Plutonium isotopes and 137Cs in Dolon settlement near the Semipalatinsk Nuclear Test Site: About 50 years after the first nuclear weapon testing

Recent controversies concerning the radiation doses for populations living in the village of Dolon due to the nuclear explosions carried out at the Semipalatinsk Nuclear Test Site (SNTS) have encouraged us to evaluate in more detail the levels and distributions of residual long-lived radionuclides¹³⁷Cs and Pu isotopes (²³⁸Pu,^239,240Pu) in soils within the village. Soil core samples up to a depth of about 30 cm and/or 100 cm were collected at 25 sites and subjected to analysis of ¹³⁷Cs and Pu isotopes. The inventories of ¹³⁷Cs and ^239,240Pu were found to be in the wide range of 790-10,310 and 530-14,320 Bq/m², respectively. Sequential leaching of Pu from the soil showed that more than ca. 80% of the ^239,240Pu was not leached by hot digestion with conc. HNO³ + H₂O₂, indicating the presence of Pu associated with fused silicates. Further, the presence of hot-particles from the Pu contaminants by a-track radiography technique using CR-39 polycarbonate was confirmed in the soil, even at present, after about 50 years from the first nuclear weapon testing. This revised version was published online in July 2006 with corrections to the Cover Date.     

Selective formation of AAB- and ABC-type heterotrimeric alpha-helical coiled coils

The alpha-helical coiled coils have a representative amino acid sequence of (abcdefg)(n) heptad repeats. We previously reported that two peptides named IZ-2A and IZ-2W formed an (IZ-2A)(2)/IZ-2W heterotrimer with an Ala-Ala-Trp interaction in the hydrophobic core. In this paper, we describe the selective formation of AAB- and ABC-type heterotrimers. To increase the selectivity of the AAB-type heterotrimeric formation, Lys residues at the f position were mutated to either an Ala or a Gln residue to form IZ-2A(fA) or IZ-2W(fQ). Separately, both IZ-2A(fA) and IZ-2W(fQ) have a random structure at pH 7 and 20 degrees C. However, together IZ-2A(fA) and IZ-2W(fQ) form a 2:1 complex with a thermal transition midpoint (Tm) of 48 degrees C. This procedure was applied to prepare the ABC-type heterotrimer, in which two sets of Ala-Ala-Trp interactions were designed in the hydrophobic core. Interhelical interaction between the e and g positions and the alpha-helical propensity of the amino acid at the f position were also considered in the design. The resultant three peptides selectively formed the ABC-type heterotrimer with a Tm of 51 degrees C. Other peptide combinations had random coil properties.     

Studies of the polymerization of diallyl compounds. XXII. Polymerization of diallyl oxalate in the evolution of carbon dioxide at elevated temperatures

The polymerization of diallyl oxalate was conducted in the presence of radical initiators at a high temperature range of 80–180°C; a large decrease in degree of polymerization, an increase in residual unsaturation of the resulting polymer, and the evolution of carbon dioxide were observed with the elevation of temperature. These findings were reasonably interpreted by considering the dismutation of the uncyclized growing radical to yield the allyl radical, carbon dioxide, and polymer carrying a terminal double bond. The kinetics of the polymerization of diallyl oxalate in the evolution of carbon dioxide at elevated temperatures were also discussed in detail.     

Selective desorption and analysis of humic substances on suspended particles in river water

The elemental analysis and morphology of individual particles indicate that the dominant suspended particles in river water are kaolin covered with hydrated iron(III) oxide which strongly sorbs humic substances. Suspended particles, about 1 mg, collected from 250 ml of water by centrifugation, are treated with 0.7 ml of 0.1M sodium hydroxide to desorb humic substances. Approximately 60% of copper and 30% of lead on or in suspended particles exist as humic complexes.     

Crystal structures and topochemical polymerizations of 7,7,8,8-tetrakis(alkoxycarbonyl)quinodimethanes

Highly conjugated monomers, 7,7,8,8-tetrakis(alkoxycarbonyl)quinodimethanes (methoxy (1a), ethoxy (1b), isopropoxy (1c), benzyloxy (1d), chloroethoxy (1e), and bromoethoxy (1f)), were synthesized. Recrystallizations of 1a, 1c, 1e, and 1f yielded two crystal forms (prisms (1a-A) and needles (1a-B), needles (1c-A) and plates (1c-B), prisms (1e-A) and plates (1e-B), and prisms (1f-A) and needles (1f-B)), which have different molecular packing modes by X-ray crystal structure analysis, indicating that the crystals are polymorphic. In the photopolymerizations of these monomer crystals in the solid state, 1a-A, 1e-A, and 1f-A polymerized topochemically to give crystalline polymers. For their thermal polymerizations in the solid state, in addition to 1a-A, 1e-A, and 1f-A, 1e-B and 1f-B polymerized, but polymers formed from the 1e-B and 1f-B were amorphous. The packing of quinodimethane molecules in the crystals was defined by four kinds of parameters, stacking distance (d(s)), the distance between the reacting exomethylene carbon atoms (d(cc)), the angles formed between the stacking axis and longer axis of the monomer molecule (theta(1)), and the shorter axis of the monomer molecule (theta(2)), and then the polymerization reactivity of these quinodimethanes in the solid state was discussed on the basis of these parameters.     

Reversed-phase partition high-pressure liquid chromatography of trace amounts of inorganic and organic mercury with silver diethyldithiocarbamate

Inorganic and organic mercury diethyldithiocarbamates have been separated by reversedphase partition high-pressure liquid chromatography. The mercury chelates were formed by an exchange reaction with silver diethyldithiocarbamate in chloroform, in the presence of acetate buffer (pH 5.0). The inorganic and organic mercury chelates in the extract were separated within 30 min on a 3.9 x 300 mm mu-Bondapak C(18) column. EDTA (10(-4)M) in methanol-water mixture (78:22 v v ) was used as eluent at a flow-rate of 0.5 ml min .     

Role of the special pair in the charge-separating event in photosynthesis

We synthesized special-pair/electron-acceptor systems consisting of a complementary slipped cofacial dimer of imidazolyl-substituted zinc porphyrin, bearing pyromellitdiimide as the electron acceptor. In the case of the dimer, the first and second oxidation potentials were split into a total of four peaks in the differential pulse voltammetry measurement. Furthermore, the shift values of the first oxidation potentials obtained by changing the solvent polarity for the dimer were almost half of those observed for the monomer. These results indicate that the radical cation is delocalized over the whole pi system of the dimer. Time-resolved transient absorption measurements revealed that, relative to the corresponding monomer, the dimer accelerated the charge separation rate, but decelerated the charge recombination rate. The smaller reorganization energy of the slipped cofacial dimer relative to that of the monomeric system demonstrates the significance of the special-pair arrangement for efficient charge separation in photosynthesis.     

Kinetic study of the electron-transfer oxidation of the phenolate anion of a vitamin E model by molecular oxygen generating superoxide anion in an aprotic medium

Electron-transfer reduction of molecular oxygen (O2) by the phenolate anion (1-) of a vitamin E model, 2,2,5,7,8-pentamethylchroman-6-ol (1H), occurred to produce superoxide anion, which could be directly detected by a low-temperature EPR measurement. The rate of electron transfer from 1- to O2 was relatively slow, since this process is energetically unfavourable. The one-electron oxidation potential of 1- determined by cyclic voltammetric measurements is sufficiently negative to reduce 2,2-bis(4-tert-octylphenyl)-1-picrylhydrazyl radical (DOPPH*) to the corresponding one-electron reduced anion, DOPPH-, suggesting that 1- can also act as an efficient radical scavenger.     

Stereospecific synthesis of eight- and nine-membered cyclic ethers by Eu(fod)3-mediated cyclization of hydroxy epoxides

An efficient and versatile method for the stereospecific construction of α,ω-cis- and α,ω-trans-disubstituted eight- and nine-membered cyclic ethers was developed. Cyclization of the hydroxy epoxides promoted by Eu(fod)₃ proceeded via an S_N2 process and exo mode to provide the corresponding cyclic ethers in excellent yields.     

Direct nanocomposite of crystalline TiO2 particles and mesoporous silica as a molecular selective and highly active photocatalyst

Well-crystallised TiO2 particles (P-25, 20-30 nm in diameter) were directly incorporated into surfactant-templated mesoporous silica particles (pore diameter: 2.7 nm), and the composite material with a high TiO2 content (60 wt%) showed molecular selective and enhanced photocatalysis for decomposition of 4-nonylphenol.