavior of the diacetylene-group connected constituents.     

Enhanced performance of photorefractive poly(N‐vinyl carbazole) composites

We present the enhanced photorefractive performance of high molecular weight poly(N‐vinyl carbazole) (PVCz)‐based composites. Higher diffraction efficiency with faster speed of grating build‐up was obtained by optimizing the composition of the PVCz composites. At relatively low applied electric field of E = 45 V μm^?1, diffraction efficiency of 26% for p‐polarized probe beam and corresponding that of 5.1% for s‐polarized probe beam were measured with faster grating build‐up speed of 48.3 s^?1 for the composite with 2,4,7‐trinitrofluorenone (TNF) as a sensitizer. Fastest speed of grating build‐up of 100 s^?1 and large optical gain up to 110 cm^?1 were measured at E = 80 V μm^?1 for the composite with fullerene derivative of PCBM as a sensitizer. These improved performances are due to a large orientational enhancement effect with faster response speed in addition to Pockels effect for the samples with appropriate glass transition temperature. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Periodic one-dimensional nanostructured arrays based on colloidal templates,applications, and devices

A novel approach to fabricate periodic one-dimensional (1D) nanostructured arrays is developed using monolayer colloidal crystals as templates or masks. This approach is more flexible and less costly than traditional lithographic techniques. The morphology and structural parameters of periodic arrays can be easily controlled, further resulting in optimized properties. Herein we introduce recent work to create periodic 1D nanostructured arrays by combining colloidal templates with other techniques, such as solution techniques, electrodeposition, wet chemical etching, reactive ion etching (RIE), pulsed laser deposition (PLD), and sputtering. These periodic 1D nanostructured arrays with controllable morphology and structural parameters have extensive applications in areas such as nanophotonics, field emitters, solar cells, light-emitting diodes, and microfluidic devices.     

Elongation of phenoxide C-O bonds due to formation of multifold hydrogen bonds: statistical, experimental, and theoretical studies

Statistical studies using the Cambridge Structural Database have revealed that there are several elongated phenoxide C-O bonds. They are characterized by the formation of 3-fold (or occasionally 2-fold) hydrogen bonds to the phenoxide oxygen atoms, and their mean bond length extends up to 1.320 ?, which is quite different from the theoretically predicted carbon-oxygen bond length of C(6)H(5)O(-) (1.26 ?). Elongated phenoxide C-O bonds associated with the formation of 3-fold hydrogen bonds were also observed in the X-ray structures of proton-transfer complexes (2X-O(-))(TEAH(+))s derived from 5'-X-substituted 5,5'-dimethyl-1,1':3',1'-terphenyl-2,2',2'-triols (2X-OHs, where X = NO(2), CN, COOCH(3), Cl, F, H, and CH(3)) and triethylamine (TEA). By comparing the X-ray structures, C-O bond elongation was found to be only slightly affected by an electron-withdrawing substituent at the para position (X). This along with strong bathochromic shifts of N-H(···O(-)) and O-H(···O(-)) stretching vibrations in the IR spectra indicates that the elongated C-O bonds in (2X-O(-))(TEAH(+))s essentially have single-bond character. This is further confirmed by molecular orbital calculations on a model complex, showing that the negatively charged phenoxide oxygen atom is no longer conjugated to the central benzene ring, and the NICS values of the three benzene rings are virtually identical. However, C-O bond elongation in (2X-O(-))(TEAH(+))s was considerably influenced by a change in the hydrogen-bond geometry. This also suggests that hydrogen bonds significantly affect phenoxide C-O bond elongation.     

Nanocrystallization of oligosilanes by a reprecipitation method: easy fabrication of H-aggregates of linear-chain oligosilane molecules

Nanocrystals of several oligosilanes have been fabricated easily by using a reprecipitation method. The nanocrystals reveal an intense absorption band at the UVB region (280 to 320 nm) and a fluorescence band with large Stokes shift. These photophysical properties show that the nanocrystals exhibit an excitonic interaction of the H-aggregate type.     

Fabrication of a mid-IR wire-grid polarizer by direct imprinting on chalcogenide glass

A mid-IR wire-grid polarizer with a 500 nm pitch was fabricated on a low toxic chalcogenide glass (Sb-Ge-Sn-S system) by the thermal imprinting of periodic grating followed by the thermal evaporation of Al metal. After imprinting, deposition of Al on the grating at an oblique angle produced a wire-grid polarizer. The fabricated polarizer showed polarization with TM transmittance greater than 60% at 5-9 μm wavelengths and an extinction ratio greater than 20 dB at 3.5-11 μm wavelengths. This polarizer with a high extinction ratio can be fabricated more simply and less expensively than conventional IR polarizers.     

Synthesis and physical properties of high birefringence phenylacetylene liquid crystals containing a cyclohexyl group

We have synthesized new phenylacetylene-based liquid crystals containing a cyclohexyl or cyclohexylethyl group and evaluated their physical properties in order to develop a range of materials having high value of birefringence. The cyclohexyl-containing compounds exhibited nematic behaviour near room temperature and moderate values of δn of around 0.3. The cyclohexylethyl-containing compounds had a very wide nematic range with a high T_NI and very high values of δn of over 0.4. They also exhibited low viscosities. The order parameter was not affected by introducing either a cyclohexyl or a cyclohexylethyl group and the values of δn based on calculated polarizabilities were obtained experimentally.