Determination of low concentrations of iodine-131 in fast-reactor coolant systems

A method has been devised for the determination of iodine-131 in the presence of mixed fission products in reactor coolants, by oxidation to elemental iodine followed by sublimation on to copper gauzes. The method reduces to a minimum contamination of the copper gauzes by ruthenium-103 and ruthenium-106 and eliminates contamination due to technetium-99 and caesium-137. It is possible to determine 10(2)cpm ml from iodine-131 in a total count of 2 x 10(6)cpm ml of fission products, with an accuracy of +/- 3%. The only activity collected on the copper gauzes was iodine-131 (62% collection efficiency) and ruthenium-103 (0.005% of total activity) which gave comparable count rates. The activity of these two isotopes was separated by single-channel gamma analysis.     

A low-volume cavity ring-down spectrometer for sample-limited applications

In atmospheric and environmental sciences, optical spectrometers are used for the measurements of greenhouse gas mole fractions and the isotopic composition of water vapor or greenhouse gases. The large sample cell volumes (tens of milliliters to several liters) in commercially available spectrometers constrain the usefulness of such instruments for applications that are limited in sample size and/or need to track fast variations in the sample stream. In an effort to make spectrometers more suitable for sample-limited applications, we developed a low-volume analyzer capable of measuring mole fractions of methane and carbon monoxide based on a commercial cavity ring-down spectrometer. The instrument has a small sample cell (9.6 ml) and can selectively be operated at a sample cell pressure of 140, 45, or 20 Torr (effective internal volume of 1.8, 0.57, and 0.25 ml). We present the new sample cell design and the flow path configuration, which are optimized for small sample sizes. To quantify the spectrometer’s usefulness for sample-limited applications, we determine the renewal rate of sample molecules within the low-volume spectrometer. Furthermore, we show that the performance of the low-volume spectrometer matches the performance of the standard commercial analyzers by investigating linearity, precision, and instrumental drift.     

Witt rings and the quaternion group

Let F be a formally real field which admits no quaternionic Galois extension. The structure of the Witt ring and the maximal pro-2 Galois group of F are investigated. Received: 3 July 1997 / Revised version: 2 February 1998     

金属的冲击波温度测量（Ⅰ）──高温计的标定和界面温度的确定

 讨论了金属材料冲击波温度测量中光学高温计的标定及金属样品/窗口界面温度的数据处理问题。给出了利用Planck辐射定律求解界面辐射能量及温度的方法。     

14 MeV neutron activation analysis applied to a non-aqueous flowing system

The feasibility and advantages of fast neutron activation analysis in a non-aqueous flowing system, using economical irradiation techniques are outlined. The application of the method to the determination in solution of elements producing isotopes with half lives in the range 588—29.4 sec, the selection of the optimum flow rate to minimise interferences for each element, and their limits of detection are also given. A method for the prediction of the optimum flow rate, on a given system, for the determination of any element producing an isotope of known half life is also given.     

Stereocontrol in organic synthesis using silicon-containing compounds. Studies directed towards the synthesis of ebelactone A

Several approaches to the synthesis of ebelactone A 2 are described, culminating in the synthesis of the benzenesulfonate of 2-epi-ebelactone A 161. All the approaches were based on three fragments A, B and C, originally defined in general terms in, but eventually used as the aldehyde 72, the allenylsilane 3 and the aldehyde 139, respectively. They were joined, first B with C, and then B+C with A. In the main routes to fragments A and C, the relative stereochemistry was controlled by highly stereoselective enolate methylations 67-->67, 68-->69, and 135-->136, in each case anti to an adjacent silyl group, and by a highly stereoselective hydroboration of an allylsilane 137-->138, also anti to the silyl group. The hydroxyl groups destined to be on C-3 and C-11 were unmasked by silyl-to-hydroxy conversions 69-->70 and 138-->139 with retention of configuration. The stereochemistry created in the coupling of fragment B to C was controlled by the stereospecifically anti S(E)2' reaction between the enantiomerically enriched allenylsilane 3 and the aldehyde 139. The double bond geometry was controlled by syn stereospecific silylcupration 148-->151, and preserved by iododesilylation 151-->152 of the vinylsilane with retention of configuration, and Nozaki-Hiyama-Kishi coupling with the aldehyde 72 gave the whole carbon skeleton 153 of ebelactone A with the correct relative configuration, all of which had been controlled by organosilicon chemistry. In the steps to remove the superfluous allylic hydroxyl, an intermediate allyllithium species 156 abstracted the proton on C-2, and its reprotonation inverted the configuration at that atom. Other routes to the fragments A and C were also explored, both successful and unsuccessful, both silicon-based and conventional, and a number of unexpected side reactions were investigated.     

Osmium Complexes of 1,4,7-Triazacyclononane (tacn) and 1,4,7-Trimethyl-1,4,7-triazacyclononane (Me(3)tacn) and the X-ray Crystal Structure of [(Me(3)tacn)Os(eta(6)-C(6)H(5)BPh(3))]BPh(4).CH(3)CN

The complexes of osmium with tacn (1,4,7-triazacyclononane) and Me(3)tacn (1,4,7-trimethyl-1,4,7-triazacyclononane), [LOs (eta(6)-C(6)H(6))](PF(6))(2) (L = tacn) and LOsCl(3) (L = tacn, Me(3)tacn), have been prepared by substitution of L on [Os(eta(6)-C(6)H(6))Cl(2)](2) or [Os(2)Cl(8)](2)(-), respectively. Reaction of LOsCl(3) with neat triflic acid leads to partial replacement of chloride and formation of the binuclear Os(III)-Os(III) complexes [LOs(&mgr;-Cl(3))OsL](PF(6))(3) (L = tacn, Me(3)tacn). The binuclear nature was established by NMR spectroscopy and elemental analysis and, for L = tacn, a partially refined X-ray crystal structure which shows the Os-Os separation to be 2.667 ?, indicative of significant metal-metal bonding. Reduction of [LOs(&mgr;-Cl(3))OsL](3+) over zinc amalgam in either aqueous or non-aqueous solution yields the intensely colored Os(II)-Os(III) mixed-valence ions [LOs(&mgr;-Cl(3))OsL](2+). Electrochemical measurements on [LOs(&mgr;-Cl(3))OsL](3+) in CH(3)CN reveal the reversible formation of the mixed valence ions. These are further reduced at lower potential to the Os(II)-Os(II) binuclear species, reversibly for L = Me(3)tacn. (Me(3)tacn)OsCl(3) is oxidized by persulfate ion to give [(Me(3)tacn)OsCl(3)](+); zinc amalgam reduction in an aqueous solution at high concentration produces the binuclear complex [(Me(3)tacn)Os(&mgr;-Cl(3))Os(Me(3)tacn)](3+) or, at low concentration, a solution containing an air sensitive osmium(II) species. Addition of BPh(4)(-) results in the eta(6)-arene zwitterion [(Me(3)tacn)Os(eta(6)-C(6)H(5)BPh(3))](+), which was characterized by X-ray diffraction on the BPh(4)(-) salt. The compound crystallizes in the triclinic space group P1 with a = 11.829(2) ?, b = 12.480(3) ?, c = 17.155(4) ?, alpha = 84.42(2) degrees, beta = 83.52(2) degrees, gamma = 71.45(2) degrees, V = 2380(2) ?(3), Z = 2, and R = 7.62%, and R(w) = 7.39%.