Structurally Diverse Polyamines: Solid‐Phase Synthesis and Interaction with DNA

A versatile solid‐phase approach based on peptide chemistry was used to construct four classes of structurally diverse polyamines with modified backbones: linear, partially constrained, branched, and cyclic. Their effects on DNA duplex stability and structure were examined. The polyamines showed distinct activities, thus highlighting the importance of polyamine backbone structure. Interestingly, the rank order of polyamine ability for DNA compaction was different to that for their effects on circular dichroism and melting temperature, thus indicating that these polyamines have distinct effects on secondary and higher‐order structures of DNA.     

STD‐NMR‐Based Protein Engineering of the Unique Arylpropionate‐Racemase AMDase G74C

Structure‐guided protein engineering achieved a variant of the unique racemase AMDase G74C, with 40‐fold increased activity in the racemisation of several arylaliphatic carboxylic acids. Substrate binding during catalysis was investigated by saturation‐transfer‐difference NMR (STD‐NMR) spectroscopy. All atoms of the substrate showed interactions with the enzyme. STD‐NMR measurements revealed distinct nuclear Overhauser effects in experiments with and without molecular conversion. The spectroscopic analysis led to the identification of several amino acid residues whose substitutions increased the activity of G74C. Single amino acid exchanges increased the activity moderately; structure‐guided saturation mutagenesis yielded a quadruple mutant with a 40 times higher reaction rate. This study presents STD‐NMR as versatile tool for the analysis of enzyme–substrate interactions in catalytically competent systems and for the guidance of protein engineering.     

Change in liquid temperature behind the impeller blades with impeller speed in boiling stirred tanks

In our previous study (Fukuda, R., Tokumura, M., Znad, H.T. and Kawase, Y., 2009, Vapour generation from the impellers in boiling stirred tank reactors. Chem Eng Res Des, 87: 452–459), it was found that in boiling stirred tanks with multiple impeller systems vapour was generated from the heater at lower impeller speeds and with an increase in impeller speed most vapour was generated from the top impeller rather than the lower impellers and the heater. The change of nucleation sites with the impeller speed might be controlled by the local liquid temperature. Therefore we measured the liquid temperature behind the impellers blades and found the decrease in liquid temperature with increasing impeller speed. In this paper, a simple model was developed to predict the change in liquid temperature behind the impeller blades in which nucleation takes place. In the proposed model based on the results for pressure distribution on the impeller blade in the literature, the liquid temperature behind the impeller blades is estimated from the measured power consumption. The validation of the proposed model was conducted using the experimental results in our previous study and reasonable agreement was obtained.     

Pt and Sn Doped Sputtered CeO2 Electrodes for Fuel Cell Applications

The interaction of Pt with CeO₂ layers was investigated by using photoelectron spectroscopy. Thirty‐nanometre‐thick Pt and Sn doped CeO₂ layers were deposited simultaneously by rf‐magnetron sputtering on a Si(001) substrate and a carbon diffusion layer of a polymer membrane fuel cell by using a composite CeO₂–Pt–Sn target. The laboratory XPS and synchrotron radiation soft X‐ray and hard X‐ray photoemission spectra showed the formation of cerium oxide with completely ionised Pt^2+,4+ species, and with Pt⁴⁺ embedded in the film bulk. Hydrogen/air fuel cell activity measurements normalised to the amount of Pt used revealed high specific power of up to 5.4 × 10⁴ mW mg^–1 (Pt). The activity of these materials is explained by the strong activity of embedded Ptⁿ⁺ cations.     

Heat Source in Infinite Plane with Elliptic Rigid Inclusion and Hole

The plane thermoelastic problems of a stationary heat source in an infinite plane with an elliptic rigid inclusion and an elliptic hole are analyzed under thermally adiabatic and isothermal boundary conditions. The problems of an elliptic rigid inclusion are derived for the following cases: (1) the case that there are rigid-body displacement and rotation; and (2) the case that there is no rigid-body displacement or rotation. To analyze these problems, the following three fundamental solutions are derived: Problem A, in which a point heat source exists within an infinite domain; Problem B, in which the inclusion has a small amount of rotation; and Problem C, in which the inclusion is subjected to concentrated loads. Two cases can be obtained by superimposing these fundamental solutions. For the hole problem, the fundamental solution (Green's function) is also derived. In analysis, the complex stress functions, the mapping function, and the thermal dislocation method are used. The complex stress functions are obtained as a closed form. For analytic examples, the stress distributions are shown under thermally adiabatic and isothermal boundary conditions. For the crack problem, the stress intensity factors are shown for the location of the heat source.     

Study on the hydrothermal drying technology of sewage sludge

Drying of sewage sludge is an effective way for treatment and utilization of sewage sludge,where reduction of energy consumption is one of the major technical challenges.So we experimentally investigated the possibility of the hydrothermal treatment.We have found that treatment of sewage sludge by saturated steam with the temperature of 190°C and pressure of 20 bar can dramatically improve the dehydration performance of the slurry like product.And the water content can be reduced down to about 55% by a mech...     

Nondestructive Quantitative Evaluation of Porosity Volume Distribution in Aluminum Alloy Die Castings by Fractal Analysis

The nondestructive and three-dimensional quantitative evaluation of porosity in aluminum alloy die castings is proposed to identify whether the predominant cause of pore formation is shrinkage or entrapped gas. The validity of this method of evaluation was shown by comparing two different regions with different ratios of pores formed by shrinkage and gas. It was shown that the proposed evaluation can be used as a quantitative indication of porosity.     

Quantification of singlet oxygen from hematoporphyrin derivative by electron spin resonance

The mechanism of the generation and the quantitative analysis of singlet oxygen (1O2) formed by the exposure of a hematoporphyrin derivative (HpD) to light was re-evaluated by electron spin resonance (ESR) combined with 2,2,6,6,-tetramethyl-4-piperidine (TMPD). The change from TMPD to 2,2,6,6,-tetramethyl-4-piperidine-N-oxide (TAN) has been reported to depend on singlet oxygen. However, we confirmed that this reagent also react with superoxide anion (O2-) and hydroxyl radicals (OH). Therefore, the reactions between TMPD and 1O2, O2- and OH were re-examined using a kinetic approach. We found that the generation of TAN was proportional to the concentration of TMPD and HpD, as well as to the duration and strength of the illumination. The generation of TAN was not inhibited by dimethyl-sulfoxide (DMSO) or superoxide dismutase (SOD). The reaction rate between TMPD and 1O2 was determined to be 5.0 x 10(-7) M min-1. The generation of 1O2 from HpD was 2.7 x 10(-7) M min-1 under our conditions. The competitive reaction observed between 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and TMPD for O2- or OH shows that TMPD reacts with both forms of active oxygen, but gave no ESR signal. The second-order reaction rate constant of TMPD between O2- and OH was calculated as 73 M-1 s-1 and 1.5 x 10(9) M-1 s-1, respectively. The photochemical generation of 1O2 from methylene blue, another sensitizer, was also demonstrated by this method. These results show that ESR signal of TAN can be used for the highly selective monitoring of 1O2.