Photoinitiation and electroinitiation in the polymerization of 2-vinylnaphthalene

The zinc chloride-catalyzed polymerization of 2-vinylnaphthalene (VN) with both photoinitiation and electronitiation methods was examined. Good yields were obtained with both methods, the electroinitiated process being somewhat faster. The mechanism for polymerization initiation was investigated through a detailed comparison of the kinetics. Both initiation methods show a similar response to increasing input energy and to change in salt to monomer mole ratio. Both methods indicate formation of a ZnCl₂–(2-VN)₂ complex as intermediate with the formation of the species being rate-determining. These results, together with other similar investigations, are then used to deduce a mechanism that involves the formation of an electronically excited donor–acceptor complex. It is argued that in certain salt-stabilized, electron-delocalized, aromatic systems, such excitation is possible in electroinitiation.     

Open- and closed-shell states in few-particle quantum mechanics. II. Classification of atomic states

The system developed in the first paper of this series for the classification of states as open- or closed-shed type is applied to atomic states. These may be classified in the isoelectronic limit (Z → ∞) from knowledge of the true wave function in this limit. One-matrix occupation numbers are tabulated for a number of states of the first-row atoms in the limit Z → ∞ and the states classified. A classification for finite Z is possible in the framework of the Z-dependent perturbation theory by use of a thoerem for the stability of a closed-shed with respect to small perturbations. Such a stability does not hold in general for open-shel states.     

Reactions of organoboranes and 2-lithio-2-alkyl-1,3-benzodithioles. A new,improved synthesis of ketones

Reactions of trialkylboranes with 2-lithio-2-alkyl-1,3-benzodithioles followed by oxidation give ketones in good yields. This method is far less subject to steric hindrance than the analogous reactions using anions derived from bis(phenylthio)alkanes.     

Detection and assessment of citrus tristeza virus antigens by computer-aided scanning densitometry

Citrus tristeza virus (CTV) extracted from Etrog citron (C.medica L.) was immunoprecipitated. The immunoprecipitate was fractionated by SDS-PAGE and western blotted onto nitrocellulose. The CTV antigens were determined by immunoblot analysis using rabbit anti-CTV IgG, and the protein-band pattern exhibited on the nitrocellulose was assessed by soft-laser scanning densitometry. The densitometric tracing revealed the presence of bands that were not visible to the naked eye. Using the superimposition mode of the instrument, it was also revealed that the protein-band patterns of different CTV samples were not identical. Computer-aided soft-laser scanning densitometry proved to be a powerful approach in the detection and assessment of protein bands revealed on nitrocellulose immunoblots, which we were previously unable to do employing conventional methods.     

THE EFFECTS OF AGGREGATION ON THE FLUORESCENCE and THE TRIPLET STATE YIELD OF HEMATOPORPHYRIN

Abstract— The fluorescence and triplet state yields of hematoporphyrin have been measured in wuter/methanol mixtures. There is a closely linked response of these yields to aggregation of the hematoporphyrin molecule. The monomer, which is the principal species present at high methanol content, has a triplet state yield of 0.91 and a fluorescence yield of 0.09. By contrast, hematoporphyrin solutions with a high water content containing aggregates have lower fluorescence and triplet state yields, e.g. 0.018 and 0.56, respectively, in water. Static, singlet state quenching in some of the aggregates is responsible for the reduced fluorescence yield. The results also show that in addition to these aggregates there are other types of aggregates where there is an increased singlet to ground state radiative transition probability, resulting from the interaction between transition dipoles in adjacent molecules.     

Overview: recent progress in three-dimensional atom probe instruments and applications.

Over the last few years there have been significant developments in the field of three-dimensional atom probe (3DAP) analysis. This article reviews some of the technical compromises that have led to different instrument designs and the recent improvements in performance. An instrument has now been developed, based around a novel reflectron configuration combining both energy compensation and focusing elements, that yields a large field of view and very high mass resolution. The use of laser pulsing in the 3DAP, together with developments in specimen preparation methods using a focused ion-beam instrument, have led to a significant widening in the range of materials science problems that can be addressed with the 3DAP. Recent studies of semiconductor materials and devices are described.     

A convenient oxazole C-2 protecting group: the synthesis of 4- and 5-substituted oxazoles via metalation of 2-triisopropylsilyloxazoles

[reaction: see text] Metalation of oxazoles at the 4 and 5 position was achieved after regioselective C-2 silyl protection. Removal of the protecting group was then accomplished under mild conditions allowing for a straightforward preparation of C-5 monosubstituted and C-4,5 disubstituted oxazoles. The first practical C-2 protecting group of oxazoles has been demonstrated.     

Effects of alkali metal halide salts on the hydrogen bond network of liquid water

Measurements of the oxygen K-edge X-ray absorption spectrum (XAS) of aqueous sodium halide solutions demonstrate that ions significantly perturb the electronic structure of adjacent water molecules. The addition of halide salts to water engenders an increase in the preedge intensity and a decrease in the postedge intensity of the XAS, analogous to those observed when increasing the temperature of pure water. The main-edge feature exhibits unique behavior and becomes more intense when salt is added. Density functional theory calculations of the XAS indicate that the observed red shift of the water transitions as a function of salt concentration arises from a strong, direct perturbation of the unoccupied molecular orbitals on water by anions, and does not require significant distortion of the hydrogen bond network beyond the first solvation shell. This contrasts the temperature-dependent spectral variations, which result primarily from intensity changes of specific transitions due to geometric rearrangement of the hydrogen bond network.     

A New Silicate Clathrate Hydrate: An X-Ray Diffraction and Nuclear Magnetic Resonance Study of a System with Octameric Silicate Anions and Trivalent Cations

The first crystal structure is reported for a silicate clathrate hydrate involving a triply charged cation [C₁₈H₃₀N₃]³⁺ and an octameric cubic silicate cage. The structure is essentially a host/guest system, with the silicate cages linked into a framework by hydrogen bonding to water molecules. The space group is P with Z = 2, and the asymmetric unit includes a complete cation and half the anion, plus 21 water molecules (4 of which are in disordered positions). Solid-state (CPMAS) ²⁹Si and ¹³CNMR spectra are consistent with the diffraction-determined structure and indicate substantial distortion of the anion from cubic symmetry. Solution-state spectra of precursor solutions and of melted material are also presented and discussed.