Determination of Mark-Houwink-Sakurada equation for phenolic resins containing alkylenediamine in the main chain and estimation of their molecular conformation in tetrahydrofuran solution

Summary Phenolic resins containing alkylenediamine in the main chain could be prepared by the co-condensation reaction of phenol, formaldehyde and alkylenediamines such as ethylenediamine and hexamethylenediamine. The molecular structures were determined by¹H-NMR spectra, IR spectra and nitrogen content. The molecular conformation of these resins in THF solution were studied from the viscosity measurements, and it became clear that the molecules were considerably compact compared with linear vinyl polymers. To clarify the reason of this phenomenon, the resins whose degrees of branching were different from each other and the resins whose phenolic hydroxyl groups were acetylated were prepared. From viscosity data, it was pointed out that the intramolecular hydrogen bonding contributes to the compaction of the phenolic resins containing alkylenediamine in the main chain more strongly than the branching does.     

The use of caproic acid to prevent aerobic deterioration of silages after opening,with special reference to the amounts and time of application

The effectiveness of caproic acid (hexanoic acid) addition to silages prepared from Italian ryegrass or cocksfoot (dry matter 16.3–34.5%) in preventing aerobic deterioration after opening was investigated in five experiments with varying amounts and times of application. Silages prepared in PVC bag silos were transferred to expanded polystyrene containers and left in a room at 25°C for 7 days with access to air. Aerobic deterioration was judged by rise in temperature, increase in pH and changes in the counts of yeasts and moulds. A low dry matter silage containing a fairly large amount of butyric acid was stable, and another low dry matter silage was relatively stable. Silages made from wilted grass deteriorated. Application of 50 mmol/kg grass at ensiling prevented deterioration in all cases. The effect was also observed with 50 mmol addition at opening, 10 mmol at ensiling and 10 mmol at opening in that order.     

Effect of cross-flow on the frequency of bubble formation from a single-hole nozzle

Bubble formation from a single-hole nozzle placed vertically upward in a rotating water bath was investigated using a high-speed video camera. Air was used as the working gas. The measured values of the frequency of bubble formation, f _B, were compared with those observed in a stationary bath, f _B0. The velocity of cross-flow, ν_θ, affected the bubble formation significantly when it exceeded a critical value, ν_θc . The ratio of f _B to f _B0 was unity for ν_θ≦ν_θc , but it changed in a complex manner for ν_θ>ν_θc . In the latter case, when the air flow rate Q _g was relatively low, f _B/f _B0 became larger than unity irrespective of Q _g, and an empirical correlation of f _B/f _B0 was proposed as a function of ν_θ and the inner diameter of the nozzle, d _ni. As the gas flow rate increased, f _B/f _B0 decreased monotonically and became smaller than unity, and an empirical correlation of f _B/f _B0 was derived as a function of Q _g, ν_θ, and d _ni. These empirical correlations could approximate the measured values of f _B/f _B0 within a scatter of −15 to +20 pct.     

Structural analysis of an N-glycan with "beta1-4 bisecting branch" from human serum IgG by negative-ion MSn spectral matching and exoglycosidase digestion

A novel N-linked oligosaccharide (N-glycan) with "beta1-4 bisecting branch (galactose beta1-4 bisecting N-acetylglucosamine)" was found in human serum IgG. Its structure was efficiently analyzed by using beta-galactosidase digestion, a MSn spectral library database, and negative-ion MS2 spectral matching. For confirmation, the novel N-glycan was synthesized by using an expected standard N-glycan (acceptor), UDP-galactose (donor), and beta1-4 galactosyltransferase. This work also demonstrates that the MSn spectral library database, in particular, negative-ion MS2 spectral matching, can efficiently reduce the number of specific, sequential exoglycosidase digestions required and is useful for rapid structural analysis of unknown glycans not in the database.     

Simultaneous analysis of 2-aminopyridine-derivatized neutral and sialylated oligosaccharides from human serum in the negative-ion mode by sonic spray ionization ion trap mass spectrometry

Neutral and acidic (sialylated) 2-aminopyridine-derivatized (PA) oligosaccharides were analyzed by using reversed-phase high-performance liquid chromatography/ion trap mass spectrometry (RP-HPLC/IT MS) with a sonic spray ionization (SSI) source. Under the RP-HPLC separation using a buffer of 1 mM ammonium acetate (pH4.3) at a flow rate of 0.2 mL/min, both PA-oligosaccharides in the negative-ion mode showed a comparable degree of ionization efficiency, differing from that of the positive-ion mode, which exhibits a wide gap between their ionization efficiencies. In addition, the ion intensities of both PA-oligosaccharides were higher in the negative-ion mode than in the positive-ion mode. These results strongly suggest that the negative-ion mode of SSI-MS is suitable for simultaneous analysis of neutral and acidic (sialylated) oligosaccharides in RP-HPLC/MS. In the present study, RP-HPLC/SSI-IT MS in the negative-ion mode was used in the analysis of PA-oligosaccharides from human serum and its usefulness was investigated. As a result, 32 neutral and sialylated PA-oligosaccharides from human serum were identified with differentiating isomeric oligosaccharides and relatively quantified by a single HPLC/MS run. This method is useful for simple and rapid analysis of the overall distribution of neutral and sialylated oligosaccharides in a complex sample such as serum.     

Electron transfer reactions of glucose oxidase at Au111 electrodes modified with phenothiazine derivatives

The catalytic reaction of glucose oxidase (GOx) mediated by 3-(10-phenothiazyl)propionic acid (PT-PA) and phenothiazine-labeled poly(ethylene oxide) (PT-PEO1000) that are covalently bonded to Au(111) electrodes has been investigated. The PT-PA and PT-PEO1000 are reacted with 2-aminoethanethiol (AET), followed by the formation of a self-assembled monolayer (SAM) onto the Au surface. The PT group immobilized on the SAM of AET acts as an effective mediator for the electron transfer (ET) between the electrode and the FAD center of freely diffusing GOx in solution. The ET rate constant estimated from the catalytic current using a newly derived equation is larger by 1 order of magnitude for the PT-PA-modified system (1.1 x 10(5) dm(3) mol(-1) s(-1)) than for the PT-PEO1000 system (1.4 x 10(4) dm(3) mol(-1) s(-1)). The order of the magnitude of the ET rate constant clearly contrasts with the GOx hybrid systems that we previously investigated (Anal. Chem. 2003, 75, 910-917), in which the presence of the PEO spacer enhances the ET reaction rate. The reduction in the apparent PT concentration at the electrode interface due to the high mobility of the PEO chain, leading to low efficiency in the formation of an enzyme-mediator complex, is a possible reason for the lower mediation ability of PT-PEO1000 than that of PT-PA for the ET between the FAD group and PT(+) immobilized on the electrode. Inhibition of the penetration of GOx molecules into the monolayer and of the accessibility of some part of PT groups to GOx molecules could also be reasons for the lower mediation ability of PT-PEO1000 thickly modified on the electrode.     

The influence of hydrochloric acid on the effect of caproic acid in preventing aerobic deterioration of silages

In five experiments of the same design using silages made from wilted Italian ryegrass (dry matter 22.7–40.9%), the effects of caproic acid (C₆) (10 mmol kg^?1) with and without 6_N-HCl (20 ml kg^?1), applied at ensiling or at opening, in preventing aerobic deterioration of silages after opening silos were investigated. Application of C₆ either at ensiling or at opening was partially effective in preventing temperature increase, pH rise and breakdown of organic acids during the 7-day aerobic exposure period after opening the silos. Addition of HCl reduced the pH of silages irrespective of the time of application. However, no improvement of the effect of C₆ due to HCl supplementation was observed as far as the prevention of the aerobic deterioration was concerned. Treatment with C₆+ HCl at ensiling inhibited silage fermentation more extensively than C₆ alone. Viable counts of yeasts and moulds in the silages treated with C₆ or C₆+ HCl at ensiling tended to be lower than those in the control silages. Considerable increases in the counts of moulds were found in the control silages during the aerobic exposure period.     

A Technique to Eliminate Redundant Inter-Processor Communication on Parallelizing Compiler TINPAR

Optimizing inter-processor (PE) communication is crucial for parallelizing compilers for message-passing parallel machines to achieve high performance. In this paper, we propose a technique to eliminate redundant inter-PE messages. This technique utilizes data-flow analysis to find a definition point that corresponds to a use point where the definition and the use occur in different PEs. If several read accesses occurred in the same PE use the data defined at the same definition point in another PE, redundant inter-PE messages are eliminated as follows: only one inter-PE communication is performed for the earliest read access and the previously received data are used for the following read. In order to guarantee the consistency of the data, a valid flag and a sent flag are provided for each chunk of received data. The control of these flags is equivalent to the coherence control by the self invalidation on a compiler aided cache coherence scheme.     

Carbon resources of residue and manure in Japanese farmland soils

This study calculated the carbon (C) input to farmland soils in Japan in an effort to investigate the potential increase in soil C of farmland soils by proper application of crop residues (straw and root) and manure. The calculation was based on inventory and activity data obtained from statistics, literature sources and inquiry reports for the year 2005. The total C resources from crop residues and manure in Japan were 6.1 Tg C year⁻¹ and 2.3 Tg C year⁻¹, of which 4.9 Tg C year⁻¹ and 1.9 Tg C year⁻¹, respectively, were applied to farmland soil. The average C application rate was 1.7 ± 1.6 Mg C ha farmland⁻¹ year⁻¹ and the proportion of manure was 23 ± 26%. One scenario that improved the allocation of manure and crop residue input to farmland soil increased the average C input to farmland soil to 1.8 ± 1.3 Mg C ha farmland⁻¹ year⁻¹. This agricultural C flow represented only a small percentage of the global warming potential of the whole of Japan. Thus, management of C resources in the agricultural sector should focus on the sustainable use of soil rather than the C sequestration potential of soil. To improve the C flow for areas with high C input, the transportation of manure to neighboring municipalities failed to reduce the excessive amount of manure since those areas are concentrated in only a few regions. Other measures were required to reduce environmental problems due to the over-supply of manure to farmland soils. For areas with low C input, the introduction of green manure, changes in cultivation methods, and land use type itself must be considered in relation to the individual C requirements specific to land use, soil type and climate conditions.