3,4-Thienylene-ethynylene Oligomers

Several well-defined 3,4-thienylene-ethynylene oligomers with different chain lengths have been synthesized and characterized. X-Ray crystallographic analyses proved their unique, totally helical conformations.     

Heterogeneous distribution of radiocesium in aerosols, soil and particulate matters emitted by the Fukushima Daiichi Nuclear Power Plant accident: retention of micro-scale heterogeneity during the migration of radiocesium from the air into ground and river systems

We analyzed ¹³⁷Cs in aerosols, rock, soil and river suspended sediment collected after the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident. Based on the results, we discuss the post-event behavior and transportation of radiocesium in the environment from the air into ground and river systems. First, radionuclides were emitted from the FDNPP as airborne ‘hot’ particles, which contained water-soluble fractions of radiocesium. Radiocesium was still present in a water-soluble fraction after deposition on the ground. Subsequent interaction of the ‘hot’ particles with water (e.g. rainfall) dissolved and strongly fixed the radiocesium on rock and soil particles, thus changing the radiocesium into insoluble forms. The distribution of ‘hot spots’ was possibly controlled by the initial position of deposition on the ground. Consequently, ‘hot spots’ were studded on the rock surface rather than being uniformly distributed. The distribution of radiocesium in river suspended particles was not homogeneous during water transportation, reflecting the heterogeneity of radiocesium in rock and soil. Leaching experiments demonstrated that radiocesium in rock, soil and river suspended sediment was fairly insoluble, showing that the adsorption reaction is irreversible. The micro-scale heterogeneous distribution of radiocesium in aerosols, soil and suspended particles was due to the presence of ‘hot’ particles in aerosols. Dissolution of radiocesium in the ‘hot’ particles in the aerosols and subsequent irreversible adsorption onto the soil particle complex are responsible for the preservation of the heterogeneity both in soil and in river suspended particles.     

Local distribution of radioactivity in tree leaves contaminated by fallout of the radionuclides emitted from the Fukushima Daiichi Nuclear Power Plant

We analyzed fresh and dead leaves collected in forests in Fukushima after the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident, using autoradiography. Both fresh and dead leaves of Cryptomeria japonica were contaminated by radionuclides (¹³⁴Cs and ¹³⁷Cs). Contamination of the fresh leaves was possibly attributed to interception of radionuclides by tree canopies, whereas the dead leaves indicated the direct deposition of radionuclides by fallout and/or washout of radionuclides intercepted by tree canopies. Translocation of radiocesium from a contaminated branch to new leaves growing after the FDNPP accident was not clearly observed, although transfer of radiocesium from leaf parts to male flowers occurred. Fallen leaves of Quercus serrata, which started growing after the FDNPP accident, did not show radioactivity, indicating that significant amounts of translocation from other parts to new leaves did not occur. Fallen leaves of Q. serrata collected from a litter showed hot spots originating from direct fallout. Needles of Pinus densiflora were also contaminated by fallout. Leaching with pure water removed soluble fractions of radiocesium and hot particles from the surface of the contaminated leaves, but significant amounts of radioactivity remained. This means that foliar absorption occurred in both fresh and dead leaves. Further leaching experiments using surfactant and acetone could not remove the remaining radiocesium from the leaves. The leaching experiments indicate that radiocesium in the contaminated leaves is strongly fixed in leaf tissues and is not readily released unless leaf tissues are decomposed.     

A Pd(II)-hydroxyporphycene: synthesis, characterization, and photoinduced proton-coupled electron transfer

A Pd(II) complex, Pd(TPrPc-OH) (1, TPrPc-OH = 9-hydroxy-2,7,12,17-tetrapropylporphycenato dianion), has been synthesized and characterized. ¹H NMR spectroscopy revealed that compound 1 exists as its enol form in solution. The H atom of the hydroxy group in 1 was exchanged with deuterium on addition of ethanol-d ₆. UV–visible spectra showed a red shift of the Q band of 1 in THF compared with that of the acetoxy derivative Pd(TPrPc-OAc) (2, TPrPc-OAc = 9-acetoxy-2,7,12,17-tetrapropylporphycenato dianion). The pK _a value of the hydroxy group in 1 was determined, by means of a UV–visible titration experiment, to be 10.56. A cyclic voltammogram of 1 in a mixture of THF and Britton–Robinson buffered aqueous solution revealed one-electron and one-proton coupled transfer in the oxidation process in the pH range from 2.7 to 10.5, which was identified by pH-varying experiments and the Pourbaix diagram. Transient absorption spectroscopy revealed that an electron-transfer reaction occurred from the triplet excited-state of 1 to 2,3,5,6-tetramethyl-1,4-benzoquinone (duroquinone, DQ) upon pulse laser irradiation at 532 nm. Such an intermolecular photoinduced electron-transfer reaction was not observed between the Ni analog, Ni(TPrPc-OH), and DQ. The reaction rate constant, k _q, was indicative of a kinetic isotope effect with k _q(H)/k _q(D) = 1.7, supporting the belief that the exited-state electron transfer from 1 to DQ is accompanied by proton transfer.     

Cyclic sample pooling using two‐dimensional liquid chromatography system enhances coverage in shotgun proteomics

We report a cyclic sample pooling technique devised in two‐dimensional liquid chromatography–electrospray ionization mass spectrometry (LC‐ESI‐MS) shotgun proteomics that renders deeper proteome coverage; we combined low pH reversed‐phase (RP) LC in trifluoroacetic acid in the first dimension, followed by cyclic sample pooling of the eluate and low‐pH RP‐LC in formic acid in the second dimension. The new protocol has a significantly higher resolving power suitable for LC‐ESI‐MS/MS shotgun proteomics. Copyright © 2013 John Wiley & Sons, Ltd.     

A Convenient Synthesis of Juglone Via Neutral Salcomine Oxidation

1,5-Dihydroxynaphthalene and its derivatives can be oxidized by molecular oxygen in the presence of catalytic amounts of salcomine under neutral conditions to afford the corresponding 1,4-naphthoquinones as the major products.     

Enzymatic silicone oligomerization catalyzed by a lipid-coated lipase

A lipid (1)-coated lipase can catalyze the oligomerization of diethoxydimethylsilane (DEDMS) in isooctane containing 2wt% water, where the polymerization occurs at the OH group of the coating lipid (1) in the enzyme cavity.     

Oligo(octithienylene-diethynylene)s as unprecedentedly long conjugated nanomolecules

[reaction: see text] A series of oligo(octithienylene-diethynylene)s alternately composed of octithiophene and diacetylene units have been prepared by a random Eglinton coupling reaction among mono- and diethynyloctithiophenes. The largest compound isolated in the oligomeric series is comprised of twelve octithiophene units and eleven diacetylene units, and its molecular length reaches ca. 43 nm, which is the longest among single-component conjugated nanomolecules.     

UV dose measurements of photosensitive dermatosis patients by polycrystalline GaN-based portable self-data-acquisition UV monitors

We have developed a UV monitor with polycrystalline (poly-) gallium nitride (GaN) UV sensors and evaluated its performance from the viewpoint of its effectiveness for use with photosensitive dermatosis patients. The poly-GaN UV sensor is sensitive to UV light from 280 to 410 nm even without optical filters. The UV monitor is a portable self-data-acquisition instrument with a minimum detection level (defined as average UV intensity over 290 to 400 nm) of 2 microW/cm2 and can store UV dose data for 128 days. It allows easy measurement of four orders of magnitude of ambient UV intensity and dose from indoor light to direct solar radiation in summer. Trial use of the UV monitor by five xeroderma pigmentosum patients started in June 2000 and was carried out for 1 year. It was demonstrated that the UV monitor was useful in improving their quality of life.     

Dynamic covalent approach to [2]- and [3]roxtanes by utilizing a reversible thiol-disulfide interchange reaction

A dynamic covalent approach to disulfide-containing [2]- and [3]rotaxanes is described. Symmetrical dumbbell-shaped compounds with two secondary ammonium centers and a central located disulfide bond were synthesized as components of rotaxanes. The rotaxanes were synthesized from the dumbbell-shaped compounds and dibenzo-[24]crown-8 (DB24C8) with catalysis by benzenethiol. The yields of isolated rotaxanes reached about 90 % under optimized conditions. A kinetic study on the reaction forming [2]rotaxane 2 a and [3]rotaxane 3 a suggested a plausible reaction mechanism comprising several steps, including 1) initiation, 2) [2]rotaxane formation, and 3) [3]rotaxane formation. The whole reaction was found to be reversible in the presence of thiols, and thermodynamic control over product distribution was thus possible by varying the temperature, solvent, initial ratio of substrates, and concentration. The steric bulk of the end-capping groups had almost no influence on rotaxane yields, but the structure of the thiol was crucial for reaction rates. Amines and phosphines were also effective as catalysts. The structural characterization of the rotaxanes included an X-ray crystallographic study on [3]rotaxane 3 a.