Second-order interference in the neutron activation analysis of arsenic in a germanium matrix

The second-order interference ⁷⁴Ge(n, γ; β^-, n, γ)⁷⁶ As can occur in the activation analysis of arsenic in a germanium matrix, using thermal neutrons. As the literature data show poor agreement, this interference was determined experimentally. A practical formula was derived, for irradiation times longer than 2 h, which showed that the interference, expressed as an apparent arsenic concentration, is proportional to the neutron flux. Experiments were performed for irradiation times of 10, 15 and 20 h at a neutron flux of 10¹⁴ n/cm²/sec, yielding apparent arsenic concentrations in the germanium matrix of respectively 223, 408 and 597 p.p.b. From these results a value of 0.48 ±0.06 barn could be calculated for the activation cross-section of ⁷⁴Ge for neutron capture.     

Preparation of thin arsenic and radioarsenic targets for neutron capture studies

A simple method for the electrodeposition of elemental arsenic (As) on a metal backing from aqueous solutions has been developed. The method was successfully applied to stable As (⁷⁵As). Thin (2.5 mg cm⁻²) coherent, smooth layers of the metalloid on Ti foils (2.5 μm thickness) were obtained. Electrodeposits served as targets for ⁷⁵As(n,γ) ⁷⁶As neutron capture experiments at Los Alamos Neutron Science Center (LANSCE). Respective ⁷³As(n,γ) ⁷⁴As experiments are planned for the near future, and ⁷³As targets will be prepared in a similar fashion utilizing the new electrodeposition method. The preparation of an ⁷³As (half-life 80.3 days) plating bath solution from proton irradiated germanium has been demonstrated. Germanium target irradiation was performed at the Los Alamos Isotope Production Facility (IPF).     

Determination of 17O and 18O isotopic abundances in 238Pu materials by γ-ray spectrometry

A procedure has been developed for nondestructive determinations of ¹⁷O and ¹⁸O isotopic abundances in ²³⁸PuO₂ fuels produced for biomedical application. Close control of these isotopes is important because they increase the neutron emission rate caused by (α, n) reactions. γ-Rays accompanying these reactions are measured by a lithium-drifted germanium [Ge(Li)] detector and related to their respective isotopic abundances. Each determination has a detection limit approximating the lowest contents encountered in PuO₂ samples of 0.005% ¹⁷O and 0.001% ¹⁸O. The average deviations for each determination are estimated to be about ±25% at their detection levels, and less than ± 10% for abundances above 0.01%.     

Neutron activation analysis correction for the calculation of bromine concentrations via the79Br(n, γ)80Br reaction

Bromine can be determined by neutron activation analysis (NNA) through either the activation of⁷⁹Br (50.69% naturally abundant) or⁸¹Br (49.31% naturally abundant). When⁷⁹Br is activated, both^80mBr and⁸⁰Br are produced.^80mBr (4.42 h) decays to⁸⁰Br (17.66 m) which then beta decays to either⁸⁰Se or⁸⁰Kr. If one would like to determine bromine concentrations with short lived NAA, special equations must be used to account for the parent daughter relationship between^80mBr after their simultaneous production. The development of the equations needed to calculate bromine concentrations with short-lived NAA is described including variations on irradiation times, decay times, and count times.     

Dissociative double electron capture,dynamics of fragmentation of the water and hydrogen sulfide negative ions

The technique of ion kinetic energy spectrometry has been used to observe the unimolecular decompositions of H₂O^?? and H₂S^?? generated by charge exchange of the corresponding high velocity positive ions. The method involves dissociative double electron capture by a high velocity ion and allows the study of unstable negative ions that may be directly observable by conventional electron capture techniques. Information on the energetics of the reaction is obtained from the kinetic energy of the product ion. The reactions under consideration are shown in (1) and (2) where X = O or S.

The kinetic energy releases accompanying the reactions given in (1) and (2) have been measured and compared to those for the collision-induced reactions which produce the corresponding positive ions. The results have been used to deduce that the sequence of steps in the formation of the fragment negative ions is that given in (1) and (2). The cross section of OH^? formation is observed to be somewhat greater than for O^? production. This result is in contrast with dissociative electron capture cross sections from the neutral species and is interpreted on the basis of the energetic requirements for the reactions under consideration. H₂O^? reacts from different electronic states in yielding OH^? on the one hand and O^? on the other. The energy partitioning associated with reaction (2) suggests that the neutral productions 2H' rather than H₂. The kinetic energy losses accompanying excitation and kinetic energy releases upon fragmentation were similar for the corresponding reactions of the sulfur and oxygen-containing ions indicating related mechanisms in the two sets of reactions.     

Slow neutron reactions in inverse kinematics for isotope production: a primer

Slow neutron inverse-kinematic reactions offer unique advantages since their kinematical conditions can be tuned to utilize very high resonance cross-sections and to separate transmuted-isotopes online. New advances in plasma sciences and thermal neutron facilities can usher practical applications of this type of reactions in some special cases. Production and implantation of isotopically-pure short-lived and spin-polarized radiotracers has been identified as a probable first application. The production rates for ^110m,gAg radio-nuclides in ¹⁰⁹Ag(n, γ) capture, that occur when a beam of ¹⁰⁹Ag ions traverses a thermal neutron column, have been calculated and the results are presented. To develop the idea of inverse reactions in physical grounds, further analyses and advances on the non-trivial technological issues related to the generation and control of high density and high volume particle beams, isotope separation methods, and high flux thermal neutron channels of matching parameters are required and a brief discussion on these aspects are also included.     

Germanium determination by flame atomic absorption spectrometry: an increased vapor pressure-chloride generation system

A new chloride generation system was designed for the direct, sensitive, rapid and accurate determination of the total germanium in complex matrices. It was aimed to improve the detection limit of chloride generation technique by increasing the vapor pressure of germanium tetrachloride (GeCl₄). In order to do so, a novel joint vapor production and gas-liquid separation unit equipped with a home-made oven was incorporated to an ordinary nitrous oxide-acetylene flame atomic absorption spectrometer. Several variables such as reaction time, temperature and acid concentration have been investigated. The linear range for germanium determination was 0.1-10 ng mL⁻¹ for 1 mL sampling volume with a detection limit (3 s) of 0.01 ng mL⁻¹. The relative standard deviation (RSD) was 2.4% for nine replicates of a 1 ng mL⁻¹ germanium solution. The method was validated by the analysis of one non-certified and two certified geochemical reference materials, respectively, CRM GSJ-JR-2 (Rhyolite), and GSJ-JR-1 (Rhyolite), and GBW 07107 (Chinese Rock). Selectivity of the method was investigated for Cd²⁺, Co²⁺, Cu²⁺, Fe³⁺, Ga³⁺, Hg²⁺, Ni²⁺, Pb²⁺, Sn²⁺, and Zn²⁺ ions and ionic species of As(III), Sb(III), Te(IV), and Se(IV).     

A New Stationary Phase for Hydrophilic Interaction Chromatography: Polyacrylate-Based Hydrophilic,Monosized-Porous Beads with Zwitterionic Molecular Brushes

Hydrophilic, polyacrylate-based, monosized-porous beads with zwitterionic molecular brushes were synthesized as a new stationary medium for hydrophilic interaction chromatography. Monosized-porous poly(glycerol-1,3-diglycerolate diacrylate-co-glycerol dimethacrylate), poly(GDGDA-co-GDMA), beads 5 μm in size were obtained by a staged-shape template polymerization. As an initiator for surface-initiated atom transfer radical polymerization (SI-ATRP), bromine functionality was obtained on the beads by reacting their hydroxyl groups with 3-(aminopropyl)triethoxysilane and α-bromoisobutyryl bromide, respectively. Zwitterionic molecular brushes on the hydrophilic poly(GDGDA-co-GDMA) beads were generated by SI-ATRP of a sulfobetaine monomer, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide (MESH). Poly(MESH)-grafted poly(GDGDA-co-GDMA), poly(MESH)g-poly(GDGDAco-GDMA), beads were slurry packed into the microbore columns with 2 mm i.d. and evaluated as stationary medium for the separation of organic acids, nucleosides and peptides using microbore columns in hydrophilic interaction chromatography with the plate numbers up to 30,000 plates m⁻¹.

     

The Contrasting Behaviour of Arsenic and Germanium Species in Seawater

The vertical profiles of inorganic arsenic [As(III)+As(V)], monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA), inorganic germanium and monomethylgermanium (MMGe) were investigated at three sampling stations in the Pacific Ocean. In addition, the concentrations of these species in various surface waters have also been determined. The vertical profile of both inorganic arsenic and germanium displayed low concentrations, 1100 to 1450 ng dm³ for inorganic arsenic and <0.7 to 2 ng dm³ for inorganic germanium, in the surface zone. The concentrations of inorganic arsenic increased with depth to maximum concentrations that varied from 1500 to 2200 ng dm³ at a depth of 2000 m and then slowly decreased to concentrations that varied from 1300 to 1900 ng dm³ at a depth of 5000 m. On the other hand, the vertical profiles of inorganic germanium displayed a relatively constant concentration (4 to 8 ng dm³) from a depth of 2000 m to 5000 m. These vertical profiles of inorganic germanium were linearly correlated with those of silicate with a Ge/Si molar ratio of 0.715×10⁶. Both MMAA and DMAA displayed maximum concentrations in surface water and abruptly dropped with depth from 0 to 200 m. The concentration in surface water was 12 ng dm³ for MMAA and varied from 48 to 185 ng dm³ for DMAA. At depths >200 m, MMAA and DMAA were generally at comparable concentrations of about 3 ng dm³. In the case of MMGe, it was uniformly distributed throughout the water column at a concentration of approximately 16 ng dm³, indicating that MMGe was not involved in the biogeochemical cycling of inorganic germanium. In deep waters (>200 m), the concentrations of both inorganic arsenic and germanium increased from the southern Tasman Sea to the north. The increase in inorganic arsenic concentration was linearly correlated with that of phosphate and the increase in inorganic germanium concentration was linearly correlated with that of silicate, with apparent δAs/δP and δGe/δSi molar ratios of 4.53×10³ and 0.73×10⁶, respectively. © 1997 by John Wiley & Sons, Ltd.     

A New Approach to the Efficient Method for the Asymmetric Synthesis of (S)-O-, M-, P-Fluorophenylalanines and Their 2-Methyl-substituted Analogs

Abstract

The reactions of asymmetric C-alkylation of glycine and alanine in Ni^II complexes of their Schiff's bases with modified chiral auxiliaries (S)-2-N-[(N′-2-chlorobenzylprolyl)amino]benzophenone and (S)-2-N-[N′-(3,4-dimethylbenzylprolyl)amino]benzophenone by fluorine-substituted benzyl halogenides have been studied. As a result, a highly stereoselective and relatively rapid method for the asymmetric synthesis of (S)-o-, m-, p-fluorophenylalanines and their 2-methyl substituted analogs has been developed.     

A computational approach to understanding the mechanism of aromatic bromination using quaternary ammonium tribromides

Quaternary ammonium tribromides (QATBs) have garnered interest for nearly a century now. Various types of tribromides have been synthesized over the years and their diverse applications have been extensively reported. However, despite the fact that these reagents are touted as safer alternatives to the very poisonous bromine, there is insufficient information on the structure of Br₃^? in QATB systems and there is still no clear explanation for how the tribromide ion (Br₃^?) participates in bromination reactions. This paper reports a through structural assessment of Br₃^?, followed by an attempt was made to fully understand the mechanistic behaviour of tribromide during bromination of aromatic compounds.     

Ein reaktivitätsvergleich von cyclopentadien-derivaten mit IVb-und/oder vb-element-liganden: umsetzungen mit vb-elementhalogeniden und mit titantetrachlorid

The reactivity of element substituted cyclopentadienes (el = Si, Ge, Sn, As, Sb) is compared by reactions with Vb-element halides and with titaniumtetrachloride. Hereby already known cp-element compounds and new cyclopentadienyl-titaniumtrichlorides with silicon, germanium, tin, arsenic and antimony substituted cp-rings are formed. The ¹H-n.m.r. spectra of these complexes are described. The following row of reactivity is found for the investigated element substituted cyclopentadienes: el = AsMe₂<SiMe₃<GeMe₃<SbMe₂<SnMe₃.     

Mechanistic aspects of the bromination of 10-substituted phenothiazines

The addition of 1 and 2 molar equivalents of bromine to a series of 10-alkylphenothiazines, 1a-d (methyl, ethyl, n-propyl, and isopropyl, respectively), yields the corresponding 3-bromo- and 3,7-dibromo-10-alkylphenothiazines ( 11a-d and 12a-d , respectively). Evidence which supports the typical clectrophilic aromatic substitution mechanism is presented. Radical cations ( 12a-d^.+ ) arc produced when 12a-d are treated with 1 or 2 molar equivalents of bromine. Upon boiling in acetic acid these radical cations are converted predominantly to 1,3,7,9-lelrabromophenothiazine ( 5 ) and the parent 3,7-dibromo-10-alkylphenothiazine ( 12a-d ) with the evolution of hydrogen bromide. The 10-methyl radical ( 12a ) gives, in addition, 1,3,7-tribromo-10-methylphenothiazine ( 15 ). A mechanism if proposed for these reactions in which initial dealkylution of 12b-d^.+ to 3.7-dibromophenothiazine radical cation ( 13 ) occurs followed by reduction of 13^.+ by bromide ion to parent 3,7-dibromophenothiazine ( 13 ). Subsequent bromination of 13 by molecular bromine produced in the previous redox reaction yields 1,3,7-tribromo-( 14 ) and 1,3,7,9-tetra-bromo-( 5 ) phenothiazines. The small size of the methyl group allows 12a to be brominated at the 1-position prior to dealkylation. In addition to undergoing bromination at the 3- and 7-position, 10-isopropylphenothiazine ( 1d ) is oxidized to the radical cation 12e^.+ when treated with bromine. 10-Benzylphenothiazine ( 1e ), however, undergoes oxidation to radical cation 1e^.+ exclusively. This radical cation debenzylates readily at room temperature and is converted finally into phenothiazine.     

Extraction and Flameless AAS Determination of Germanium in Lignite Fly Ash

Abstract

The use of dicyclohexyl-18-crown-6 methyl isobutyl ketone solution in extraction and flamelessatomic absorption spectrophotometry (AAS) determination of germanium in lignite fly ashes have been studied.

Germanium is usually determined in lignites after the carbonaceous part of the sample has been burnt by a dry or wet ashing method. However, methods are described for direct determination of germanium.

In the present paper a wet ashing method is reported for the determination of germanium in lignite fly ashes by flameless AAS after extraction into dicyclohexyl-18-crown-6 methyl isobutyl ketone (MIBK) solution. Solvent extraction is a known hydrometallurgical method that could be applied in germanium recovery.     

Pre-equilibrium effects on proton, deuteron, and alpha induced reactions for the production of 72As as a PET imaging radioisotope

In this study, the production methods and the applications of ⁷²As are reviewed with special attention to the feasibility of the cyclotron production of ⁷²As. TALYS-1.4 and ALICE/ASH codes were employed to illustrate the formation of the ⁷²As via ^natGe(p, xn)⁷²As, ^72,73,74Ge(p, xn)⁷²As, ⁷²Ge(d, 2n)⁷²As, and ⁶⁹Ga(α, n)⁷²As reactions. Hybrid model and geometry dependent hybrid model were used in ALICE/ASH code to calculate the pre-equilibrium neutron-production cross sections. The excitation functions of the reactions were taken from the TENDL-2011 database and compared with the reported experimental measurement. The equilibrium and pre-equilibrium effects on the reactions were also discussed. An optimum energy range and the level of impurities for each reaction were determined. The ⁷²As production yield was evaluated with concentration on the excitation function calculations and the stopping powers of the projectiles in the targets.     

The production of 172Tm by triple neutron capture in nuclear reactors

The production of ¹⁷²Tm by the triple capture through the reaction chain of triple neutron capture: ¹⁶⁹Tm(n,γ)¹⁷⁰Tm(n,γ)¹⁷¹Tm(n,γ)¹⁷²Tm is informed. The experimental details of irradiations and measurements, as well as the verification of the identity of the radionuclide and the reactions leading to its formation, are described.     

Synthesis,Structures, and Properties of Branched Oligogermanes

Abstract

We have employed the hydrogermolysis reaction for the preparation of rare branched oligogermanes, and have obtained for the first time the X-ray crystal structures of several branched tetragermanes, including (Ph₃Ge)₃GePh, (Ph₃Ge)₃GeH, and (Ph₃Ge)₃GeX (X = Cl or Br). We also have at our disposal branched tetragermanes having the formula (EtOCH₂CH₂Bu ⁿ ₂Ge)₃GePh, where the ethoxyethyl substituent serves as a protecting group for a germanium–hydride active site. These reagents have been employed for the stepwise synthesis of higher branched systems having up to 13 bonded germanium atoms in the oligomer backbone. The synthesis, structures, and physical characteristics of these systems are described.

GRAPHICAL ABSTRACT     

Determination of Germanium in Zinc by Differential Cathode Ray Polarography

Abstract

A differential cathode ray polarographic method is described for determining traces of germanium in zinc and its compounds. The germanium was previously extracted with carbon tetrachloride from the sample solution in hydrochloric acid. After reextraction with water the germanium content was determined polarographically in 1.4 M perchloric acid ? 5.10^?2 M pyrogallol. The detection limit was 0.0012 μg/ml, allowing to detect about 4 ppb of germanium in zinc using 5 g samples.     

Radiological hazard analysis of Malaysia’s ceramic materials using generic and RESRAD-BUILD computer code approach

In this study, 52 samples of ceramic materials were studied for ²²⁶Ra, ²²²Rn, ²³²Th and ⁴⁰K natural radionuclides using high-purity germanium detector and relevant radiological hazards parameters were also appraised. Furthermore, the long-term variations of the total effective dose equivalent (TEDE) and effects of wall thickness on TEDE were established and analyzed using RESRAD-BUILD computer code. The observed percentage variations of TEDE are 2% and 8% for ²²⁶Ra and ²³²Th, respectively, while no variation observed for external dose due to ⁴⁰K. The estimated indoor doses from the studied ceramic materials are all below the recommended maximum limit.