Characterization of TcCl4 and β-TcCl3 by X-ray absorption fine structure spectroscopy

Technetium tetrachloride and β-TcCl₃, synthesized from the reaction of Tc metal and Cl_2(g) in sealed tubes, were characterized by X-ray absorption fine structure spectroscopy. Extended X-ray absorption fine structure (EXAFS) spectroscopy measurements are in good agreement with the X-ray diffraction structures of the two compounds. For TcCl₄, the absorbing Tc atom is surrounded by Cl atoms at 2.34(2) Å and Tc atoms at 3.66(4) Å. For β-TcCl₃, the absorbing Tc atom is surrounded by Cl atoms at 2.40(2) Å and Tc atoms at 2.81(3), 3.66(4) and 5.71(6) Å. EXAFS spectroscopy indicates that the TcCl₄ and β-TcCl₃ samples obtained by sealed tube reactions are single phase. The X-ray absorption near edge structure spectra of TcCl₄ and β-TcCl₃ were recorded; the positions of the Tc K-edges of β-TcCl₃ (21,050.5 eV) and TcCl₄ (21,053.0 eV) are compared to the ones measured for α-TcCl₃ (21,051.0 eV) and TcCl₂ (21,048.8 eV). A correlation between the positions of the Tc K-edges and the oxidation state of the Tc atom in technetium binary chlorides was determined.     

First emission studies of Tc2X8(2-) systems (X = Cl, Br)

The emission spectra of the solids [n-Bu(4)N](2)Tc(2)X(8) (X = Cl, Br) have been investigated at room temperature and 77 K. In each case, the emission originates in the (1)δ-δ* excited state, as with the rhenium homologues, but has a shorter lifetime.     

Technetium dichloride: a new binary halide containing metal-metal multiple bonds

Technetium dichloride has been discovered. It was synthesized from the elements and characterized by several physical techniques, including single crystal X-ray diffraction. In the solid state, technetium dichloride exhibits a new structure type consisting of infinite chains of face sharing [Tc(2)Cl(8)] rectangular prisms that are packed in a commensurate supercell. The metal-metal separation in the prisms is 2.127(2) ?, a distance consistent with the presence of a Tc≡Tc triple bond that is also supported by electronic structure calculations.     

Precise mass measurement of a double-stranded 500 base-pair (309 kDa) polymerase chain reaction product by negative ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) has been used to determine the mass of a double-stranded 500 base-pair (bp) polymerase chain reaction (PCR) product with an average theoretical mass of the blunt-ended (i.e. unadenylated) species of 308 859.35 Da. The PCR product was generated from the linearized bacteriophage Lambda genome which is a double-stranded template. Utilization of ethanol precipitation in tandem with a rapid microdialysis step to purify and desalt the PCR product was crucial to obtain a precise mass measurement. The PCR product (0.8 pmol/μL) was electrosprayed from a solution containing 75% acetonitrile, 25 mM piperidine, and 25 mM imidazole and was infused at a rate of 200 nL/min. The average molecular mass and the corresponding precision were determined using the charge-states ranging from 172 to 235 net negative charges. The experimental mass and corresponding precision (reported as the 95% confidence interval of the mean) was 309 406 +/- 27 Da (87 ppm). The mass accuracy was compromised due to the fact that the PCR generates multiple products when using Taq polymerase due to the non-template directed 3'-adenylation. This results in a mixture of three PCR products with nearly identical mass (i.e. blunt-ended, mono-adenylated and di-adenylated) with unknown relative abundances that were not resolved in the spectrum. Thus, the experimental mass will be a weighted average of the three species which, under our experimental conditions, reflects a nearly equal concentration of the mono- and di-adenylated species. This report demonstrates that precise mass measurements of PCR products up to 309 kDa (500 bp) can be routinely obtained by ESI-FTICR requiring low femtomole amounts. Copyright 1999 John Wiley & Sons, Ltd.     

Synthesis and characterization of Th2N2(NH) isomorphous to Th2N3

Using a new, low-temperature, fluoride-based process, thorium nitride imide of the chemical formula Th(2)N(2)(NH) was synthesized from thorium dioxide via an ammonium thorium fluoride intermediate. The resulting product phase was characterized by powder X-ray diffraction (XRD) analysis and was found to be crystallographically similar to Th(2)N(3). Its unit cell was hexagonal with a space group of P3m1 and lattice parameters of a = b = 3.886(1) and c = 6.185(2) ?. The presence of -NH in the nitride phase was verified by Fourier transform infrared spectroscopy (FTIR). Total energy calculations performed using all-electron scalar relativistic density functional theory (DFT) showed that the hydrogen atom in the Th(2)N(2)(NH) prefers to bond with nitrogen atoms occupying 1a Wyckoff positions of the unit cell. Lattice fringe disruptions observed in nanoparticle areas of the nitride species by high-resolution transmission electron microscopic (HRTEM) images also displayed some evidence for the presence of -NH group. As ThO(2) was identified as an impurity, possible reaction mechanisms involving its formation are discussed.     

Synthesis and structure of technetium trichloride

Technetium trichloride has been synthesized by reaction of Tc(2)(O(2)CCH(3))(4)Cl(2) with HCl(g) at 300 °C. The mechanism of formation mimics the one described earlier in the literature for rhenium. Tc(2)(O(2)CCH(3))(2)Cl(4) [P1?; a = 6.0303(12) ?, b = 6.5098(13) ?, c = 8.3072(16) ?, α = 112.082(2)°, β = 96.667(3)°, γ = 108.792(3)°; Tc-Tc = 2.150(1) ?] is formed as an intermediate in the reaction at 100 °C. Technetium trichloride is formed above 250 °C and is isostructural with its rhenium homologue. The structure consists of Tc(3)Cl(9) clusters [R3?m; a = b = 10.1035(19) ?, c = 20.120(8) ?], and the Tc-Tc separation is 2.444(1) ?. Calculations on TcX(3) (X = Cl, Br) have confirmed the stability of TcCl(3) and suggest the existence of a polymorph of TcBr(3) with the ReBr(3) structure.     

Principle and analytical applications of resonance lonization mass spectrometry

Resonance ionization mass spectrometry (RIMS) is a very sensitive analytical technique for the detection of trace elements. This method is based on the excitation and ionization of atoms with resonant laser light followed by mass analysis. It allows element and, in some cases, isotope selective ionization and is applicable to most of the elements of the periodic table. A high selectivity can be achieved by applying three step photoionization of the elements under investigation and an additional mass separation for an unambiguous isotope assignment.An effective facility for resonance ionization mass spectrometry consists of three dye lasers which are pumped by two copper vapor lasers and of a linear time-of-flight spectrometer with a resolution better than 2500. Each copper vapor laser has a pulse repetition rate of 6.5 kHz and an average output power of 30 W.With such an apparatus measurements with lanthanide-, actinide-, and technetium-samples have been performed. By saturating the excitation steps and by using autoionizing states for the ionization step a detection efficiency of 4 × 10^–6 and 2.5 × 10^–6 has been reached for plutonium and technetium, respectively, leading to a detection limit of less than 10⁷ atoms in the sample. Measurements of isotope ratios of plutonium samples were in good agreement with mass-spectrometric data. The high elemental selectivity of the resonance ionization spectrometry could be demonstrated.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria