A general nonlinear expansion form for electronic wave functions

A new expansion form is presented for electronic wave functions. The wave function is a linear combination of product basis functions, and each product basis function in turn is formally equivalent to a linear combination of configuration state functions that comprise an underlying linear expansion space. The expansion coefficients that define the basis functions are nonlinear functions of a smaller number of variables. The expansion form is appropriate for both ground and excited states and to both closed and open shell molecules. The method is formulated in terms of spin-eigenfunctions using the graphical unitary group approach (GUGA), and consequently it does not suffer from spin contamination.     

Considerations on Gaussian expanded generator coordinate wave functions

The recently developed integral discretization technique for the generator coordinate method is applied to discuss some features of Gaussian expanded wave functions. Using the hydrogen atom ground state, it is shown that the nuclear cusp problem has an interesting relation with the generator coordinator weight function, which allows the production of accurate wave functions by an integration criterion.     

A simple technetium generator

A systematic study on the extraction of⁹⁹Mo and its daughter^99mTc by pure organic diluents and dinonylnaphthalinesulfonic acid (DNNS) is described. The aqueous phases used are H₂SO₄, HCl, KI and their binary mixture solutions. The effect of alcohols on the distribution coefficient has been investigated. As a result of the study, a simple and rapid generator is built for the production of pure^99mTc from⁹⁹Mo.     

A computer-based programmable waveform generator

The programmable waveform generator, which is capable of producing complex voltage—time programs, is based on a PDP-$\text{11}\text{34}$ minicomputer with associated DIGITAL hardware. The desired waveform is obtained by clock-controlled output of a symmetrical triangular voltage sweep. The software can be readily adapted to any computer system. Ramp sections of 1 mV s^-1—50 V s^-1 and potential pulses of 50 μs—500 s can be obtained.     

A Cu(II)-mediated C-H oxygenation of sterically hindered tripyridine ligands to form triangular Cu(II)3 complexes

Two sterically hindered tris-pyridyl methane ligands, tris(6-methyl-2-pyridyl)methane (L1) and bis(6-methyl-2-pyridyl)pyridylmethane (L2), are newly synthesized. Under aerobic conditions, Ln (n = 1 or 2) reacts with CuX2 (X = Cl or Br), oxygenated at the methine position to LnOH or LnOMe. The former alcoholate ligand creates trinuclear Cu(II) complexes [Cu3(X)(LnO)3](PF6)2 [(X, n) = (Br, 1) 1, (C1, 1) 2, (Br, 2) 3, or (C1, 2) 4] in which the alkoxide oxygen atoms bridge copper centers. The crystal structures of 1-4 are presented along with their magnetic susceptibility data. The weak antiferromagnetic coupling between the Cu(II) centers in this trinuclear arrangement is due to weak interaction of the magnetic orbitals (dz2) which are oriented along three alternate sides in a hexagon of the Cu3O3 core in 1-4. Under anaerobic conditions, L1 reacts with CuBr2 to form a square pyramidal complex [CuL1Br2] (9) with the ligand facially capping. [Cu(Br)2(L1OMe)] (10) was obtained after the suspension of 9 in MeOH was stirred under air for 48 h. In the presence of cyclohexene, 9 is converted to [Cu(Br)(L1)]m (m = 1 or 2) 5 quantitatively to give trans- 1,2-dibromocyclohexane, indicating that Br2 is generated during the reaction. The FAB MS spectrum of [18O]-1 prepared by the reaction of L1 with CuBr2 under 18O2 shows that the ligand of [18O]-1 is L1(18O-.) L1(18OH), L1OCD3, and bis(6-methyl-2-pyridyl) ketone were obtained from reaction of L1 with CuBr2 in CD3OD under 18O2. These results indicate that the origins of the O atom in L1OH and L1OMe are O2 and MeOH, respectively. On the basis of these results, a mechanism of the oxygenation of L1 in the present system will be proposed.     

A useful triangular plot of triatomic potential energy surfaces

A triangular plot of triatomic potential energy surfaces is suggested in which the hidden coordinate - the perimeter of the molecule or the sum of squares of the three bond distances - is allowed to relax in order to give the lowest potential energy. This graphical representation preserves the full permutational symmetry of the problem. Examples are presented for the H₃ and HO₂ systems.     

A new continuous hydride generator for ICP-AES

With the construction of a tubular hydride generator some of the technical inconveniences of the hydride generation technique are overcome. The system allows the determination of hydride forming elements and mercury with a sample uptake rate of 1 ml/min without loss of sensitivity. Due to the small volume of the reactor and the performed neutralization of the reaction mixture in the siphon the memory effect is reduced. The sodium hydroxide used for neutralization also prevents the generation of an excess of hydrogen and therefore removes its negative influence on the plasma discharge.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria     

A109Cd/109mAg generator

Sorption of Cd and Ag by a cation exchange resin has been studied at different molarities of nitric acid. The sorption capacity of Cd on a cation exchanger has been determined. A¹⁰⁹Cd/^109mAg generator is suggested, based on the sorption of Cd on AG 50W-X8 organic cation exchanger at 0.01M HNO₃.^109mAg is eluted with 0.2M NaCl, physiologically compatible for human use.     

A modified sorbent for99mTc generator

A modified sorbent for^99mTe generators of higher activities has been developed. The sorbent consists of two layers. The layer in which (F.P.)⁹⁹Mo is adsorbed contains alumina and silica gel mixture in the weight ratio 40∶60%. The underlaying layer contains 0.5% g of pure alumina. The performances of the columns filled with this sorbent are compared to these containing pure alumina with respect to the total elution efficiency of^99mTc and the elution efficiency ratio of subsequent elutions. Radiochemical and radionuclidic purities (⁹⁹Mo breakthrough) of eluates from both kinds of columns have also been determined and compared.     

A generator for preparation of carrier-free224Ra

The construction of a dynamic generator for the separation of carrier-free²²⁴Ra is described. The mother²²⁸Th was extracted on the top of the column with di-(2-ethylhexyl)phosphoric acid on hydrophobized Chromosorb W DMCS. The function of the generator was checked during 6 months by measuring the decontamination of²²⁴Ra from²²⁸Th. Simultaneously the yield of²²⁴Ra was determined as a function of the HCl concentration and of the means of milking. The best results were obtained with 0.01–0.1M HCl; the yield was about 75% of the theoretical value, and the²²⁴Ra contained less than 0.01% of²²⁸Th.     

A new method for99mTc generator preparation

The authors report here a new approach for making^99mTc generators based on neutron irradiation of metallic molybdates and direct elution eliminating intermediate chemical processing steps. This approach tested using zirconium molybdate was found to yield^99mTc with good yield and purity. This seems to be the simplest way of making column type^99mTc generator even using low flux reactors and merits further detailed evaluation.     

A high voltage asymmetric waveform generator for FAIMS

High field asymmetric waveform ion mobility spectrometry (FAIMS) has been used increasingly in recent years as an additional method of ion separation and selection before mass spectrometry. The FAIMS electrodes are relatively simple to design and fabricate for laboratories wishing to implement their own FAIMS designs. However, construction of the electronics apparatus needed to produce the required high magnitude asymmetric electric field oscillating at a frequency of several hundred kilohertz is not trivial. Here we present an entirely custom-built electronics setup capable of supplying the required waveforms and voltages. The apparatus is relatively simple and inexpensive to implement. We also present data acquired on this system demonstrating the use of FAIMS as a gas-phase ion filter interface to an ion trap mass spectrometer.     

A generator of peroxynitrite activatable with red light

The generation of reactive oxygen species (ROS) and reactive nitrogen species (RNS) as “unconventional” therapeutics with precise spatiotemporal control by using light stimuli may open entirely new horizons for innovative therapeutic modalities. Among ROS and RNS, peroxynitrite (ONOO⁻) plays a dominant role in chemistry and biology in view of its potent oxidizing power and cytotoxic action. We have designed and synthesized a molecular hybrid based on benzophenothiazine as a red light-harvesting antenna joined to an N-nitroso appendage through a flexible spacer. Single photon red light excitation of this molecular construct triggers the release of nitric oxide (˙NO) and simultaneously produces superoxide anions (O₂˙⁻). The diffusion-controlled reaction between these two radical species generates ONOO⁻, as confirmed by the use of fluorescein-boronate as a highly selective chemical probe. Besides, the red fluorescence of the hybrid allows its tracking in different types of cancer cells where it is well-tolerated in the dark but induces remarkable cell mortality under irradiation with red light in a very low concentration range, with very low light doses (ca. 1 J cm⁻²). This ONOO⁻ generator activatable by highly biocompatible and tissue penetrating single photon red light can open up intriguing prospects in biomedical research, where precise and spatiotemporally controlled concentrations of ONOO⁻ are required.

Excitation of a molecular hybrid with highly biocompatible red light generates cytotoxic peroxynitrite, produces red fluorescence useful for cell tracking and induces remarkable cancer cell death at very low concentrations and very low light doses.     

Closed‐form rectangular atomic wave functions of an N‐dimensional atom

A closed‐form expression has been derived to obtain the N‐dimensional rectangular atomic wave functions. The wave functions can be obtained straightforwardly with the knowledge of the angular momentum quantum numbers and the dimension and there is no need to employ recursive methods as in previous works. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem 88: 263–274, 2002     

A simple method to synthesize triangular silver nanoparticles by light irradiation

We describe a simple method to synthesize triangular silver nanoparticles by photoreducing the silver ions by citrate. A noteworthy difference of the present method as compared with the previous photo-induced methods is that good shape control over the nanoparticles can be realized in the absence of soft templates or polymer directing agents. The formation process of the silver nanoparticles was investigated by UV-vis spectroscopy and transmission electron microscopy (TEM). It was found that the concentration of reactant plays important role in the morphology control of produced silver nanoparticles. As one of the applications of these nanoparticles, they were used as surface-enhanced Raman scattering substrates and 1,4-bis[2-(4-pyridyl)ethenyl]-benzene (BVPP) was used as a Raman probe to evaluate the enhancement ability of the triangular silver nanoparticles.     

A new test gas generator for atmospheric trace compounds

A new device for generating atmospheric trace gases for calibration purposes is described, which allows to adjust test gas concentrations with fast response times and constant carrier gas flow. It consists of a permeation tubing surrounded by a solution of the substance of interest. Inside of the tubing a movable piston is placed. The position of this piston determines the available fraction of the permeation surface and hence the output of the test gas source. The device has been tested for the trace gas production of SO₂ and formaldehyde in the ppbv range. It shows linear dependence of the produced concentrations on the position of the piston, fast response times and good reproducibilities.Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday