Chelatbildung mit N-unsubstituierten 1.2-Diiminliganden

Fe^II, Co^III, Ni^II, Pd^II, and Rh^III chelates with the N-unsubstituted 1-2-diimine ligands benzildiimine and 9.10-phenanthrenequinonediimine have been prepared. The compounds are characterised chemically, spectroscopically (uv, vis, ir) and polarographically. The results indicate remarkable π-back bonding in the chelates. The unusual magnetic moments of the Fe^II, Co^III and Rh^III chelates are caused by temperature-independent paramagnetism. Fe^II, Co^III, Ni^II and Cu^II chelates of the partially deprotonated phenanthrenequinone diimine are obtained.     

Measurement of lead-210, bismuth-210, and polonium-210 in environmental samples

Mathematical equations governing the ratio of²¹⁰Bi/²¹⁰Pb and²¹⁰Po/²¹⁰Pb activities are used to explain the ingrowth of²¹⁰Bi and²¹⁰Po in environmental samples during post collection. Procedures are described for radiochemical separation of²¹⁰Pb,²¹⁰Bi, and²¹⁰Po in a state of radioactive disequilibrium and quantification by alpha- and beta-counting. Also, the special case is considered where²¹⁰Bi is in equilibrium with²¹⁰Pb, but both are in disequilibrium with²¹⁰Po. In this case, the activities of both²¹⁰Pb and²¹⁰Po are computed by measuring²¹⁰Po activity twice, using alpha-counting.     

On the electronic structure of MoO: Spin-polarized density functional calculations of spectroscopic properties of low-lying quintet,triplet, and septet states

Density functional theory (DFT ) calculations for the ground state and four excited quintet, two septet, and two triplet states of the molybdenum oxide molecule are reported. Equilibrium geometries and other spectroscopic constants are determined for these states and compared both with recent spectroscopic measurements and other theoretical calculations, where available. Experimental assignments of the ⁵II ground state and excited ⁵Σ⁺, ⁵Σ^?, ⁵Δ, and B^{' 5}II states are confirmed; also candidates for low-lying triplet³ Δ and ³Σ^? and septet ⁷II and ⁷Σ⁺ are presented. Theoretical calculations for ⁵Σ^?, B^{' 5}II, and ³Σ^? states are reported for the first time. The results are in many cases in better agreement with experiment than are other calculations, already at the simplest level of approximation within DFT , which confirms that this method is a useful tool for investigation of transition-metal compounds. © 1994 John Wiley & Sons, Inc.     

EPR and optical study of coupled Yb<Superscript>3+</Superscript> ion pairs in weakly doped LiNbO<Subscript>3</Subscript>:Yb single crystal

The results of electron paramagnetic resonance and optical spectroscopy studies of Yb³⁺ ions in LiNbO₃:1% Yb host crystal are reported. Also some results of Raman spectra measurements are presented. The observed features are assigned to single Yb³⁺ ions and pairs of dissimilar ions (with different g value) of the type of ^evenYb³⁺-^evenYb³⁺. The values of the components of the g-tensor for both ions and interaction exchange tensors are estimated. The value of J = ?0.0283 cm^?1 shows that the exchange interactions are of antiferromagnetic nature. The most probably the ^evenYb³⁺-^evenYb³⁺ pairs substitute for neighborhood Li⁺-Nb⁵⁺ positions what induces gain of distance between ions of about 1 Å. There are no observed dissimilar ion pairs of the type ^oddYb³⁺-^oddYb³⁺.     

Ab initio study on NH+: Transition dipole moments,transition probabilities,and radiative lifetimes

The transition electric dipole moments between low-lying valence states of NH⁺ are calculated by an ab initio effective valence-shell Hamiltonian (H^v) method. The H^v calculated transition moments are found to be in good agreement with those by other accurate ab initio methods. The spontaneous emission probabilities for the A²− → X²Π, B²Δ → X²Π, and C²−⁺ → X²Π transitions of NH⁺ are computed. Also, radiative lifetimes for A²∑⁻, B²Δ, and C²∑⁺ states are all theoretically determined using the potential energy functions by H^v. Also, the H^v results are well compared with those computed using the Morse potentials and the rkr potentials which are obtained from experimental data. © 1996 John Wiley & Sons, Inc.     

Synthesis and structure of transition metal complexes derived from a novel polynucleating oxaza macrocycle having diazine and phenoxo bridging components

Novel Co^II, Ni^II, Cu^II and Zn^II complexes of the polynucleating oxaza macrocyclic ligand (LH₄) derived from the 2:2 condensation of pyrazole-3,5-dicarbohydrazide and 2,6-diformyl-4-methylphenol have been synthesized. Ligand and complexes were characterized on the basis of elemental analysis, IR, ¹HNMR, UV–Visible, magnetic susceptibility, ESR and conductivity measurements, FAB-mass and thermal analysis. Present Zn^II and Cu^II complexes are binuclear in nature with octahedral geometry, where as Co^II and Ni^II complexes are tetranuclear with square-planar geometry. Cu^II and Co^II complexes are paramagnetic whereas Zn^II and Ni^II complexes are diamagnetic. Only the copper complex has shown redox property in the applied potential range while the ligand and other complexes are found to be electrochemically innocent.     

Mixed Beds for Selective Removal of Ammonium Carbonate in Dialysate

We have studied experimentally and theoretically the exchange of NH₄ ⁺, Na⁺, K⁺, Ca⁺⁺, Mg⁺⁺, and H⁺ ions in zeolite beds, weakly-acidic resin beds, and mixed beds of the zeolite and the resin. The zeolite is highly selective for NH₄ ⁺ and K⁺, whereas the resin with carboxyl functional groups is highly selective for Ca⁺⁺ and Mg⁺⁺. The effluent histories of single exchanger beds can be well predicted by the Multicomponent Chromatography Theory developed by Helfferich and Klein (1970). These histories are mainly the result of ion competition for ion exchanger sites; they can not be adjusted to meet the goal that NH₄ ⁺ ions are removed and simultaneously the pH and concentrations of all the major physiological cations are maintained at normal values. The effluent histories of mixed beds, on the other hand, can be adjusted. We have designed a mixed bed which can meet the goal except that for each equivalent of NH₄ ⁺ removed, 0.3 equivalents of Na⁺ are returned. The effluent histories of K⁺ and NH₄ ⁺ for the mixed beds are similar to those of the zeolite beds, whereas the Ca⁺⁺ and Mg⁺⁺ histories are similar to those of the resin beds.     

Theoretical study of [F−; e+] and [CN−; e+]

Ab initio calculations are presented for the [F^?; e⁺] and [CN^?; e⁺] complexes. Positron affinities of 4.99 and 3.79 eV are obtained for F^? and CN^?, respectively. The excitation energies to the low-lying excited states of the positron complexes are also calculated.     

Mangifera indica leaf-assisted biosynthesis of well-dispersed silver nanoparticles

Natural fluorite crystals containing oxygen impurities are colored electrolytically by using a pointed cathode and a flat anode at various temperatures and voltages. F and F₂ color centers are produced in colored fluorite crystals. O²⁻–V_a⁺, O²⁻–V_a⁺ aggregate, Yb²⁺, Ce³⁺ and Sm²⁺ absorption bands are observed in absorption spectra of uncolored fluorite crystals. O²⁻–V_a⁺, O²⁻–V_a⁺ aggregate, Yb²⁺, Ce³⁺, Sm²⁺, F, M (F₂) absorption bands and group of four absorption bands are observed simultaneously in absorption spectra of colored fluorite crystals. Current−time curve for electrolytic coloration of natural fluorite crystal and its relationship with electrolytic coloration process are given. Production and conversion of color centers are explained.     

Linear Copper Complex Arrays as Versatile Molecular Strings: Syntheses,Structures, Luminescence,and Magnetism

The defined linear arrangement of metal atoms in discrete coordination complexes or polymers is still one of the most intriguing challenges in synthetic chemistry. These chain arrangements are of fundamental importance, because of their potential applications as molecular wires and single molecule magnets (SMM) in microelectronic devices on a molecular scale. Oligonuclear Group 11 metal complexes with suitable bridging ligands, specifically those that are based on copper as the first choice of a cheap precursor coinage metal, are of particular interest in this regard. This is due to the superior luminescence properties of these linear clusters that often show d¹⁰⋅⋅⋅d¹⁰ interactions in their molecular structures. The combination of Cu^I with heavier coinage metal ions results in tunable emissive arrays that are also stimuli-responsive. Thus, both linear multinuclear Cu^I and linear heteropolymetallic Cu^I/Ag^I as well as Cu^I/Au^I clusters are excellent candidates for applications in molecular/organic light-emitting devices (OLEDs). Alternatively, paramagnetic multinuclear cupric arrays are prominent as potential molecular wires with enhanced magnetic properties through multiple coupled d⁹ centers. This Review covers the whole range of linear multinuclear assemblies of cuprous and cupric ions in complexes and coordination polymers, their syntheses, photophysical behavior, and magnetic properties. Moreover, recent advances in the rapidly progressing field of hetero-Cu^I/Ag^I and Cu^I/Au^I molecular strings are also discussed.     

Organylselenoacetylene und selenocyanate; 77Se- und 13C-NMR-chemische verschiebungen und 77Se- 13C-spin-kopplungskonstanten

⁷⁷Se and ¹³C NMR chemical shifts and ⁷⁷Se-¹³C spinspin coupling constants of mono- and bis(organylseleno)acetylenes and organyl selenocyanates are shown. The changes of ⁷⁷Se chemical shifts caused by variation of the organyl groups are well reflected by known increments. The δ(⁷⁷Se) and ¹J(⁷⁷Se¹³C) values of the investigated compounds are discussed in relation to the corresponding alkyl- and vinyl-selenides. The ¹J(⁷⁷Se¹³C) values of the selenoacetylenes and selenocyanates as well as alkyl- and vinyl-selenides are linearly dependednt (i) on ¹J(¹³C¹H) values of the corresponding hydrocarbons, hydrogen cyanide respectively and (ii) on the product of the s-characters of the coupled Se and C atoms. These linear correlations prove the predominance of the Fermi contact term for changes of the one-bond ⁷⁷Se¹³C coupling in dependence on hybridization.     

Ab initio calculations of doublet states of NH+

The eight low-lying doublet states of the NH⁺ ion are investigated with an ab initio configuration interaction method including all single and double excitations from a multi-reference configuration space (MRSD CI). The spectroscopic constants for the X²Π, A²Σ⁻,B²Δ and C²Σ⁺ states and the transition moments for X²Π-A ²Σ⁻¹ and X²Π-B²Δ are calculated. The results are compared with experiments and other calculations.     

SYNTHESES OF SOME 35S-LABELLED ORGANIC COMPOUNDS AT BORIS KIDRIČ INSTITUTE - VINČA

Abstract

³⁵-labelled organic compounds are widely used in different fields: medicine, chemistry, biochemistry, biology, etc. Some of these compounds are known as chemoprotectors and ³⁵S-labelled forms are used in the investigation of such protective mechanism. Details of the chemical and biochemical syntheses of some ³⁵S-labelled organic compounds are given in the paper: DL-cysteine hydrochloride-³⁵S (1-amino-2-mercaptopropionic acid), vitamin B₁-³⁵S (thiamin hydrochloride), thiourea-³⁵S, carbon disulphide-³⁵S and L-methionine-³⁵S (1-amino-4-methyl- thiobutyric acid). Products of high specific activities are obtained: 5–10 mCi/mM DL-cysteine hydrochloride-³⁵S; 60–120 mCi/mM vitamin B₁-³⁵S; 100–200 mCi/mM thiourea-³⁵S; 20–100 mCi/mM carbon disulphide- ³⁵S and 1–10 Ci/mM L-methionine-³⁵S. All the products are of high chemical and radiochemical purity, which were determined by thin layer chromatography.     

Negative-ion-negative-ion neutralization-reionization (−NR−)

There are four neutralization-reionization processes which can be studied. In the first two, gaseous cations are collisionally reduced and the resulting fast neutrals are either oxidized by collisional electron removal (NR) or reduced further by collisional electron attachment (NR^?). In the third and fourth processes, gaseous anions are collisionally oxidized and the resulting fast neutrals are either oxidized further by collisional electron removal (^?NR) or reduced by collisional electron attachment (^?NR^?). These four processes are illustrated briefly using the interrelated species [SF₅]⁺ and [SF₅]^?. Negative-ion-negative-ion neutralization-reionization (^?NR^?) processes are illustrated for [CH₃O]^?, [C₂H₅O]^?, [CO₃]^? and [HCO₃]^? and compared with ^?NR processes. In addition, collisional electron attachment ionization of fast neutrals formed in unimolecular fragmentation of cations is illustrated. The ^?NR^? studies of [CO₃]^? and [HCO₃]^? show that both CO₃ and HCO₃ are stable neutral species with lifetimes greater than 0.7 μs.     

Wide-area aquatic sampling and analysis for the detection of nuclear proliferation

Nuclear proliferation signature radionuclides can be delivered to the aquatic environs via direct liquid discharges or atmospheric routes. The candidate radionuclides for detection are ³H, ⁹⁰Sr, ⁹⁵Nb, ⁹⁵Zr, ⁹⁹Tc, ¹⁰⁶Ru, ¹²⁵Sb, ¹²⁹I, ¹³⁴Cs, ¹³⁷Cs, ¹⁴⁴Ce, ¹⁴⁷Pm, ^NatU, ²³⁸U, ²³⁵U, ²³⁷Np, ²³⁹Pu, ²⁴⁰Pu, and ²⁴¹Pu. The criteria for detection are the limits of radionuclide analysis, the nature and variability of background oncentrations, and the transport characteristics between the source and sample site. The type of sample to be taken is determined by the signature radionuclides sorption on/in the media sampled. Non-sorbing radionuclides such as ³H, ⁹⁹Tc, and ¹²⁹I are in the water, whereas the Pu radionuclides are in the transported sediments. Results are discussed for monthly releases of radionuclides such as ⁹⁰Sr, ¹³⁷Cs, and ²³⁹Pu for variable flow-rate conditions with typical backgrounds and typical detection limits.     

Dérivés Alléniques de l'Étain,du Plomb et du Mercure. Signes Relatifs des Constantes de Couplage Métal-Proton á Travers Deux et Quatre Liaisons

Satellites corresponding to metal-proton coupling constants through two and four bonds are observed in PMR spectra of Pb, Sn and Hg allenic derivatives. The relative signs of these coupling constants are deduced from analysis of the satellite spectra: ²J(X? H) and ⁴J(X? H) are of opposite signs for X = ²⁰⁷Pb, ¹¹⁹Sn, ¹¹⁷Sn and of same sign for X = ¹⁹⁹Hg. Probable absolute signs of reduced coupling constants are discussed in relation to published data: ²K(X? C? H) is probably positive for X = ²⁰⁷Pb, ¹¹⁹Sn, ¹¹⁷Sn and ¹⁹⁹Hg. ⁴K(X? C?C?C? H) is probably negative for X = ²⁰⁷Pb, ¹¹⁹Sn, ¹¹⁷Sn and positive for X = ¹⁹⁹Hg.     

Heterodyne measurements of hot bands and isotopic transitions of N2O near 7.8 µm

Heterodyne frequency measurements are reported for absorption transitions of N₂O in the frequency range from 1257 to 1335 cm^?1. The measurements use a CO laser as a transfer oscillator whose frequency is measured directly against combinations of frequencies of two stabilized CO₂ lasers whose frequencies are well known. A tunable diode laser is locked to the N₂O absorption feature and the frequency difference is measured between the diode laser and the CO laser. Thev ₃ fundamental bands of the¹⁵N¹⁴N¹⁶O and¹⁴N¹⁵N¹⁶O isotopes are reported. Measurements are also given for the 00⁰2–00⁰1, 02⁰1–02⁰0, and 02²1–02²0 vibrational transitions of N₂O. A table of frequencies is given for the 00⁰2–00⁰0 band near 2560 cm^?1 based on these and earlier measurements.     

Study of the intensity of M+, M2+ and MO+ signals in ICP-MS as a function of instrumental parameters

In addition to peaks from singly charged ions (M⁺), signals from oxide (MO⁺), hydroxide (MOH⁺) and doubly charged (M²⁺) ions, which may lead to spectral overlap interferences, are observed in ICP-MS spectra. Using a VG PlasmaQuad ratios of MO⁺/M⁺, MOH⁺/M⁺ and M²⁺/M⁺ were determined for a number of elements, covering a wide range of atomic masses, first and second ionisation energies and chemical properties. The temporal stability of the MO⁺/M⁺ and M²⁺/M⁺ ratios was investigated. The correlation between the ratios of MO⁺/M⁺ and M²⁺/M⁺ with the M-O bond strength and the difference between the second and the first ionisation energy respectively is discussed. The influence of several instrumental parameters, associated with sample introduction and plasma operation, on the M⁺, M²⁺ and MO⁺ signals and on the MO⁺/M⁺ and M²⁺/M⁺ ratios is studied. Simple qualitative explanations are given in order to explain some of the observed results. No quantitative results are given for the MO⁺/M⁺ and M²⁺/M⁺ ratios as the experiments pointed out that they are influenced to a large extent by several instrumental parameters.     

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.