Sustained photobiological hydrogen production in the presence of N2 by nitrogenase mutants of the heterocyst-forming cyanobacterium Anabaena

Heterocyst-forming cells of the cyanobacterium Anabaena sp. strain PCC 7120 ΔHup, lacking an uptake hydrogenase, photobiologically produce H₂ by nitrogenase. Under N₂-rich atmosphere, the nitrogenase activity declines in a rather short time due to the sufficiency of combined nitrogen. From the parental ΔHup strain, site-directed double-crossover variants, dc-Q193S and dc-R284H, were created with amino acid substitutions presumed to be located in the vicinity of the FeMo-cofactor of nitrogenase. Unlike the case for the ΔHup strain, H₂ production activities of the variants were not decreased by the presence of high concentrations of N₂ and they continuously produced H₂ over 21 days with occasional headspace gas replacement. This property of N₂ insensitivity is a potentially useful strategy for reducing the cost of the culture gas in future practical applications of sustainable biofuel production. This Anabaena strain has only the Mo-containing nitrogenase which reduces acetylene to ethylene, but the dc-Q193S variant also produced ethane at low but measurable rates along with greater rates of ethylene production.     

Liquid phase growth of graphene on silicon carbide

We developed a novel method to produce graphene on silicon carbide (SiC) at a temperature as low as 1000 °C. The method is based on liquid phase growth (LPG) of graphene mediated by liquid gallium, which acts not only as a flux to store carbon dissolved from a surface of SiC when heated, but also as a catalyst to promote the formation of graphene on SiC when cooled. Our experimental results revealed that gallium-treated SiC substrates are coated with uniform and continuous graphene films. The LPG method is able to supply graphene films consisting of one to several hundreds of layers, depending on heating temperatures. Our approach can not only provide an alternative way to form graphene natively on SiC, but will also bring a technological breakthrough in industrial applications of graphene, e.g. the realization of graphene-on-insulator substrates.     

Cloning and characterization of a β-N-acetylglucosaminidase (BmFDL) from silkworm Bombyx mori

In insects, β-N-acetylglucosaminidase (GlcNAcase) participates in critical physiological processes such as fertilization, metamorphosis, and glycoconjugate degradation. Insects produce glycoproteins carrying paucimannosidic-type N-glycans, the terminal GlcNAc residue of which is cleaved by a GlcNAc-linkage specific GlcNAcase, also known as the fused lobes (FDL) protein. To obtain information on the structure of GlcNAcases and insight into their contribution to physiological processes, we cloned Bombyx mori FDL (BmFDL) from silkworm larvae. The full-length cDNA (1.9 kb) encoded a protein of 633 amino acids with 42% amino acid sequence identity to Drosophila melanogaster FDL (DmFDL). Recombinant BmFDL cleaved only β-1,2-linked GlcNAc residues from the α-1,3 branch of biantennary N-glycan. This substrate specificity was similar to that of DmFDL. Microsomal FDL activity was inhibited by anti-BmFDL antibodies. Taken together, our results suggest that BmFDL is a N-glycan-processing GlcNAcase in B. mori.     

Solid and thermal properties of ABA‐type triblock copolymers designed using difunctional fluorine‐containing polyimide macroinitiators with methyl methacrylate

BACKGROUND: ABA‐type poly(methyl methacrylate) (PMMA) and fluorine‐containing polyimide triblock copolymers are potentially beneficial for electric materials. In the work reported here, triblock copolymers with various block lengths were prepared from fluorine‐containing difunctional polyimide macroinitiators and methyl methacrylate monomer through atom‐transfer radical polymerization. The effects of structure on their solid and thermal properties were studied. RESULTS: The weight ratios of the triblock copolymers derived using thermogravimetric analysis were shown to be almost identical to the ratios determined using ¹H NMR. The solid properties (film density and maximum d‐spacing value) and thermal properties (glass transition and thermal expansion) were shown to be strongly dependent on the weight ratios of both PMMA and polyimide components. Furthermore, a porous film, which showed a lower dielectric constant of 2.48 at 1 MHz, could be prepared by heating a triblock copolymer film to induce the thermal degradation of the PMMA component. CONCLUSION: The use of the polyimide macroinitiator was useful in the preparation of ABA‐type triblock copolymers to control each block length that influences the solid and thermal properties. Additionally, the triblock copolymers have great potential in preparing porous polyimides in the application of electric materials as interlayer insulation membranes of large‐scale integration. Copyright © 2009 Society of Chemical Industry     

How small the contacts could be optimal for nanoscale organic transistors?

We report on a study seeking an optimized contact configuration for organic transistors that minimizes contact effects but maintains smallest contact size. We begin with the bulk access resistance in staggered transistors which results from the charge transport through the organic semiconductor film. Bulk access resistance is an intrinsic contributor to the contact resistance which has been little understood due to lack of a reliable study tool. In this work, we utilize the inner transported power inside the semiconductor film as a medium to investigate the contact resistance and the relevant contact effects. We examine the influences of the organic film thickness (t_SC), the channel length (L), the underlying charge transport and various organic semiconductor materials with variable carrier mobility. A roughly optimal contact length (L_C) of L_C0 ≈ 6t_SC is obtained. The results reveal that besides the device architecture the underlying charge transport should be also taken into account in designing organic transistors for practical application.     

Effect of degree of polymerization on gelation and flow processability of poly(vinyl chloride)

The effect of degree of polymerization (DP) on the gelation and flow processability of poly(vinyl chloride) (PVC) was studied. Sheets with adjusted degree of gelation were prepared by rolling rigid pipe formulation suspension PVC compounds with DPs of 800, 1050 and 1300 by changing the milling temperature. Their degrees of gelation were measured with DSC and their capillary flow properties were measured with a capillary rheometer at 150, 170 and 190°C and the effect of DP on the relation between gelation and flow processabilities was studied. Because of the higher shearing heat during milling, the sample with the higher DP had a higher history temperature and thus tended to show a higher degree of gelation. The viscosity increased as the gelation increased. The dependency of viscosity on DP was higher at higher milling and extrusion temperatures and thus at a higher degree of gelation and a lower shear rate. This was assumed to be attributed to the more prominent uniform molecular flow as against the particle flow. The die swell increased with increasing the milling and extrusion temperatures and hence with increasing the gelation. A sample with a lower DP tended to show a larger die swell and this tendency was even more pronounced at the higher extrusion temperature. The melt fracture easily occurred when a sample with advanced gelation was extruded at low temperature. Whereas at low milling temperatures a sample with the lower DP showed a lower critical shear rate at onset of melt fracture, and thus easily generating melt fracture, at high milling temperatures it showed a higher critical shear rate and hence scarcely generated melt fracture. These experimental results were explained by the fact and concept that a sample with a lower DP shows a higher increase in the gelation during extrusion and/or the slighter feature of particle flow as against the uniform molecular flow at the same gelation level. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1915–1938, 2004     

Complex formation, thermal properties, and in-vitro digestibility of gelatinized potato starch-fatty acid mixtures

Effects of the type and amount of fatty acid (0-2.0 mmol/g-starch of lauric, myristic, palmitic, stearic, oleic, and linoleic acids) on the complex formation, thermal properties, and in-vitro digestibility of gelatinized potato starch-fatty acid mixtures were investigated. Complex index (CI) evaluated by the reduction in the iodine binding capacity of starch increased with an increase in the amount of fatty acids, and reached a plateau depending on the type of fatty acid. The maximum CI value was higher in the order of lauric (49.9%), linoleic (47.6%), myristic (42.4%), oleic (36.7%), stearic (35.3%), and palmitic acid (30.9%). From the calorimetric study, it was demonstrated that melting temperature of the complexes was higher in the order of stearic (96.7 °C) > lauric, myristic, palmitic, and oleic (89.6-92.1 °C) > linoleic acid (78.3 °C). Melting enthalpy for complexes was roughly related to the CI value (R² = 0.667). From the in-vitro digestibility measurement, it was found that a certain amount of fatty acid reduced the starch content hydrolyzed at a given condition. Among them, 0.50 mmol/g-starch lauric and oleic acid samples showed the largest reduction in the hydrolyzed starch content. This result was related to the extent of complex formation characterized by CI value and its helical order characterized by melting temperature. In addition, there was a possibility of the complex formation between amylose and unsaturated fatty acid during the hydrolysis of gelatinized starch.