Formation of Supramolecular Nanostructures through in Situ Self-Assembly and Post-Assembly Modification of a Biocatalytically Constructed Dipeptide Hydrazide**

Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging.     

Improvement in flow-sheet of extraction chromatography for trivalent minor actinides recovery

Journal of Radioanalytical and Nuclear Chemistry - Extraction chromatography flow-sheet employing octyl(phenyl)-N,N-diisobutylcarbonoylmethylphosphine oxide and bis(2-ethylhexyl) hydrogen phosphate...     

Theory of chemical bonds in metalloenzymes XXII: a concerted bond-switching mechanism for the oxygen–oxygen bond formation coupled with one electron transfer for water oxidation in the oxygen-evolving complex of photosystem II

ABSTRACT

QM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S₄ state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)₄–O₍₅₎ bond and the π*-LUMO of the Mn(V)₁=O₍₆₎ bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn₄O₆ cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)₁=O₍₆₎ bond to the σ*-LUMO of the Mn(IV)₄–O₍₅₎ bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)₄–O₍₅₎]^-? part is relaxed to the ?Mn(III)₄?…?O₍₅₎^- structure and the cation radical [O₍₆₎=Mn(V)₁]⁺ ? part is relaxed to the ⁺O₍₆₎–Mn(IV)₁? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)₄->Mn(III)₄ and Mn(V)₁->Mn(IV)₁. On the other hand, the O₍₅₎^- and O₍₆₎⁺ sites generated undergo the O–O bond formation in the CaMn₄O₆ cluster. The Ca(II) ion in the cubane- skeleton of the CaMn₄O₆ cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)₁=O₍₆₎ and σ*-LUMO of Mn(IV)₄–O₍₅₎, indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism.     

Ion-pair formation of a copper(II)-ammine complex with an anionic surfactant and the recovery of copper(II) from ammonia medium by the surfactant-gel extraction method.

The extraction and separation of copper(II), zinc(II), cobalt(II), and cadmium(II) were investigated. Both copper(II) and zinc(II) formed ammine-complexes, while cadmium(II) and cobalt(II) formed hydroxide precipitates in an ammonia medium. By the addition of sodium dodecylsulfate (SDS), a copper(II) complex formed an ion-pair (copper-ammine-DS), which was extracted into the SDS phase. However, a zinc(II) complex did not form an ion-pair, and was soluble in water. Copper(II) ion was recovered by stripping (back-extraction) after the addition of hydrochloric acid. This method was applied to the separation of copper(II) in a brass alloy.     

Large-volume injection electrothermal AAS combined with tungsten-treated pyrolytic graphite furnace: determination of cadmium in tap, snow and river water samples with phosphate modifier.

A large-volume (100 microl) injection-ETAAS with W-treated PG furnace combined with a phosphate modifier was applied to the determination of unpolluted levels of Cd in tap, snow and river-water samples. The limit of detection of 1.1 ng l(-1) was observed for a 4 w/v% NH4H2PO4 modifer. Matrix interference studies were tested for major ion species well found in fresh water. The direct determination of Cd in certified river water (12 +/- 2 ng l(-1)) was carried out and the observed value was in agreement with the certified one. The good recoveries of Cd added to real environmental water samples were also observed. This method was applied to the determination of Cd in unpolluted environmental water samples.     

Enhancement of Magneto-Optic Effect in Optical Isolator with Semiconductor Guiding Layer by Selective Oxidation of AlInAs

Selective oxidation of an AlInAs layer was investigated for enhancement of magneto-optic effect in an optical isolator. Twelve times nonreciprocal phase shift enhancement was estimated from a measured AlInAs-oxide refractive index.     

Radiation pasteurised oil palm empty fruit bunch fermented with Pleurotus sajor-caju as feed supplement to ruminants

In solid state fermentation, Pleurotus sajor-caju has been found to be able to degrade at least 30% oil palm empty Fruit Bunch (EFB) fibre leaving 70 % useful materials. Conditions under which fermentation carried out were investigated. It was found that, in the temperature range between 25– 28 °C, relative ph between 6–8, moisture between 60–70 % and medium composition of CaCO₃: rice bran 2 %: 5 % were the optimum conditions. The results showed in fermented products that, there were substantial reduction in cellulosic component such as Crude Fiber (CF, 18 %); Acid Detergent Fibre (ADF, 45 %), Neutral Detergent Fibre (NDF, 61 %) and Acid Detergent Lignin (ADL, 14 %). However, Crude Protein (CP, 10%) increased resulted from single cell protein enrichment of mycelial microbial mass. The mass reductions of substrate in fermentation process corresponds to the CO₂ released during fermentation. Hence, attributable to the decreased in content of CF, ADF, NDF, and ADL. The digestibility study has also been carried out to determine the useful level of this product to ruminant. Aflatoxin content was detected low in both the initial substrates and products. Based on nutritional value and low content of aflatoxin, the product is useful as a source of roughage to ruminant.     

Near-infrared photorefractivity in Cr-doped potassium sodium strontium barium niobate single crystal

We report on the photorefractive properties of a Cr-doped (K_1–x Na _x )_2A–2 (Sr _y Ba_1–y )_2–A Nb₁₀O₃₀ (x=0.586, y=0.659, A=1.12) single crystal in the near-infrared spectrum. The sample exhibits photorefractivity for wavelengths up to at least 840 nm where the steady-state two-beam coupling gain is found to be larger than 2 cm^–1. Photorefractive gain and decay rate are measured as a function of wavelength, grating spacing and intensity. The wavelength dependence of gain fluctuations in two-beam coupling are also measured.     

Influence of nuclear reactor accident at Chernobyl' on the environmental radioactivity in Toyama

The environmental radioactivity caused by the reactor accident at Chernobyl' was investigated from May 7 to May 31 of 1986 in Toyama. Measurement of radioactivities in airborne particles, rain water, drinking water, milk, and mugwort are carried out by gamma-ray spectrometry (pure Ge detector; ORTEC GMX-23195). Ten different nuclides (103Ru, 106Ru, 131I, 132Te-I, 134Cs, 136Cs, 137Cs, 140Ba-La) are identified from samples of airborne particles. In the air samples, a maximum radioactivity concentration of each nuclide is observed on 13th May 1986. The time of the reactor shut-down and the flux of thermal neutron at the reactor were calculated from 131I/132I and 137Cs/134Cs ratio. The exposure dose in Toyama by this accident is given as follows: internal exposure; [thyroid] adult-59 microSv, child-140 microSv, baby-130 microSv, [total body] adult-0.2 microSv, child, baby-0.4 microSv, external exposure; 7 microSv, effective dose equivalent; adult-9 microSv, child-12 Sv, baby-11 microSv.