Electrical conduction of organic ultrathin films evaluated by an independently driven double-tip scanning tunneling microscope

The electrical transport properties of organic thin films within the micrometer scale have been evaluated by a laboratory-built independently driven double-tip scanning tunneling microscope, operating under ambient conditions. The two tips were used as point contact electrodes, and current in the range from 0.1 pA to 100 nA flowing between the two tips through the material can be detected. We demonstrated two-dimensional contour mapping of the electrical resistance on a poly(3-octylthiophene) thin films as shown below. The obtained contour map clearly provided an image of two-dimensional electrical conductance between two point electrodes on the poly(3-octylthiophene) thin film. The conductivity of the thin film was estimated to be (1-8) × 10(-6) S cm(-1). Future prospects and the desired development of multiprobe STMs are also discussed.     

Characterization of a Recombinant Flocculent Saccharomyces cerevisiae Strain that Co-ferments Glucose and Xylose: I. Influence of the Ratio of Glucose/Xylose on Ethanol Production

Glucose/xylose mixtures (90 g/L total sugar) were evaluated for their effect on ethanol fermentation by a recombinant flocculent Saccharomyces cerevisiae, MA-R4. Glucose was utilized faster than xylose at any ratio of glucose/xylose, although MA-R4 can simultaneously co-ferment both sugars. A high percentage of glucose can increase cell biomass production and therefore increase the rate of glucose utilization (1.224 g glucose/g biomass/h maximum) and ethanol formation (0.493 g ethanol/g biomass/h maximum). However, the best ratio of glucose/xylose for the highest xylose consumption rate (0.209 g xylose/g biomass/h) was 2:3. Ethanol concentration and yield increased and by-product (xylitol, glycerol, and acetic acid) concentration decreased as the proportion of glucose increased. The maximum ethanol concentration was 41.6 and 21.9 g/L after 72 h of fermentation with 90 g/L glucose and 90 g/L xylose, respectively, while the ethanol yield was 0.454 and 0.335 g/g in 90 g/L glucose and 90 g/L xylose media, respectively. High ethanol yield when a high percentage of glucose is available is likely due to decreased production of by-products, such as glycerol and acetic acid. These results suggest that ethanol selectivity is increased when a higher proportion of glucose is available and reduced when a higher proportion of xylose is available.     

Chemical synthesis of Helicobacter pylori lipopolysaccharide partial structures and their selective proinflammatory responses

Helicobacter pylori is a common cause of gastroduodenal inflammatory diseases such as chronic gastritis and peptic ulcers and also an important factor in gastric carcinogenesis. Recent reports have demonstrated that bacterial inflammatory processes, such as stimulation with H. pylori lipopolysaccharide (LPS), initiate atherosclerosis. To establish the structures responsible for the inflammatory response of H. pylori LPS, we synthesized various kinds of lipid A structures (i.e., triacylated lipid A and Kdo‐lipid A compounds), with or without the ethanolamine group at the 1‐phosphate moiety, by a new divergent synthetic route. Stereoselective α‐glycosylation of Kdo N‐phenyltrifluoroacetimidate was achieved by use of microfluidic methods. None of the lipid A and Kdo‐lipid A compounds were a strong inducer of IL‐1β, IL‐6, or IL‐8, suggesting that H. pylori LPS is unable to induce acute inflammation. In fact, the lipid A and Kdo‐lipid A compounds showed antagonistic activity against cytokine induction by E. coli LPS, except for the lipid A compound with the ethanolamine group, which showed very weak agonistic activity. On the other hand, these H. pylori LPS partial structures showed potent IL‐18‐ and IL‐12‐inducing activities. IL‐18 has been shown to correlate with chronic inflammation, so H. pylori LPS might be implicated in the chronic inflammatory responses induced by H. pylori. These results also indicated that H. pylori LPS can modulate the immune response: NF‐κB activation through hTLR4/MD‐2 was suppressed, whereas production of IL‐18 and IL‐12 was promoted.     

Superconducting properties of ZnO-doped (Bi, Pb)-2223 thick film on Ni and NiO substrates prepared by spray deposition technique

The superconductivity of ZnO-doped (Bi, Pb)-2223 thick film on the Ni and NiO substrates, which was prepared by the spray deposition technique with cold forging, was investigated by characterizing the critical current density (J_c), the critical temperature (T_c), the orientation factor (f), and the microstructure of the film. The thickness of the thick film prepared by the spray deposition method was approximately 10 μm. The maximum J_c value of (Bi, Pb)-2223 film on NiO substrate was approximately 2200 A/cm² (I_c = 110 mA) when the film was sintered at 865 °C for 1 h with a cooling rate of 0.5 °C/min from 865 °C to 650 °C; in the case of Ni substrate, a maximum J_c value of approximately 2000 A/cm² (I_c = 100 mA) was obtained for the (Bi, Pb)-2223 thick film when a cooling rate was 3 °C/min. Such a difference in the J_c values of (Bi, Pb)-2223 thick film on Ni and NiO substrates is attributed to the presence of reaction layer at the (Bi, Pb)-2223 and substrate interface. In addition, the variations in the orientation factor of (Bi, Pb)-2223 thick film on NiO substrate related to those of J_c values. The J_c values of (Bi, Pb)-2223 film on NiO substrate with ZnO doping extremely depended on the amount of ZnO doping and the 0.5 wt% ZnO-doped (Bi, Pb)-2223 thick film deposited on NiO substrate, which was sintered at 835 °C for 1 h in air with a cooling rate of 1 °C/min, showed a J_c value of approximately 1200 A/cm² (I_c = 60 mA). Thus, it is considered that a small amount of ZnO doping was effective in lowering the sintering temperature of (Bi, Pb)-2223 thick film, resulting the improvement in the intragranular weak bonding or Josephson junction.     

Miscibility of poly(vinyl chloride) with chitin derivatives having poly(2-methyl-2-oxazoline) side chains

Binary blends of poly(vinyl chloride) (PVC) and chitin-graft-poly(2-methyl-2-oxazoline) showed miscibility in the blend fraction range of the latter lower than ca. 10 wt.-%. The glass transition temperature of PVC, which was determined by differential scanning calorimetry, changed to lower temperatures with increasing modified chitin contents up to 10 wt.-%. Segmental interaction between PVC and the graft copolymer was confirmed by the carbonyl stretching band shift in the FT-IR analysis.     

Chemical modification of hydroxyl groups of poly(vinyl alcohol) by a glycosidation reaction

A new procedure for chemical modification of poly(vinyl alcohol) (PVA) was established by a glycosidation reaction of hydroxyl groups in PVA with triacetylated sugar oxazoline 1 . ¹H and ¹³C NMR analyses indicated that triacetylated N‐acetyl‐D‐glucosamine (GlcNAc) was introduced onto a PVA backbone selectively via a β‐O‐glycoside linkage. Deacetylation of triacetylated GlcNAc‐substituted PVA 2 resulted in GlcNAc‐substituted PVA 3 in good yield. These modified PVAs 2 and 3 exhibited solubilities and thermal properties different from the original PVA.     

Selective synthesis of organic sulfides and disulfides by the reduction of elemental sulfur with samarium diiodide

Elemental sulfur can be reduced to the corresponding thiolate anion species (S²⁻ and S²⁻₂) selectively by samarium diiodide in the presence and absence of HMPA, respectively. The subsequent alkylation of the thiolate anion species provides a useful synthetic route to dialkyl sulfides and disulfides. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9: 581–584, 1998     

New chitin-based polymer hybrids, 1. Miscibility of poly(vinyl alcohol) with chitin derivatives

As a new class of biopolymer-based hybrid materials, the present paper describes the binary blends of a modified chitin and poly(vinyl alcohol) (PVA) which are miscible in the whole range of compositions. The blend films were prepared by the solvent cast method from a homogeneous aqueous solution of PVA and a chitin derivative having poly(2-methyl-2-oxazoline) side chains. Miscibility between PVA and poly(2-methyl-2-oxazoline) homopolymer was also revealed. Differential scanning calorimetry and FT-IR analyses were used to investigate the blends.     

Room-Temperature Alkyl-Diphenylpyrene Liquefication by Molecular Desymmetrization

Achieving the lowest phase transition temperature with minimal chemical modification in highly crystalline π-conjugated molecules is a universal problem in related research fields. This paper reports room-temperature liquefication of diphenylpyrene isomers by introducing bulky yet flexible branched alkyl chains through molecular desymmetrization. Six isomers with different symmetries depending on the positions of the phenyl groups and alkyl groups were synthesized, and three of the isomers were found to be liquids at 25 °C, a state in which they have remained for more than five years. Although it is generally believed that the lower the symmetry of a molecule, the less likely it is to crystallize, one molecule with a relatively high molecular symmetry unexpectedly did not crystallize, which was evidenced by the kinetic inhomogeneity of this amorphous material (practically stable liquid) assessed by rheological analysis.