Recent developments and on-line tests of uranium carbide targets for production of nuclides far from stability

The capacity of uranium carbide target materials of different structure and density for production of neutron-rich and heavy neutron-deficient nuclides have been investigated. The yields of Cs and Fr produced by a 1 GeV proton beam of the PNPI synchrocyclotron and release properties of different targets have been measured. Yields and release efficiencies of Cs and Fr produced from a high density UC target material and from low density UCx prepared by the ISOLDE method at IRIS in the collaboration with PARRNe group from Orsay are compared. The yields from ISOLDE original target are presented for comparison as well.     

改善芯部加料效率的新机制研究

对五种不同组合的固态氢同位素靶丸H2、HD、D2、DT和T2在聚变等离子体中的消融率作了同位素修正。结果表明,由于这种新机制———同位素效应,引起的靶丸半径烧蚀率修正从氢靶丸的1下降到氚靶丸的0.487。因而在消融率计算时是不可忽略的,这些修正可导致更深的靶丸消融物质沉积因而改善芯部加料效率。更重要的是,考虑到同位素效应后,对ITER的加料困难有适度的减轻。进一步的数值计算工作表明,以低场侧注入半径rp0=0.5cm的DT靶丸,同样渗入ITER等离子体100cm,按Kuteev的2D透镜模型,同位素修正使要求靶丸的初速度从vp0=24.27×105cm·s-1减小到16.2×105cm·s-1,而对Parks模型,从vp0=8.07×105cm·s-1减小到5.4×105cm·s-1。如果从中平面高场侧注入尺寸rp0=0.5cm的DT靶丸,当合并考虑同位素修正和由于消融云内外比压差产生的净垂直极化电流引起的沿大半径方向漂移后,vp0可降低到工程技术上比较容易实现的低速1.73×104cm·s-1从而可能使靶丸的消融物质沉积到ITER等离子体中心。     

Development of chemical isotope labeling liquid chromatography mass spectrometry for silkworm hemolymph metabolomics

Silkworm (Bombyx mori) is a very useful target insect for evaluation of endocrine disruptor chemicals (EDCs) due to mature breeding techniques, complete endocrine system and broad basic knowledge on developmental biology. Comparative metabolomics of silkworms with and without EDC exposure offers another dimension of studying EDCs. In this work, we report a workflow on metabolomic profiling of silkworm hemolymph based on high-performance chemical isotope labeling (CIL) liquid chromatography mass spectrometry (LC-MS) and demonstrate its application in studying the metabolic changes associated with the pesticide dichlorodiphenyltrichloroethane (DDT) exposure in silkworm. Hemolymph samples were taken from mature silkworms after growing on diet that contained DDT at four different concentrations (1, 0.1, 0.01, 0.001 ppm) as well as on diet without DDT as controls. They were subjected to differential ¹²C-/¹³C-dansyl labeling of the amine/phenol submetabolome, LC-UV quantification of the total amount of labeled metabolites for sample normalization, and LC-MS detection and relative quantification of individual metabolites in comparative samples. The total concentration of labeled metabolites did not show any significant change between four DDT-treatment groups and one control group. Multivariate statistical analysis of the metabolome data set showed that there was a distinct metabolomic separation between the five groups. Out of the 2044 detected peak pairs, 338 and 1471 metabolites have been putatively identified against the HMDB database and the EML library, respectively. 65 metabolites were identified by the dansyl library searching based on the accurate mass and retention time. Among the 65 identified metabolites, 33 positive metabolites had changes of greater than 1.20-fold or less than 0.83-fold in one or more groups with p-value of smaller than 0.05. Several useful biomarkers including serine, methionine, tryptophan, asymmetric dimethylarginine, N-Methyl-D-aspartic and tyrosine were identified. The changes of these biomarkers were likely due to the disruption of the endocrine system of silkworm by DDT. This work illustrates that the method of CIL LC-MS is useful to generate quantitative submetabolome profiles from a small volume of silkworm hemolymph with much higher coverage than conventional LC-MS methods, thereby facilitating the discovery of potential metabolite biomarkers related to EDC or other chemical exposure.     

The Cope Rearrangement of 1,5‐Dimethylsemibullvalene‐2(4)‐d1: Experimental Evidence for Heavy‐Atom Tunneling

As an experimental test of the theoretical prediction that heavy‐atom tunneling is involved in the degenerate Cope rearrangement of semibullvalenes at cryogenic temperatures, monodeuterated 1,5‐dimethylsemibullvalene isotopomers were prepared and investigated by IR spectroscopy using the matrix isolation technique. As predicted, the less thermodynamically stable isotopomer rearranges at cryogenic temperatures in the dark to the more stable one, while broadband IR irradiation above 2000 cm⁻¹ results in an equilibration of the isotopomeric ratio. Since this reaction proceeds with a rate constant in the order of 10⁻⁴ s⁻¹ despite an experimental barrier of E_a=4.8 kcal mol⁻¹ and with only a shallow temperature dependence, the results are interpreted in terms of heavy‐atom tunneling.     

Development of an improved method to perform single particle analysis by TIMS for nuclear safeguards

A method is described that allows measuring the isotopic composition of small uranium oxide particles (less than 1 μm in diameter) for nuclear safeguards purposes. In support to the development of reliable tools for the identification of uranium and plutonium signatures in trace amounts of nuclear materials, improvements in scanning electron microscopy (SEM) and thermal ionization mass spectrometry (TIMS) in combination with filament carburization and multiple ion counting (MIC) detection were investigated. The method that has been set up enables the analysis of single particles by a combination of analytical tools, thus yielding morphological, elemental and isotopic information. Hereby individual particles of certified reference materials (CRMs) containing uranium at femtogram levels were analysed. The results showed that the combination of techniques proposed in this work is suitable for the accurate determination of uranium isotope ratios in single particles with improved capabilities for the minor abundant isotopes.     

Differential Contribution of Albumin and Lipids to the Hydrophobic Extraction of Bis-(2-ethylhexyl) Phthalate from Hemodialysis Tubing by Human Serum: Analysis by Gas Chromatography - Stable Isotope Dilution Mass Spectrometry

Abstract

A method is presented which allows quantitative assignment of hydrophobic human serum components to the extraction of bis-(2-ethylhexyl) phthalate (DEHP) from medical tubing. Under optimized conditions (sample pH 5.5; fluid-fluid extraction with ethyl acetate + tert-butyl methyl ether 1 + 1 v/v; DEHP-ring-D4 as internal standard with ratios of endogenous (m/z = 149) and added deuterated DEHP (m/z = 153) adjusted to around 1.0; equilibration of added internal standard with the hydrophobic sample for 24 hours), a high precision can be achieved with an intra-assay coefficient of variation of 1.5% (n = 7) for sample DEHP quantification. Phthalate migration from hemodialysis tubing was quantified by use of a peristaltic pump and recirculation (200 minutes) of serum with different degrces of hypertriglyceridemia (range from 2.26 to 14.5 g/L) or solutions of human albumin (10 to 50 g/L). Only DEHP, but no other phthalates are detected in the extracts. There exist linear relations between DEHP extraction and triglyceride content (increase by 1.01 μg DEHP/g tubing material per g triglyceride/L serum) as well as between DEHP extraction and albumin content (0.59 μg DEHP/g tubing material per g albumin/L). Under physiological conditions, the total amount of albumin extracts 17.7-fold more DEHP than the total triglyceride amount in human serum. The suitability of the proposed method as a candidate reference method as well as consequences for dyslipidemic and hypalbuminemic patients on hemodialysis schemes are discussed.     

Precise determination of dissolved silica in seawater by ion-exclusion chromatography isotope dilution inductively coupled plasma mass spectrometry

Ion exclusion chromatograph (IEC) isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP–MS) (IEC–ID–ICP–MS) was developed for measurement of dissolved silica in seawater, which was applied to production of certified reference materials (CRMs) of three concentration levels of nutrients (high, medium and low levels). IEC–ICP–MS has been employed to separate dissolved silica from seawater matrix. In the present study, in order to solve substantial problems due to spectral interference in ICP–MS and to improve the accuracy of IEC–ICP–MS beyond standard addition or conventional calibration methods, ID method was coupled with ICP-sector field mass spectrometry (operated under medium resolution,i.e., m/Δm = 4000). In addition, effects of various operating parameters in ICP–MS on a silicon background level were also investigated to obtain lower background equivalent concentration (BEC). As a result, 3 ng g⁻¹ of the BEC and 0.5 % of relative standard uncertainties were achieved in the analyses of dissolved silica in seawater samples at concentration levels from 4.0 mg kg ^-1 to 0.8 mg kg⁻¹ as silicon. The developed method was successfully validated by analyses of an artificial seawater containing a known amount of silicate and the seawater certified reference material MOOS-2 produced by the National Research Council Canada.     

Accurate determination and certification of bromine in plastic by isotope dilution inductively coupled plasma mass spectrometry

The accurate analytical method of bromine (Br) in plastic was developed by an isotope dilution inductively coupled plasma mass spectrometry (ID-ICPMS). The figures of merit of microwave acid digestion procedures using polytetrafluoroethylene (PTFE) or quartz vessels were studied and the latter one was suitable for Br analysis since its material was free from Br contamination. The sample dilution procedures using Milli-Q water or ammonium (NH₃) solution were also studied to remove memory effect for ICPMS measurement. Although severe memory effect was observed on Milli-Q water dilution, NH₃ solution could remove it successfully. The accuracy of the ID-ICPMS was validated by a certified reference material (CRM) as well as the comparison with the analytical result obtained by an instrumental neutron activation analysis (INAA) as different analytical method. From these results, the ID-ICPMS developed in the present study could be evaluated as accurate analytical method of Br in plastic materials and it could apply to certification of Br in candidate plastic CRM with respect to such regulations related to RoHS (restriction of the use of hazardous substances in electrical and electronics equipment) directive.     

Resonance-enhanced multiphoton ionization (REMPI) spectroscopy of the Cl and Cl isotopomers of p-chloroanisole

The geometric structures and vibrations of p-chloroanisole isotopomers in the first electronically excited state were studied by mass-analyzed resonance-enhanced two-photon ionization spectroscopy and by theoretical calculations. The band origins of the S₁ ← S₀ electronic transitions of ³⁵Cl and ³⁷Cl isotopomers were found to be equivalent at 34 859 ± 3 cm⁻¹. Assignments of the observed vibrational bands of the two isotopomers were made mainly based on the CIS/cc-PVDZ calculations and on conformity with the available data in the literature. Although the general spectral features of these two isotopomers are similar, the frequencies of some vibrational modes are different. This frequency shift partially depends on the degree of involvement of the chlorine atom in the molecular vibrations.