Separation and recovery of Cm from Cm–Pu mixed oxide samples containing Am impurity

Curium was separated and recovered as an oxalate from a Cm–Pu mixed oxide which had been a ²⁴⁴Cm oxide sample prepared more than 40 years ago and the ratio of ²⁴⁴Cm to ²⁴⁰Pu was estimated to 0.2:0.8. Radiochemical analyses of the solution prepared by dissolving the Cm–Pu mixed oxide in nitric acid revealed that the oxide contained about 1 at% of ²⁴³Am impurity. To obtain high purity curium solution, plutonium and americium were removed from the solution by an anion exchange method and by chromatographic separation using tertiary pyridine resin embedded in silica beads with nitric acid/methanol mixed solution, respectively. Curium oxalate, a precursor compound of curium oxide, was prepared from the purified curium solution. 11.9 mg of Cm oxalate having some amounts of impurities, which are ²⁴³Am (5.4 at%) and ²⁴⁰Pu (0.3 at%) was obtained without Am removal procedure. Meanwhile, 12.0 mg of Cm oxalate (99.8 at% over actinides) was obtained with the procedure including Am removals. Both of the obtained Cm oxalate sample were supplied for the syntheses and measurements of the thermochemical properties of curium compounds.     

Mix-mode TiO-C18 monolith spin column extraction and GC-MS for the simultaneous assay of organophosphorus compounds and glufosinate, and glyphosate in human serum and urine

A rapid, specific, and sensitive method for the simultaneous quantitation of organophosphates (fenitrothion (MEP), malathion, and phenthoate (PAP)), glufosinate (GLUF), and glyphosate (GLYP) in human serum and urine by gas chromatography-mass spectrometry (GC-MS) has been validated. All of the targeted compounds together with the internal standard were extracted from the serum and urine using a mix-mode TiO-C(18) monolithic spin column. The recovery of organophosphates from serum and urine ranged from 12.7 to 49.5%. The recovery of GLUF and GLYP from serum and urine ranged from 1.9 to 7.9%. The intra- and inter-accuracy and precision (expressed as relative standard deviation, %RSD) were within 96.7-107.7% and 4.0-13.8%, respectively. The detection and quantitation limits for serum and urine were 0.1 and 0.1 μg/ml, respectively, for organophosphates, 0.1 and 0.5 μg/ml, respectively for GLUF and GLYP. The method had linear calibration curves ranging from 0.1 to 25.0 μg/ml for organophosphates and 0.5-100.0 μg/ml for GLUF, and GLYP. The validated method was successfully applied to a clinical GLYP poisoning case.     

Phenylsulfanylation of 3',4'-unsaturated adenosine employing thiophenol-N-iodosuccinimide leads to 4'-phenylsulfanylcordycepin: synthesis of 4'-substituted cordycepins on the basis of substitution of the phenylsulfanyl leaving group

Upon reaction of the 3',4'-unsaturated adenosine derivative 2 with N-iodosuccinimide (NIS) and thiophenol, an unexpected electrophilic hydrophenylsulfanylation proceeded to provide 4'-phenylsulfanylcordycepin 7 in 79% yield with the ratio 7a/7b = 6.6/1. A study of the reaction mechanism revealed that hydrogen iodide (HI) generated from NIS and PhSH acted as an active species. On the basis of a deuterium experiment using PhSD, initial protonation occurred at the β face of the double bond to furnish the β-π complex III, which underwent anti addition of PhSH as a major pathway. Nucleophilic substitution of N(6)-pivaloylated 9 with various alcohols in the presence of N-bromosuccinimide (NBS) gave the respective 4'-α-alkoxycordycepins 15a-21a as the major stereoisomers. Use of DAST in place of an alcohol gave the 4'-α-fluoro analogue 23a stereoselectively. Radical-mediated carbon-carbon bond construction was also applicable to 7, giving 4'-α-allylcordycepin (24a) and 4'-α-cyanoethylcordycepin (25) derivatives.     

An access to the β-anomer of 4'-thio-C-ribonucleosides: hydroboration of 1-C-aryl- or 1-C-heteroaryl-4-thiofuranoid glycals and its regiochemical outcome

We have developed a novel method for the synthesis of the β-anomer of 4'-thio-C-ribonucleosides from 3,5-O-(di-tert-butylsilylene)-4-thiofuranoid glycal. Palladium-catalyzed coupling of 1-tributylstannyl-4-thiofuranoid glycal with iodobenzene or a heteroaryl halide gave 1-C-phenyl- or 1-C-heteroaryl-glycals. Hydroboration of these glycals proceeded at the α-face, and subsequent alkaline hydrogen peroxide treatment of the resulting 2'-α-borane furnished the respective β-anomer of 4'-thio-C-ribonucleosides. These results demonstrate that this synthetic method has a wider scope in terms of heterocyclic base structure. During this study, unexpected Markovnikov-oriented hydroboration has been observed to lead to the respective 1'-α-boranes. These 1'-boranes were converted into either the ring-opened structure or the 2'-deoxy derivatives depending upon their stability.     

Pressure broadening coefficients of the water vapor lines at 556.936 and 752.033 GHz

The air induced broadening coefficients of the pure rotational transitions of H₂O at 556.936 GHz (1₁₀←1₀₁), and 752.033 GHz (2₁₁←2₀₂) were measured by terahertz time-domain spectroscopy. The air broadening coefficient was determined to be for the 556.936 GHz line and for the 752.033 GHz line, respectively. The present broadening coefficients for the 556.936 GHz water line are significantly smaller than those of Markov and Krupnov [Measurements of the pressure shift of the 1(10)-1(01) water line at 556.936 GHz produced by mixtures of gases. J Mol Spect 1995:172;211-4] but relatively close to the values of the HITRAN database. The measured data may improve the accuracy of the abundance of water vapor retrieved from spectra obtained by the Odin/SMR satellite instrument. The effect on the satellite retrieval processing is discussed.     

Coherent and Incoherent Excitations of Electron-Doped SrTiO3

Resonant photoemission at the Ti 2p and O 1s edges on a Nb-doped SrTiO(3) thin film revealed that the coherent state (CS) at the Fermi level (E(F)) had a mainly Ti 3d character whereas the incoherent in-gap state (IGS) positioned approximately 1.5 eV below E(F) had a mixed character of Ti 3d and O 2p states. This indicates that the IGS is formed by a spectral-weight transfer from the CS and subsequent spectral-weight redistribution through d-p hybridization. We discuss the evolution of the excitation spectrum with 3d band filling and rationalize the IGS through a mechanism similar to that proposed by Haldane and Anderson.     

Kinetics of CO Molecules Taking into Account Resonant VE Exchanges in a Nonequilibrium Nozzle Flow

The kinetics of CO molecules with excited electronic levels for a nonequilibrium flow in nozzles is studied. Three electronic energy levels are taken into account; the VV exchanges of the vibrational energy within each electronic energy level, VT transitions from the vibrational energy to the translational energy, and VE exchanges between the vibrational energy and the electronic terms occur in the system. The system of equations of vibrational level kinetics and gasdynamics, which is written in the zeroth approximation of the Chapman–Enskog method, is solved numerically. Special attention is paid to estimating the effect of the VE exchanges of the vibrational energy on the formation of nonequilibrium populations of the vibrational levels. It is shown that resonant VE transitions considerably affect the relaxation process and noticeably change the population of the upper vibrational levels even in the absence of recombination and dissociation processes; VE exchanges also affect the time dependence of the vibrational temperature.     

Enzymatic Synthesis of Chitin‐ and Chitosan‐graft‐Aliphatic Polyesters

Summary: The title polymers, in which both the stem and the graft are biodegradable, have been synthesized for the first time in a one‐pot, lipase‐catalyzed, graft‐polymerization reaction (in bulk, at 70 °C) of β‐butyrolactone (β‐BL) and ε‐caprolactone (ε‐CL) onto chitin and chitosan. The reactivity order of the lactones was found to be ε‐CL > β‐BL ≫ γ‐BL (no reaction). All the graft polymers prepared are insoluble in common organic solvents.

Synthesis of chitin‐ or chitosan‐graft‐aliphatic polyesters.