Theoretical study of electronic structure of rhodium mononitride and interpretation of experimental spectra

Potential energy curves of 22 electronic states of RhN have been calculated by the complete active space second‐order perturbation theory method. The X¹Σ₀⁺ is assigned as the ground state, and the first excited state a³Π₀+ is 978 cm^?1 higher. The ¹Δ(I) and B¹Σ⁺ states are located at 9521 and 13,046 cm^?1 above the ground state, respectively. The B¹Σ⁺ state should be the excited state located 12,300 cm^?1 above the ground state in the experimental study. Moreover, two excited states, C¹Π and b³Σ⁺, are found 14,963 and 15,082 cm^?1 above the X¹Σ⁺ state, respectively. The transition C¹Π₁–X¹Σ₀⁺ may contribute to the experimentally observed bands headed at 15,071 cm^?1. There are two excited states, D¹Δ and E¹Σ⁺, situate at 20,715 and 23,145 cm^?1 above the X¹Σ⁺ state. The visible bands near 20,000 cm^?1 could be generated by the electronic transitions D¹Δ₂–a³Π₁ and E¹Σ⁺₀–X¹Σ⁺₀ because of the spin–orbit coupling effect. © 2013 Wiley Periodicals, Inc.     

Preparation of manganese-53

The nuclide⁵³Mn was produced by the following three nuclear reactions,⁵²Cr(d, n)⁵³Mn,⁵¹V(³He n)⁵³Mn and⁵⁰Cr(α, n), (α, p)⁵³Mn. Enriched⁵²Cr and⁵⁰Cr metal targets were prepared on copper plate holder by electrodeposition. The commercially available natural vanadium foil was used for the⁵¹V(³He, n)⁵³Mn reaction. Each target was bombarded in a cyclotron. Manganese was extracted and purified without using carrier from the bombarded targets by anion and cation exchanges and solvent extraction. The isotopic ratio⁵³Mn/⁵⁵Mn was measured by mass spectrometry and the amount of⁵⁵Mn was determined by neutron activation analysis. The activity of⁵³Mn obtained was 7 dpm by 750 millicoulombs in³He bombardment (E³He=20 MeV). The activity due to by-product⁵⁴Mn was about several thousands times higher than that of⁵³Mn in³He and deuteron bombardments, which were produced through⁵¹V(³He, γ)⁵⁴Mn and⁵³Cr(d, n)⁵⁴Mn. In alpha bombardment (E_α=15 MeV), the activity of⁵³Mn produced was 8 dpm by 95 millicoulombs. The activity ratio, dpm⁵⁴Mn/dpm⁵³Mn, was about 3, and this ratio was the best one among the results so far obtained.     

CI study of rovibrational dependence of nuclear quadrupole coupling constants of all isotopic variants of OH+ in the X3Σ− state

The ¹⁷O and ²H quadrupole coupling constants of rovibrational levels of ¹⁷O¹H⁺, ¹⁷O²H⁺, and ¹⁶O²H⁺ in their X³Σ⁻ state have been calculated from molecular wave functions that explicitly describe nuclear motion. The ¹⁷O quadrupole coupling is predicted to be strong and its vibrational dependence differs from that known for other nuclei A in the first-row hydrides AH or AH⁺. The deuterium coupling in ¹⁷O²H⁺ and ¹⁶O²H⁺ is found to be weak and its behavior is similar to that of other first-row hydrides. The change with rotational excitation is unimportant. The quadrupole hyperfine patterns of ¹⁷O²H⁺ in its ground state are dominated by the strong oxygen coupling. © 1996 John Wiley & Sons, Inc.     

Viscoelasticity and birefringence of polyisoprene

The complex Young's modulus, E^*(ω), and the complex strain-optical coefficient, O^*(ω), which is the ratio of the birefringence to the strain, were measured for polyisoprene (PIP) over a frequency range of 1 ～ 130 Hz and a temperature range of 22 ～ ?100°C. The imaginary part of O^*, O″, was positive at low frequencies and negative at high frequencies. The real part, O′, was always positive and showed a maximum. The complicated behavior of O^* could be understood by the assumption that E^* = E_R^* + E_G^* and O^* = C_RE_R^* + C_GE_G^*, where E_R^* and E_G^* were complex quantities and C_R and C_G were constants. The C_R value, equal to the ordinary stress-optical coefficient measured in the rubbery plateau zone, was 2.0 × 10^?9 Pa^?1. The C_G value, defined as the ratio O″/E″ in the glassy zone, was ?1.1 × 10^?11 Pa^?1. The E_G^*, which was the major component of E^* in the glassy zone, showed almost the same frequency dependence as that of polystyrene and polycarbonate. The E_R^*, which was dominant in the rubbery zone, was described well by the bead-spring theory. The temperature dependence of the E_G^* was stronger than that of the E_R^*. This difference caused the breakdown of the thermorheological simplicity for E^* and O^* around the glass-to-rubber transition zone. © 1995 John Wiley & Sons, Inc.     

New developments in the production of theranostic pairs of radionuclides

A brief historical background of the development of the theranostic approach in nuclear medicine is given and seven theranostic pairs of radionuclides, namely ^44gSc/⁴⁷Sc, ⁶⁴Cu/⁶⁷Cu, ⁸³Sr/⁸⁹Sr, ⁸⁶Y/⁹⁰Y, ¹²⁴I/¹³¹I, ¹⁵²Tb/¹⁶¹Tb and ¹⁵²Tb/¹⁴⁹Tb, are considered. The first six pairs consist of a positron and a β^?-emitter whereas the seventh pair consists of a positron and an α-particle emitter. The decay properties of all those radionuclides are briefly mentioned and their production methodologies are discussed. The positron emitters ⁶⁴Cu, ⁸⁶Y and ¹²⁴I are commonly produced in sufficient quantities via the (p,n) reaction on the respective highly enriched target isotope. A clinical scale production of the positron emitter ^44gSc has been achieved via the generator route as well as via the (p,n) reaction, but further development work is necessary. The positron emitters ⁸³Sr and ¹⁵²Tb are under development. Among the therapeutic radionuclides, ⁸⁹Sr, ⁹⁰Y and ¹³¹I are commercially available and ¹⁶¹Tb can also be produced in sufficient quantity at a nuclear reactor. Great efforts are presently underway to produce ⁴⁷Sc and ⁶⁷Cu via neutron, photon and charged particle induced reactions. The radionuclide ¹⁴⁹Tb is unique because it is an α-particle emitter. The present method of production of ¹⁵²Tb and ¹⁴⁹Tb involves the use of the spallation process in combination with an on-line mass separator. The role of some emerging irradiation facilities in the production of special radionuclides is discussed.     

Production of charge-induced X-rays during PIXE studies using light and heavy ion-beams

A recently discovered phenomenon of excessively high X-ray production is discussed. The high yield is attributed to the build-up of potential on non-conducting targets irradiated with accelerated ion beams, and the subsequent discharge. Ion-beams of¹H⁺,¹H₂ ⁺,²H⁺,²H₂ ⁺,³He⁺,³He²⁺,⁴He⁺,¹⁴N⁺,¹⁴N²⁺,¹⁶O⁺ and²⁰Ne⁺ were used. A new mechanism of X-ray excitation is proposed. The increased X-ray fluxes produced by this process are suitable for analytical applications of high specificity. The mechanism of excitation associated with the process, factors affecting the high X-ray yields, applications and a general overview of the studies undertaken with the various ion beams are given.     

Radioactivity of coals and fly ashes

The level and the behavior of the naturally occurring primordial radionuclides ²³⁸U, ²²⁶Ra, ²¹⁰Pb, ²³²Th, ²²⁸Ra and ⁴⁰K in coals and fly ashes are described. The activity concentrations of the examined coals and originated from coal mines in Greece ranged from 117 to 435 Bq·kg⁻¹ for ²³⁸U, from 44 to 255 Bq·kg⁻¹ for ²²⁶Ra, from 59 to 205 Bq·kg⁻¹ for ²¹⁰Pb, from 9 to 41 Bq·kg⁻¹ for ²²⁸Ra and from 59 to 227 Bq·kg⁻¹ for ⁴⁰K. These levels are comparable to those appeared in coals of different countries worldwide. The activity concentrations of the examined fly ashes and produced in coal-fired power plants in Greece ranged from 263 to 950 Bq·kg⁻¹ for ²³⁸U, from 142 to 605 Bq·kg⁻¹ for ²²⁶Ra, from 133 to 428 Bq·kg⁻¹ for ²¹⁰Pb, from 27 to 68 Bq·kg⁻¹ for ²²⁸Ra and from 204 to 382 Bq·kg⁻¹ for ⁴⁰K. The results showed that there is an enrichment of the radionuclides in fly ash relative to the input coal during the combustion process. The enrichment factors (EF) ranged from 0.60 to 0.76 for ²³⁸U, from 0.69 to 1.07 for ²²⁶Ra, from 0.57 to 0.75 for ²¹⁰Pb, from 0.86 to 1.11 for ²²⁸Ra and from 0.95 to 1.10 for ⁴⁰K.     

Radioargon production through the irradiation of calcium oxide

The production of radioargon through the irradiation of CaO was performed in an in-core facility within the The University of Texas at Austin MARK II TRIGA reactor. The major radioargon isotope produced was ³⁷Ar via the ⁴⁰Ca(n,α)³⁷Ar reaction pathway. The CaO powder was vacuumed sealed in a quartz ampoule. The sample was irradiated in a Cd-lined Al alloy canister for 2 h at 500 kW. After the irradiation, the sample was counted using an HPGe detector five times with increasing count times. ⁴¹Ar, ⁴²K, ⁴³K, and ⁴⁷Ca were detected in the spectra. The induced activities of ³⁷Ar, ³⁹Ar, ⁴¹Ar, ⁴²K, ⁴³K, and ⁴⁷Ca were calculated using a 63-group energy-dependent neutron flux determined utilizing a neutron energy flux profile calculated from a MCNPX model of the TRIGA reactor core. The production ratios generated from the model allowed for the estimation of induced ³⁷Ar and ³⁹Ar activities through the measured induced activities of ⁴¹Ar, ⁴²K, ⁴³K, and ⁴⁷Ca.     

Exploration of the potential application of plutonium isotopes in source identification of sandstorm in the atmosphere of Beijing

Plutonium (Pu) is an anthropogenic radionuclide which mainly derived from atmospheric nuclear tests in the environment. In this study, the Pu isotopes (²³⁹Pu and ²⁴⁰Pu) in aerosol samples collected during the sandstorm and non-sandstorm period were measured by accelerator mass spectrometry (AMS) and the behavior of Pu was studied. The activity concentrations of ²³⁹Pu and ²⁴⁰Pu in the aerosol samples of Beijing were ranged from 0.62 nBq/m³ to 99.6 nBq/m³ for ²³⁹Pu and 3.51 nBq/m³ to 60.23 nBq/m³ for ²⁴⁰Pu, respectively. ²³⁹Pu and ²⁴⁰Pu concentrations exhibited a remarkable seasonal variation trend, with the higher results showed in spring, and the relatively lower concentrations in winter. The observed higher concentration of ²³⁹Pu and ²⁴⁰Pu detected in sandstorm samples further indicated Pu was closely related to the occurrence of sandstorms. The global fallout characteristics of ²⁴⁰Pu/²³⁹Pu atom ratios (average 0.20, ranging from 0.16 to 0.27) in aerosol samples indicating that global fallout was the major source of Pu in the atmosphere. Using aluminum (Al) as an indicator of soil resuspension, significant positive correlation between ²³⁹Pu and Al (r² = 0.934), ²⁴⁰Pu and Al (r² = 0.525) revealed that soil resuspension was a primary source of atmospheric Pu in Beijing. These results implied that the combination of ²³⁹Pu, ²⁴⁰Pu and Al could be used as the potential tracer of sandstorm.     

Adsorption characteristics of radionuclides on nickel hexacyanoferrate(ii)

The composition of nickel hexacyanoferrate(II) complexes depends on the ratios of sodium hexacyanoferrate(II) and nickel nitrate solutions mixed. The adsorption behavior of nickel hexacyanoferrate(II) is described; acid treatment of Ni₂Fe(CN)₆ accelerates the adsorption rate of cesium, but does not increase the adsorption capacity. The Ni—Cs exchange ratios of Ni₂Fe(CN)₆ are discussed. In concentrated salt solutions, the distribution coefficients of ⁵⁹Fe, ⁶⁰Co, ⁶⁵Zn. ¹³⁷Cs, ⁹⁵Zr and ¹⁴⁴Ce are determined together with those of ⁸⁵Sr and ¹⁰⁶Ru. A simple determination of ¹³⁷Cs in sea water containing ⁵⁹Fe, ⁶⁰Co, ⁶⁵Zn, ⁹⁵Zr, ¹⁴⁴Ce, ⁸⁵Sr and ¹⁰⁶Ru is described.     

Determination of radionuclides in the environment using gamma-spectrometry

Summary Seventy nine samples, including soil and rock, were collected from the agrestic region of the State of Pernambuco, Brazil. The activity concentrations of ²³⁸U and ²²⁶Ra in the samples were determined by gamma-spectrometry using an HPGe detector. The concentrations of ²³⁸U were 22 Bq ^. kg^-1 to 22 kBq ^. kg^-1. The concentrations of ²²⁶Ra were 14 Bq ^. kg^-1 to 17 kBq ^. kg^-1. The ²³⁸U/²²⁶Ra ratios in the soil were 0.7 to 3.4 (arithmetic mean 1.7). The radiometric data were evaluated to explain ²³⁸U and ²²⁶Ra migration in the soil and the possible consequences to the environment.     

Studies on the structure-activity relationship of delta-sleep inducing peptide

DSIP and its fourteen analogs as well as three short peptides were synthesized by solid phase method. The design of the analogs was based on the consideration of the introduction of D-amino acid into the molecules to inhibit the enzymatic hydrolysis and the introduction of amino acids with a hydrophobic side chain. The modification was placed on the position of 1, 3, 4, 5, 8 and 9, e.g. D- Trp¹, Tyr¹, Tyr¹ Phe⁵, D-Trp¹ Phe⁸, Trp^3,4, D-Trp^1,3,4 Phe⁸, D-Trp3^,4 Phe⁸ D-Glu⁹, D-pF-Phe^3,4 Phe⁸ D-Glu⁹, Phe⁵, Glu⁵ Asp⁹, Tyr⁶ Asp⁹, Asp⁹ and Ala⁷-DSIP as well as Trp-Ala-Gly-Gly-Asp, Trp-Ala-Gly-Gly-Glu and Trp-Gly-Glu. DSIP and Phe⁵-DSIP were also prepared by pentafluorophenyl ester method. The purity of the synthetic peptides was checked by amino acid analysis, elemental analysis, thin layer chromatography and paper electrophoresis. The biological assay showed that the analogs of D-Trp¹, Tyr¹, Tyr¹ Phe⁵ and Ala⁷-DSIP as well as three short peptides were inactive whereas Phe⁵-DSIP showed similar activity as that of synthetic DSIP.     

Synthesis,characterization and applications of schiff base chemosensor for determination of Cu2+ ions

A novel thiazole-based Schiffbase chemosensor SB1 with N- and O- donor atoms was synthesized and characterized by different techniques (UV–vis, ¹³C NMR, ¹H NMR, and FT-IR analysis). The chemosensor SB1 was used for the determination of Cu²⁺ ions in various samples. The significant spectral changes in absorption spectra of chemosensor SB1 at 220 and 416 nm and the color change from light yellow to yellowish-brown indicate high selectivity and sensitivity towards Cu²⁺ ions as compared to other cations (Na⁺, K⁺, Ag⁺, Zn²⁺, Ni²⁺, Pb²⁺, Mn²⁺, Mg²⁺, Co²⁺, Cd²⁺, Sn²⁺, Hg²⁺, Cr³⁺, Fe^3+, and Al³⁺). The sensing mechanism of SB1 was investigated through various techniques such as FT-IR, UV–vis and ¹H NMR titration experiment and further confirmed by DFT computational studies. The 2:1 binding mode between SB1 and Cu²⁺ ions was confirmed by Job‘s plot using UV–vis spectrophotometry. The limit of detection (LOD) and limit of quantification (LOQ) were found to be 0.015 and 0.0471 µg mL^?1, respectively. The percent recovery of Cu²⁺ from various environmental samples was found to be 95.00–103.33% at various levels. These obtained results demonstrate that chemosensor SB1 is a cost-effective, facile, selective, sensitive, and colorimetric sensing platform to detect trace amounts of Cu²⁺ ions in variousenvironmental and agricultural samples.     

Some problems of parametric neutron activation analysis based on the use of radioactive daughters of longer-lived mothers with low mother/daughter half-life ratios

The theoretical and practical aspects of the use of radioactive daughters originated from the decay of longer-lived radioactive mothers in parametric activation analysis, when the ratio: mother half-life to daughter half-life is less than 10, are discussed. The mother-daughter relationships: ⁴⁷Ca/⁴⁷Sc; ⁹⁵Zr/⁹⁵Nb; ¹⁴⁰Ba/¹⁴⁰La; ⁹⁹Mo/^99mTc and ¹¹⁵Cd/^115mIn are selected as models for the study. The cases when the radionuclide of interest is formed through both direct and indirect routes are also analyzed. As illustrative example, the direct reaction and the reaction chain: ⁴⁷Ti(n,p)⁴⁷Sc/⁴⁶Ca(n,γ)⁴⁷Ca(β⁻)⁴⁷Sc are evaluated with respect to the determination of the elements involved and their reciprocal interferences.     

Efficiency calibration of HPGe detector in far and close geometries

The absolute total and full-energy peak (FEP) efficiencies of a high purity germanium (HPGe) photon detector are measured in the energy range from 40 keV to 1500 keV. The functional parameters are fitted to the calibration points from 14 long-lived standard sources (¹²⁹I,²⁴¹Am,¹⁰⁹Cd,⁵⁷Co,¹³⁹Ce,¹³⁷Cs,⁵⁴Mn,⁶⁵Zn,⁶⁰Co,²²Na,¹³³Ba,¹⁵²Eu,¹⁵⁴Eu and^166mHo) within an accuracy better than the quoted uncertainty of the calibration sources. The efficiencies in far and close geometries are compared.     

UV absorption spectrum of CF3CFClO2 and kinetics of the self reaction of CF3CFCl and CF3CFClO2 and the reactions of CF3CFClO2 with NO and NO2

The ultraviolet absorption spectrum of CF₃CFClO₂ and the kinetics of the self reactions of CF₃CFCl and CF₃CFClO₂ radicals and the reactions of CF₃CFClO₂ with NO and NO₂ have been studied in the gas phase at 295 K by pulse radiolysis/transient UV absorption spectroscopy. The UV absorption cross section of CF₃CFCl radicals was measured to be (1.78 ± 0.22) × 10^?18 cm² molecule^?1 at 220 nm. The UV spectrum of CF₃CFClO₂ radicals was quantified from 220 nm to 290 nm. The absorption cross section at 250 nm was determined to be (1.67 ± 0.21) × 10^?18 cm² molecule^?1. The rate constants for the self reactions of CF₃CFCl and CF₃CFClO₂ radicals were (2.6 ± 0.4) × 10^?12 cm³ molecule^?1 s^?1 and (2.6 ± 0.5) × 10^?12 cm³ molecule^?1 s^?1, respectively. The reactivity of CF₃CFClO₂ radicals towards NO and NO₂ was determined to (1.5 ± 0.6) × 10^?11 cm³ molecule^?1 s^?1 and (5.9 ± 0.5) × 10^?12 cm³ molecule^?1 s^?1, respectively. Finally, the rate constant for the reaction of F atoms with CF₃CFClH was determined to (8 ± 2) × 10^?13 cm³ molecule^?1 s^?1. Results are discussed in the context of the atmospheric chemistry of HCFC-124, CF₃CFClH. © 1994 John Wiley & Sons, Inc.     

The polarizability of a pair of hydrogen atoms at long range

The coefficients of R^?6 and R^?9 in the long-range expansion of the parallel and perpendicular components of the polarizability of a pair of hydrogen atoms at a separation R have been calculated. The results are A⁽⁶⁾₆ = 2558.59. A⁽⁶⁾_⊥ = 1268.25, A⁽⁸⁾₆ = 90639.5 and A⁽⁸⁾_⊥ = 22010.3 au. The values of A⁽⁶⁾₆ and A⁽⁶⁾₆ and A⁽⁶⁾_| are somewhat larger than previous theoretical estimates and much larger than the classical values of 729 and 182.25 au. The terms in R^?8 arise from distortion associated with the dispersion forces and from the field of the quadrupole moment induced by the field-gradient at each atom.     

Measurement of the neutron capture cross-section of 238U using the neutron activation technique

The ²³⁸U(n, ??)²³⁹U reaction cross-section at average neutron energy of 3.7?±?0.3?MeV from the ⁷Li(p, n)⁷Be reaction has been determined using activation and off-line ??-ray spectrometric technique. The ²³⁸U(n, ??)²³⁹U and ²³⁸U(n, 2n)²³⁷U reaction cross-sections at average neutron energy of 9.85?±?0.38?MeV from the same ⁷Li(p, n)⁷Be reaction have been also determined using the above technique. The experimentally determined ²³⁸U(n, ??)²³⁹U and ²³⁸U(n, 2n)²³⁷U reaction cross-sections were compared with the evaluated data of ENDF/B-VII, JENDL-4.0, JEFF-3.1 and CENDL-3.1. The experimental values were found to be in general agreement with the evaluated value based on ENDF/B-VII, and JENDL-4.0 but not with the JEFF-3.1 and CENDL-3.1. The present data along with literature data in a wide range of neutron energies were interpreted in terms of competition between different reaction channels including fission. The ²³⁸U(n, ??)²³⁹U and ²³⁸U(n, 2n)²³⁷U reaction cross-sections were also calculated theoretically using the TALYS 1.2 computer code and were also found to be in agreement experimental data.     

Reevaluation of the half-lives of several nuclides

The half-lives of⁶⁴Cu,⁷²Ga,⁷⁶As,⁸²Br,⁸⁸Rb,¹²⁸I,¹⁶¹Tb and¹⁷¹Er have been measured more accurately than previously.