High-fidelity Recognition of Organotrifluoroborate Anions (R−BF3−) as Designer Guest Molecules

The recognition of boron compounds is well developed as boronic acids but untapped as organotrifluoroborate anions (R−BF₃⁻). We are exploring the development of these and other designer anions as anion-recognition motifs by considering them as substituted versions of the parent inorganic ion. To this end, we demonstrate strong and reliable binding of organic trifluoroborates, R−BF₃⁻, by cyanostar macrocycles that are size-complementary to the inorganic BF₄⁻ progenitors. We find that recognition is modulated by the substituent's sterics and that the affinities are retained using the common K⁺ salts of R−BF₃⁻ anions.     

Flatness in analytic mappings I. On an announcement of Hironaka

We present a stratification by “normal flatness” associated to an analytic mapping, analogous to Hironaka's classical result for analytic spaces. Our construction is based on a generic normal flatness theorem for mappings, proved using techniques concerning the variation of modules of meromorphically parametrized formal power series [1]. The existence of such a stratification was announced by Hironaka [13], but the other claims made in [13] are false. Counterexamples are also presented here.     

Enantiodiscrimination of racemic electrophiles by diketopiperazine enolates: asymmetric synthesis of methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates

Enolates of (S)-N,N′-bis-(p-methoxybenzyl)-3-iso-propylpiperazine-2,5-dione exhibit high levels of enantiodiscrimination in alkylations with (RS)-1-aryl-1-bromoethanes and (RS)-2-bromoesters, affording substituted diketopiperazines containing two new stereogenic centres in high de. Deprotection and hydrolysis of the resultant substituted diketopiperazines provides a route to the asymmetric synthesis of homochiral methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates in high de and ee.     

High-temperature expansions to fifteenth order

High-temperature series expansions of the susceptibility and second moment to 15th order are calculated for zero external field on the linear chain (LC), plane square (PSQ), simple cubic (SC), and body-centered cubic (BCC) lattices. Checks for specific models against pertinent work in the literature are detailed.     

Anionic iron(II) alkoxides as initiators for the controlled ring‐opening polymerization of lactide

Hetero‐bimetallic Fe(II) alkoxide/aryloxides were evaluated as initiators for the ring‐opening polymerization of rac‐lactide. [(THF)NaFe(O^tBu)₃]₂ ( 1 ) and [(THF)₄Na₂Fe(2,6‐diisopropylphenolate)₄] ( 2 ) (THF = tetrahydrofuran) both polymerized lactide efficiently at room temperature, with complex 1 affording better control over the molecular weight parameters of the resultant polymer. At conversions below 70%, a linear increase in molecular weight with conversion was observed, indicative of a well‐controlled polymerization process. Complex 2 is the first example of a dianionic Fe(II) alkoxide and has been structurally characterized to reveal a distorted square planar FeO₄ array in which both Na counterions bridge two aryloxide ligands and are further complexed by two THF ligands. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3798–3803, 2003     

Canonical desingularization in characteristic zero by blowing up the maximum strata of a local invariant

Summary. This article contains an elementary constructive proof of resolution of singularities in characteristic zero. Our proof applies in particular to schemes of finite type and to analytic spaces (so we recover the great theorems of Hironaka). We introduce a discrete local invariant whose maximum locus determines a smooth centre of blowing up, leading to desingularization. To define , we need only to work with a category of local-ringed spaces satisfying certain natural conditions. If , then depends only on . More generally, is defined inductively after any sequence of blowings-up whose centres have only normal crossings with respect to the exceptional divisors and lie in the constant loci of . The paper is self-contained and includes detailed examples. One of our goals is that the reader understand the desingularization theorem, rather than simply “know” it is true. Oblatum 27-VII-1995 & 30-V-1996     

The Interaction of Shocks with Dispersive Waves II. Incompressible-Integrable Limit

This is the second in a two-part series of articles in which we analyze a system similar in structure to the well-known Zakharov equations from weak plasma turbulence theory, but with a nonlinear conservation equation allowing finite time shock formation. In this article we analyze the incompressible limit in which the shock speed is large compared to the underlying group velocity of the dispersive wave (a situation typically encountered in applications). After presenting some exact solutions of the full system, a multiscale perturbation method is used to resolve several basic wave interactions. The analysis breaks down into two categories: the nonlinear limit and the linear limit, corresponding to the form of the equations when the group velocity to shock speed ratio, denoted by ε, is zero. The former case is an integrable limit in which the model reduces to the cubic nonlinear Schrödinger equation governing the dispersive wave envelope. We focus on the interaction of a “fast” shock wave and a single hump soliton. In the latter case, the ε=0 problem reduces to the linear Schrödinger equation, and the focus is on a fast shock interacting with a dispersive wave whose amplitude is cusped and exponentially decaying. To motivate the time scales and structure of the shock-dispersive wave interactions at lowest orders, we first analyze a simpler system of ordinary differential equations structurally similar to the original system. Then we return to the fully coupled partial differential equations and develop a multiscale asymptotic method to derive the effective leading-order shock equations and the leading-order modulation equations governing the phase and amplitude of the dispersive wave envelope. The leading-order interaction equations admit a fairly complete analysis based on characteristic methods. Conditions are derived in which: (a) the shock passes through the soliton, (b) the shock is completely blocked by the soliton, or (c) the shock reverses direction. In the linear limit, a phenomenon is described in which the dispersive wave induces the formation of a second, transient shock front in the rapidly moving hyperbolic wave. In all cases, we can characterize the long-time dynamics of the shock. The influence of the shock on the dispersive wave is manifested, to leading order, in the generalized frequency of the dispersive wave: the fast-time part of the frequency is the shock wave itself. Hence, the frequency undergoes a sudden jump across the shock layer.In the last section, a sequence of numerical experiments depicting some of the interesting interactions predicted by the analysis is performed on the leading-order shock equations.