Total synthesis of escherichia coli lipid A

The first total synthesis of E. coli lipid A ($\text{1}$) is described. The synthetic compound was identical with a natural specimen and exhibited the full endotoxic activity. It was thus conclusively proved by this chemical synthesis that lipid A is the active principle of bacterial endotoxin.     

Internal flow in polymer solution droplets deposited on a lyophobic surface during a receding process

When a polymer solution droplet is deposited on a lyophobic surface, the contact line is moved back to some degree and subsequently pinned. An experimental setup is constructed to investigate not only the receding process but also an internal flow of polystyrene-acetophenone and -anisole solutions. As a result, the time variation of the evaporation rate per unit area during receding does not strongly depend on the initial solute concentration. The average solute concentration at the pinning of the contact line increases as the initial solute concentration increases. A convective circulation flow that is upward at the axis of symmetry is observed. This flow pattern is different from those of pure liquids such as water, acetone, benzene, and so forth, which have been previously reported. Furthermore, the observed flow is enhanced as the initial solute concentration increases, contrary to an increase in the fluid viscosity. To resolve these discrepancies, the mechanism of the flow is numerically investigated using a hemispherical droplet model considering the density and surface tension distributions. The numerical results demonstrate that the circulation flow that is experimentally observed is actually caused. It is also found that the solutal Rayleigh effect initially induces the internal flow, and subsequently the solutal Marangoni effect dominates the flow. Both effects are enhanced as the initial concentration increases because of the evaporative mass balance at the free surface.     

Fluorescence study on the nyctinasty of Phyllanthus urinaria L. using novel fluorescence-labeled probe compounds

We report the synthesis of fluorescence-labeled probes based on phyllanthurinolactone 1, which is a leaf-closing substance of Phyllanthus urinaria L. The fluorescence study using biologically active probe 2 and inactive probes (epi-2 and 31) revealed that the target cell for 1 is a motor cell and suggested that some receptors, which recognize the aglycon of 1 exist on the plasma membrane of the motor cell, as with leaf-opening substances. Moreover, binding of probe 2 was specific to the plant motor cell contained in the plants belonging to the genus Phyllanthus. These results showed that the binding of probe 2 with a motor cell is specific to the plant genus and suggested that the genus-specific receptor for the leaf-closing substance would be involved in nyctinasty.     

Annual variations of the elemental concentrations of PM10 in ambient air of Nagoya City as determined by ICP-AES and ICP-MS.

PM10 samples were collected at an urban site of Nagoya City during September, 2003, to August, 2004, and annual variations of the concentrations of the elements in PM10 samples were examined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The annual concentration variations of ca. 30 elements in ambient air were in the range from sub-ng m(-3) to several microg m(-3). From an evaluation by the enrichment factors of the elements, elements such as Al, Ca, Fe, Mg, Ti, Mn, Ba, Sr, Ce, La, Nd, Co, Cs, and Pr, in PM10 samples were found to have originated mostly from natural sources, while the elements such as S, Zn, Pb, Cu, Ni, Sb, Sn, Cd, Bi, W, Tl, and In originated from anthropogenic emission sources. Furthermore, in seasonal variations of the elemental concentrations of PM10 samples in ambient air, the elements originated mostly from natural sources provided significantly high concentrations in spring during the "Kosa" period (the dust season from March to May). On the other hand, the elements mainly from anthropogenic emission sources provided relatively higher concentrations in autumn and winter, which may be explained by the fact that the urban atmospheric structure is stabilized by the temperature-inversion layer formed over the city in those seasons. In addition, all of the elements provided significantly low concentrations in the summer, due to the dilution effect of the oceanic winds as well as due to the convection of air mass up to the high levels.     

Enantio-differential approach using fluorescence-labeled phyllanthurinolactone, a leaf-closing factor of Phyllanthus urinaria L.

We report here the synthesis of enantio-pair-type fluorescence-labeled probes based on phyllanthurinolactone (1), which is a leaf-closing substance of Phyllanthus urinaria L. Moreover, the application of an enantio-differential approach to distinguish between specific and nonspecific binding of ligands and receptors was performed. Fluorescence studies using a natural-type probe 6 and a nonnatural-type probe 7 revealed that the target cell for 1 is a motor cell. Furthermore, our results lead to the suggestion that some receptors, which recognize the stereochemistry of the aglycon of 1, exist on the plasma membrane of the motor cell, as do leaf-opening substances.     

Deposition of Diamond-Like Carbon Film and Mass Spectrometry Measurement in CH4/O2 RF Plasma

The deposition of diamond-like carbon (DLC) film and the measurements of ionic species by means of mass spectrometry were carried out in a CH ₄ /O ₂ RF (13.56 MHz) plasma. The film deposition rate greatly decreased with increasing O ₂ content up to 10% O ₂ . The oxygen ion density indicated the remarkable increase with the increase of O ₂ content up to 10%. The hydrocarbon ion density is increased considerably by the addition of 5% O ₂ , and then decreased monotonically for O ₂ contents more than 5%. Many oxygenated hydrocarbon ions were detected in the CH ₄ /O ₂ plasma. They were classified into three kinds of ions: C _n H _m O ⁺ , C _n H _m OH ⁺ , and C _n H _m O ₂ H ⁺. When the O ₂ content was increased, the higher hydrocarbon C _n H _m ⁺ (n2) ion densities (except C ₂ H ₄ ⁺ ) decreased more than the principal (CH ₃ ⁺ and CH ₄ ⁺ ) ion densities, since the generation of higher hydrocarbon ions would be suppressed by the formation of oxygenated hydrocarbons. It was also suggested that the great decrease in the film deposition rate in the CH ₄ /O ₂ plasma was mainly associated with considerable decrease in the higher hydrocarbon ion densities. The properties of DLC film obtained in CH ₄ /O ₂ plasma did not indicate considerable change from those obtained in pure CH ₄ plasma.     

Perfluoropentacene: high-performance p-n junctions and complementary circuits with pentacene

We report the synthesis and characterization of perfluoropentacene as an n-type semiconductor for organic field-effect transistors (OFETs). Perfluoropentacene is a planar and crystalline material that adopts a herringbone structure as observed for pentacene. OFETs with perfluoropentacene were constructed using top-contact geometry, and an electron mobility of 0.11 cm2 V-1 s-1 was observed. Bipolar OFETs with perfluoropentacene and pentacene function at both negative and positive gate voltages. The improved p-n junctions are probably due to the similar d-spacings of both acenes. Complementary inverter circuits were fabricated, and the transfer characteristics exhibit a sharp inversion of the output signal with a high-voltage gain.     

二维光子晶体分束器和偏转器

针对二维光子晶体在光束调整和光束偏转中的应用,采用平面波展开法、二维有限时域差分法和完全匹配层吸收边界条件,从理论上研究了二维方形光子晶体结构中TM模式的自准直现象.通过分析光子晶体的能带结构和等频图,基于二维光子晶体的自准直效应和光子带隙,对光波在二维光子晶体中的传播特性进行了讨论.数值计算表明,通过在合适的方向引入不同的线缺陷,可以实现自准直光束的1×2和1×3分束以及光束偏转.最后讨论了透射光束和偏转光束的能量随线缺陷半径的变化关系.所设计的器件极大地扩展了光子晶体在高密度光学集成电路中的应用.     

Synthesis of Zinc Chlorophyll Homo/Hetero‐Dyads and their Folded Conformers with Porphyrin,Chlorin, and Bacteriochlorin π‐Systems

Zinc complex of pyropheophorbide‐b, a derivative of chlorophyll‐b, was covalently dimerized through ethylene glycol diester. The synthetic homo‐dyad was axially ligated with two methanol molecules from the β‐face and both the diastereomerically coordinating methanol species were hydrogen bonded with the keto‐carbonyl groups of the neighboring chlorin in a complex. The resulting folded conformer in a solution was confirmed by visible, ¹H NMR and IR spectra. All the synthetic zinc chlorin homo‐ and hetero‐dyads consisting of pyropheophorbides‐a, b and/or d took the above methanol‐locked and π–π stacked supramolecules in 1% (v/v) methanol and benzene to give redmost (Qy) electronic absorption band(s) at longer wavelengths than those of the corresponding monomeric chlorin composites. The other zinc chlorin and bacteriochlorin homo‐dyads completely formed similar folded conformers in the same solution, while zinc inverse chlorin and porphyrin homo‐dyads partially took such supramolecules. The J‐type aggregation to folded conformers and the redshift values of composite Qy bands were dependent on the electronic and steric factors of porphyrinoid moieties in dyads.