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Ion structure of keto and enol and McLafferty rearrangements determined by ion cyclotron resonance spectroscopy
Molecular rearrangements of nitrene intermediates, suggesting role in bond formation and breaking at nitrogen
Synthesis of 1-oxacyclopent-1-enyl cations from cyclopropyl ketones on heating in strong acids noting rearrangement rates
Dialkyl ketone ion in double McLafferty rearrangement, applying ion cyclotron resonance to structural study
Isomeric 1-phenylheptenes mass spectra, investigating electron impact induced rearrangements of double bond
Photochemical molecular rearrangement of NN- dimethylphenylethynylamine into alpha- phenylisobutyronitrile by irradiation at 254 nm
Amidoximes dehydration with and without rearrangement, suggesting carbodiimide formation from O-benzenesulfonyl ester
Ion cyclotron resonance application to propanol ion structure formed in double McLafferty rearrangement, demonstrating direct enol ion formation instead of by isomerization or ketonization
It is shown that in a rearrangement collision leading to the formation of the highly excited hydrogenlike states the cross section in all orders of the Born approximation behaves as 1/n sq, with n the principal quantum number, thus invalidating the Brinkman-Kramers approximation for large n. Similarly, in high energy inelastic electron-hydrogenlike atom collisions the exchange cross section for sufficiently large n dominates the direct excitation cross section.
It is shown that in a rearrangement collision leading to the formation of highly excited hydrogenlike states the cross section at high energies behaves as 1/n-squared, with n the principal quantum number, thus invalidating the Brinkman-Kramers approximation for large n. Similarly, in high-energy inelastic electron-hydrogenlike-atom collisions the exchange cross section for sufficiently large n dominates the direct excitation cross section.
A three body general rearrangement collision is considered where the initial and final bound states are described by the hydrogen-like wave functions. Mathematical models are developed to establish the relationships of quantum number, the reduced mass, and the nuclear charge of the final state. It is shown that for the low lying levels, the reciprocal of n cubed scaling law at all incident energies is only approximately satisfied. The case of the symmetric collisions is considered and it is shown that for high n and high incident energy, E, the cross section behaves as the reciprocal of E cubed. Zeros and minima in the differential cross sections in the limit of high n for protons on atomic hydrogen and positrons on atomic hydrogen are given.
A three-body general-type rearrangement collision is considered in which the initial and final bound states are described by hydrogen-like wave functions. It is shown that the charge-exchange amplitude in the first Born approximation can be expanded at all incident energies in terms of the inverse powers of the principal quantum number (n). By expanding the exchange amplitude in this way, it is demonstrated conclusively that the cross section for capture into the s, p, and d states as well as for the sum over all the angular-momentum states is proportional to 1/n-cubed plus terms proportional to higher inverse odd powers of n. It is found that the low-lying levels cannot be scaled to the 1/n-cubed law irrespective of the value of the incident energy except in the case of capture into the s states in accordance with the Oppenheimer-Brinkman-Kramers approximation. Zeros and minima in the differential cross sections are given in the limit of high principal quantum number for electron capture by protons from atomic hydrogen and for positronium formation by proton-atomic hydrogen collisions.
Experiments were conducted to measure and compare the accuracy with which subjects pointed to visual targets before and after an exposure period in which they received systematic proprioceptive misinformation about the locations of visual targets. The crucial factor determining whether adaptation will be elicited is shown to be the presence of a discordance in the positional information being conveyed over two different sensory modalities. Another experiment was carried out to study the effectiveness of active and passive movements in eliciting adaptation when the subjects were exposed to a systematic discordance between the visual and proprioceptive locations of external targets without being permitted sight of their hands. Superiority of active over passive movements in producing adaptation to visual rearrangement is due to the greater accuracy of position sense information about voluntarily moved limbs, partly derived from the contribution of muscle afferent signals.
Cytoplasmic rearrangements which follow fertilization were mentioned in normal and inverted eggs. A set of yolk compartments was resolved by cytological analyses of both normally oriented and inverted eggs. Those compartments were characterized by their yolk platelet compositions and movement during egg inversion. It is found that during egg inversion the yolk compartments shift minor cytoplasmic compartments which line the egg cortex. Those yolk mass shifts occurred only after the inverted egg was activated. The direction of shift of the major yolk components, rather than the sperm entrance site, determines the dorsal/ventral polarity of the inverted egg. Among different spawnings the rate of shift varied. Eggs that displayed the fastest rate of shift exhibited the highest frequency of developmental abnormalities during organogenesis. Interpretation of novel observations on cytoplasmic organization provide criticism of some earlier models. A new density compartment model is presented as a coherent way to view the organization of the egg cytoplasm and the development of bilateral symmetry.
After a short overview on the European tendencies about a Land Mobile Satellite Service, this paper describes an advanced system architecture, based on multiple spot-beams and on-board processing, capable of providing message and voice services over a wide European coverage, including some North-Africa and Middle-East countries. A remarkable problem associated with spot-beam configurations is the requirement for flexibility in the capacity offer to the various coverage areas. This means incorporating procedures for changing the on-board modulator-to-spot associations, respecting the constraints imposed by frequency reuse. After discussing the requirements of the rearrangement procedure, an on-purpose algorithm is presented. This paper is derived from work performed on contract to the European Space Agency (ESA).
The computational steps in calculating quantum mechanical reactive scattering amplitudes by the L2 generalized Newton variational principle are discussed with emphasis on computational strategies and recent improvements that make the calculations more efficient. Special emphasis is placed on quadrature techniques, storage management strategies, use of symmetry, and boundary conditions. It is concluded that an efficient implementation of these procedures provides a powerful algorithm for the accurate solution of the Schroedinger equation for rearrangements.
The stability of the PNA (peptide nucleic acid) thymine monomer inverted question markN-[2-(thymin-1-ylacetyl)]-N-(2-aminoaminoethyl)glycine inverted question mark and those of various PNA oligomers (5-8-mers) have been measured at room temperature (20 degrees C) as a function of pH. The thymine monomer undergoes N-acyl transfer rearrangement with a half-life of 34 days at pH 11 as analyzed by 1H NMR; and two reactions, the N-acyl transfer and a sequential degradation, are found by HPLC analysis to occur at measurable rates for the oligomers at pH 9 or above. Dependent on the amino-terminal sequence, half-lives of 350 h to 163 days were found at pH 9. At pH 12 the half-lives ranged from 1.5 h to 21 days. The results are discussed in terms of PNA as a gene therapeutic drug as well as a possible prebiotic genetic material.
Approximately 65-70% of the crew members now experience motion sickness of some degree during the first 72 h of orbital flight on the Space Shuttle. Lack of congruence among signals from spatial orientation systems leads to sensory conflict, which appears to be the basic cause of space motion sickness. A project to develop training devices and procedures to preadapt astronauts to the stimulus rearrangements of microgravity is currently being pursued. The preflight adaptation trainers (PATs) are intended to: demonstrate sensory phenomena likely to be experienced in flight, allow astronauts to train preflight in an altered sensory environment, alter sensory-motor reflexes, and alleviate or shorten the duration of space motion sickness. Four part-task PATs are anticipated. The trainers are designed to evoke two adaptation processes, sensory compensation and sensory reinterpretation, which are necessary to maintain spatial orientation in a weightless environment. Recent investigations using one of the trainers indicate that self-motion perception of linear translation is enhanced when body tilt is combined with visual surround translation, and that a 270 degrees phase angle relationship between tilt and surround motion produces maximum translation perception.