Condensation of all-cis-tetraphenylcyclotetrasiloxanetetraol in ammonia: new method for preparation of ladder-like polyphenylsilsesquioxanes

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The mechanism of ethylene polymerization by nickel salicylaldiminato catalysts - Agostic interactions and their kinetic isotope effects

The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (k_H/k_D = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active.     

Influence of the sulfonate countercation on the thermal stability of nafion perfluorosulfonate membranes

We report a strong dependence of the thermal stability of Nafion® perfluorosulfonate ionomer on the nature of the counterion associated with the fixed sulfonate site. These results were obtained using thermal gravimetric analysis on a series of alkali metal and alkyl ammonium cation-exchanged Nafion films. We have found that the temperature of decomposition of Nafion is inversely dependent on the size of the exchanged cation; i.e., Nafion films show improved thermal stability as the size of the counter cation decreases. We attribute this inverse relationship of thermal stability with counterion size to an initial decomposition reaction which is strongly influenced by the strength of the sulfonate-coun-terion interaction. © 1993 John Wiley & Sons, Inc.     

Randomized greedy matching

We consider a randomized version of the greedy algorithm for finding a large matching in a graph. We assume that the next edge is always randomly chosen from those remaining. We analyze the performance of this algorithm when the input graph is fixed. We show that there are graphs for which this Randomized Greedy Algorithm (RGA) usually only obtains a matching close in size to that guaranteed by worst-case analysis (i.e., half the size of the maximum). For some classes of sparse graphs (e.g., planar graphs and forests) we show that the RGA performs significantly better than the worst-case. Our main theorem concerns forests. We prove that the ratio to maximum here is at least 0.7690…, and that this bound is tight.     

Microlocal Analysis of an FBP Algorithm for Truncated Spiral Cone Beam Data

In this article we propose an FBP-type algorithm for inversion of spiral cone beam data, study its theoretical properties, and illustrate performance of the algorithm by numerical examples. In particular, it is shown that the algorithm does not reconstruct f exactly, but computes the result of applying a pseudo-differential operator (PDO) with singular symbol to f. Away from critical directions the amplitude of this PDO is homogeneous of order zero in the dual variable, bounded, and approaches one as the pitch of the spiral goes to zero. Numerical experiments presented in the article show that even when the pitch is relatively large, the accuracy of reconstruction is quite high. On the other hand, under certain circumstances, the algorithm produces artifacts typical of all FBP-type algorithms.     

When random proportional subspaces are also random quotients

We discuss when a generic subspace of some fixed proportional dimension of a finite-dimensional normed space can be isomorphic to a generic quotient of some proportional dimension of another space. We show (in Theorem 4.1) that if this happens (for some natural random structures) then for any proportion arbitrarily close to 1, the first space has a lot of Euclidean subspaces and the second space has a lot of Euclidean quotients.     

A finiteness result for Heegaard splittings

In this paper we show that for a given 3-manifold and a given Heegaard splitting there are finitely many preferred decomposing systems of 3g−3 disjoint essential disks. These are characterized by a combinatorial criterion which is a slight strengthening of Casson-Gordon's rectangle condition. This is in contrast to fact that in general there can exist infinitely many such systems of disks which satisfy just the Casson-Gordon rectangle condition.     

A Triangle Inequality for Measurement

We introduce the triangle inequality for measurement. This is a property that when satisfied by a measurement enables one to construct a metric on the set of elements with measure zero that yields the relative Scott topology. The naturality of this construction permits a categorical solution to the model problem in domain theory for locally compact metric spaces. The first time such a solution has been achieved.     

Volumetric and infrared measurements on amorphous ice structure

We have simultaneously used adsorption isotherm volumetry and Fourier transform infrared spectroscopy in order to take the investigations on amorphous ice structure a step further, especially concerning porosity and annealing-induced modifications. We have studied surface reorganization during annealing and found that the number of surface sites decreases before crystallization, their relative ratios being different for amorphous and crystalline ice. We also present results confirming that ice can have a large specific surface area and nevertheless be non-microporous.