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At least 55 records · Page 3

Steric effects in light-induced solvent proton abstraction

The significance of solvent structural factors in the excited-state proton transfer (ESPT) reactions of Schiff bases with alcohols is reported here. In this work, we use the super photobase FR0-SB and a series of primary, secondary, and tertiary alcohol solvents to illustrate the steric issues associated with solvent to photobase proton transfer. Steady-state and time-resolved fluorescence data show that ESPT occurs readily for primary alcohols, with a probability proportional to the relative –OH concentration. For secondary alcohols, ESPT is greatly diminished, consistent with the barrier heights obtained using quantum chemistry calculations. ESPT is not observed in the tertiary alcohol. We explain ESPT using a model involving an intermediate hydrogen-bonded complex where the proton is “shared” by the Schiff base and the alcohol. The formation of this complex depends on the ability of the alcohol solvent to achieve spatial proximity to and alignment with the FR0-SB* imine lone pair stabilized by the solvent environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

(abstract) Final Galileo Propulsion System In-Flight Characterization (Extended Abstract)

The Galileo Retropropulsion Module (RPM) has performed excellently during nearly seven years of Galileo mission operations. The RPM was provided by the Federal Republic of Germany to NASA to provide directed impulse to the Galileo spacecraft during all phases of the Galileo mission following Inertial Upper Stage (IUS) jettison. This paper documents the in-flight performance of the Galileo propulsion system since July 1993.

Galileo Galileo Retropropulsion Module propellants↗

Abstraction and Problem Reformulation

In work done jointly with Toby Walsh, the author has provided a sound theoretical foundation to the process of reasoning with abstraction (GW90c, GWS9, GW9Ob, GW90a). The notion of abstraction formalized in this work can be informally described as: (property 1), the process of mapping a representation of a problem, called (following historical convention (Sac74)) the 'ground' representation, onto a new representation, called the 'abstract' representation, which, (property 2) helps deal with the problem in the original search space by preserving certain desirable properties and (property 3) is simpler to handle as it is constructed from the ground representation by "throwing away details". One desirable property preserved by an abstraction is provability; often there is a relationship between provability in the ground representation and provability in the abstract representation. Another can be deduction or, possibly inconsistency. By 'throwing away details' we usually mean that the problem is described in a language with a smaller search space (for instance a propositional language or a language without variables) in which formulae of the abstract representation are obtained from the formulae of the ground representation by the use of some terminating rewriting technique. Often we require that the use of abstraction results in more efficient .reasoning. However, it might simply increase the number of facts asserted (eg. by allowing, in practice, the exploration of deeper search spaces or by implementing some form of learning). Among all abstractions, three very important classes have been identified. They relate the set of facts provable in the ground space to those provable in the abstract space. We call: TI abstractions all those abstractions where the abstractions of all the provable facts of the ground space are provable in the abstract space; TD abstractions all those abstractions wllere the 'unabstractions' of all the provable facts of the abstract space are provable in the ground space; and TC abstractions all those abstractions where a fact is provable in the ground space if and only if its abstraction is provable in the abstract space.

Giunchiglia, Fausto↗