Rapid activation analysis of trace vanadium in tissue using 3.8-minute vanadium-52

Submicrogram amounts of vanadium in rat liver tissue have been analyzed by rapid activation analysis. A 5-min radiochemical separation coupled with γ-ray spectrometry permitted utilization of the 3.8-min vanadium-52 radioisotope. With this procedure the lower limit of detection at a thermal neutron flux of 10¹² n/cm²/sec was about 3·10^-9 g of vanadium.     

Distribution of reaction products (theory). Investigation of an ab initio energy-surface for F + H2 ⇀ HF + H

Bender, O'Neil, Pearson and Schaefer (BOPS) have computed ab initio energies for 232 collinear configurations of FHH, using extensive configuration interaction. We have fitted these points using an LEPS-type function. Comparison with semi-empirical surfaces for FHH shows that the general form of these surfaces is in good accord with the ab initio findings. Evidence is presented which indicates that the BOPS ab initio surface exhibits too great a drop in energy along the favoured route into the exit valley.     

Eroded myelin figures

Myelin figures with unusual surface morphology were observed on contacting Tween85 with water. Myelins, which are normally smooth rodlike forms in other surfactants, are in this system found to be with an irregular, rough surface with vesiclelike structures adhered to the myelin tubes. Besides these, smooth myelin figures were also observed. We term the myelin figures with a rough surface eroded myelin figures. The same myelin could show a coexistence of smooth and rough areas with a sharp boundary between the smooth surface at one end whereas the other end shows a rough texture. The transformation of smooth myelins into eroded forms were observed often whereas the reverse is quite rare. In the later stage, the tip of the eroded myelin figures transforms into tentacles and acts as a source for new myelins and the growth of vesiclelike structures which were expelled into the surrounding medium. The eroded myelin figures are stable for a longer period in comparison to simple, smooth rodlike forms. By studying the myelin growth at different temperatures, it was found that eroded myelin figures were stable in the temperature range of 22-42 degrees C and at > 42 degrees C only smooth myelin figures were observed.     

Synthesis of 1-Aza-8-thiabicyclo[4.2.1]nona-2,4-diene 8,8-dioxide and its conversion to a strained spirocycle via photoinduced SO2-N bond cleavage

A route to the doubly unsaturated bridgehead sultam 12 has been developed. When irradiated at 350 nm, this conjugated diene is isomerized via a two-photon process to the structurally novel spiro heterocycle 17 constituted of cyclobutene, thietane dioxide, and pyrrolidine rings. A probable mechanism for the generation of 17 and select reactions thereof are reported. [reaction: see text]     

Studies of surface properties of Na- and La-montmorillonites

This paper presents possible applications of thermal analysis, sorptometry and porosimetry to study physico-chemical properties of Na- and La-montmorillonite samples, especially for determination of total surface heterogeneity. The quasi-isothermal thermogravimetric (Q-TG) mass loss and its first derivative (Q-DTG) curves with respect to temperature and time obtained during programmed liquid thermodesorption under quasi-isothermal conditions have been used to study adsorbed layers and heterogeneous properties of the Na- and La-montmorillonites. Calculations of the desorption energy distribution functions by analytical procedure using mass loss Q-TG and differential mass loss Q-DTG curves of thermodesorption under quasi-isothermal conditions of polar and non-polar liquid vapours preadsorbed on a material surface are presented. Parameters relating to porosity of samples were determined by sorptometry, mercury porosimetry and atomic force microscopy (AFM). From nitrogen sorption isotherms from sorptometry and porosimetry methods, the fractal dimensions of montmorillonites have been calculated. Moreover, a new approach is proposed to calculate fractal dimensions of materials obtained from Q-TG curve; this is compared with values obtained by the above methods. The total heterogeneous properties (energy distribution function and pore-size distribution functions) of samples studied were estimated. The radius and pore volume of the tested samples calculated on the basis of thermogravimetry, sorptometry and porosimetry techniques were compared and good correlations obtained.     

REVERSIBLE PHOTOCHEMISTRY IN THE α-SUBUNIT OF PHYCOERYTHROCYANIN: CHARACTERIZATION OF CHROMOPHORE AND PROTEIN BY MOLECULAR DYNAMICS AND QUANTUM CHEMICAL CALCULATIONS

The ground and excited state properties of two regions in the Δ15-configurational space of the phycoviolobilin chromophore in the α-subunit of phycoerythrocyanin are analyzed. Molecular dynamics calculations reveal that the chromophore geometry determines the active-site dynamics. The excited state torsional potential surface shows a negative barrier for isomerization and trapping of an activated complex. Strong coupling of excited states localized in the chromophore and charge transfer states from the surrounding polar residues provides favorable prerequisites for fast excited state surface crossing in competition with other deactivation processes. The formation of a photoreduced intermediate following the photoinduced charge transfer may trigger subsequent chemical reactions.     

Linear and nonlinear optical studies of CdS1−x Se x quantum dots

In this contribution we present and discuss our measurements on CdS_1?x Se _x quantum dots in a glass matrix. In linear absorption measurements we find the typical blue shift of the transitions with decreasing crystallite radius due to quantization. The luminescence shows a significant Stokes shift with respect to absorption, which is interpreted in terms of strong exciton-phonon coupling and allows to deduce the Huang-Rhys factor S. Under high excitation we find an additional emission band on the high energy side, which can be attributed to the recombination of an excited two electron-hole pair state to a one electron-hole pair state in agreement with theory. Pump and probe beam experiments give a bleaching but no hole burning. Finally we discuss some open questions especially concerning the high energy structures in the absorption spectrum.     

Development of pork fat reference material for OCPs BCR-CRM 430

Summary A pork fat sample was prepared and tested as candidate reference material for 10 organochlorine pesticides and metabolites (OCPs): hexachlorobenzene, -, - and -HCH, -heptachlor epoxide, dieldrin, endrin, p,p'-DDT, p,p'-TDE and p,p'-DDE. Preparation and testing for homogeneity and stability of the OCPs in the pork fat are discussed. The coefficient of variation of pesticide determinations carried out to test the between-ampoule homogeneity ranged from 2.4–5.8% and was found to be very similar to that for the analytical method (2.5–4.9%). This means that the homogeneity is very good. Stability data over 12 months do not show any trends that suggest lack of stability.     

Partial oscillator strengths for the photoionization of N2O and CO2 (20–60 eV)

The photoelectron branching ratios and the partial oscillator strengths (cross sections) for photoionisation of the valence orbitals of N₂O and CO₂ have been obtained in the energy range 20–60 eV using the magic angle dipole (e, 2e) method. In addition to single electron ionization processes there is a large contribution from multiple electron transitions at higher energies in agreement with recent theoretical predictions. The photoionization efficiency and the dipole oscillator strenght for total photoabsorption have also been measured.     

The use of a chelating resin column for preconcentration of trace elements from sea-water in their determination by neutron-activation analysis

A Chelex-100 resin column has been employed for the preliminary concentration of trace elements in water samples before their determination by neutron-activation analysis. The column, filled with a 1:1 mixture of the resin (50-100 mesh) and Pyrex glass powder of the same mesh-size, is shown to maintain a constant flow-rate and give reproducible results. By a combination of preconcentration and neutron-activation analysis it is possible to determine Ba, Ca, Cd, Ce, Co, Cr, Cu, Fe, La, Mg, Mn, Sc, U, V and Zn in sea-water and/or fresh water simultaneously at the parts per milliard level.