Studies of Hindered Rotation and Magnetic Anisotropy by 1H, 13C and 19F NMR. The Diels-Alder Adduct of N- Pentafluorophenylmaleimide and Phencyclone: A Model for Drugs.

The potent Diels-Alder diene, phencyclone, 1, reacts with N-pentafluorophenylmaleimide, 2, to form an adduct, 3, characterized by ¹H, ¹³C, and ¹⁹F NMR at 300, 75 and 282 MHz, respectively. The one-dimensional (1D) and two-dimensional (2D) ¹H and ¹³C NMR spectra of 3 at ambient temperatures imply a slow exchange limit (SEL) regime with respect to rotation of the unsubstituted bridgehead phenyl groups about severely hindered C(sp²)-C(sp³) bonds. Major non-bonded interactions are expected between the ortho protons of the C₆H₅ groups and H-1, 8 of the phenanthrenoid moiety of 3. ¹⁹F 1D and 2D (COSY) NMR spectra show that the SEL regime also obtains for rotation about the N-C₆F₅ bond of 3, with five separate fluorine signals seen, consistent with a preferred conformation in which the C₆F₅ may lie roughly perpendicular to the plane of the pyrrolidinedione moiety, and may be in the mirror symmetry plane of 3. The results are considered relevant to hindered aryl rotations in numerous Pharmaceuticals. Selected spectral data for 2 and precursors are also presented.     

A remark on a maximal function over a Cantor set of directions

LetM _e ⁰ be the maximal operator over segments of length 1 with directions belonging to a Cantor set. It has been conjectured that this operator is bounded onL ². We consider a sequence of operators over finite sets of directions converging toM _e ⁰ . We improve the previous estimate for the (L ²,L ²)-norm of these particular operators. We also prove thatM _e ⁰ is bounded from some subsets ofL ² toL ². These subsets are composed of positive functions whose Fourier transforms have a very weak decay or are supported in a vertical strip. Partially supported by Spanish DGICYT grant no. PB90-0187.     

Coxeter–Petrie Complexes of Regular Maps

Coxeter–Petrie complexes naturally arise as thin diagram geometries whose rank 3 residues contain all of the dual forms of a regular algebraic map M. Corresponding to an algebraic map is its classical dual, which is obtained simply by interchanging the vertices and faces, as well as its Petrie dual, which comes about by replacing the faces by the so-called Petrie polygons. Jones and Thornton have shown that these involutory duality operations generate the symmetric groupS₃ , giving in all six dual forms, and whose source is the outer automorphism group of the infinite triangle group generated by involutions s₁, s₂, s₃, subject to the additional relation s₁s₃ =  s₃s₁. In fact, this outer automorphism group is parametrized by the permutations of the three commuting involutions s₁,s₃ , s₁s₃. These involutions together with the involutions₂ can be taken to define the nodes of a Coxeter diagram of shape D₄(with the involution s₂at the central node), and when the original map M is regular, there is a natural extension from M to a thin Coxeter complex of rank 4 all of whose rank 3 residues are isomorphic to the various dual forms of M. These are fully explicated in case the original algebraic map is a Platonic map.     

Examination of time-reversal acoustics in shallow water and applications to noncoherent underwater communications

The shallow water acoustic communication channel is characterized by strong signal degradation caused by multipath propagation and high spatial and temporal variability of the channel conditions. At the receiver, multipath propagation causes intersymbol interference and is considered the most important of the channel distortions. This paper examines the application of time-reversal acoustic (TRA) arrays, i.e., phase-conjugated arrays (PCAs), that generate a spatio-temporal focus of acoustic energy at the receiver location, eliminating distortions introduced by channel propagation. This technique is self-adaptive and automatically compensates for environmental effects and array imperfections without the need to explicitly characterize the environment. An attempt is made to characterize the influences of a PCA design on its focusing properties with particular attention given to applications in noncoherent underwater acoustic communication systems. Due to the PCA spatial diversity focusing properties, PC arrays may have an important role in an acoustic local area network. Each array is able to simultaneously transmit different messages that will focus only at the destination receiver node.     

Continuous approximation of linear impulsive systems and a new form of robust stability

The time-scale tolerance for linear ordinary impulsive differential equations is introduced. How large the time-scale tolerance is directly reflects the degree to which the qualitative dynamics of the linear impulsive system can be affected by replacing the impulse effect with a continuous (as opposed to discontinuous, impulsive) perturbation, producing what is known as an impulse extension equation. Theoretical properties related to the existence of the time-scale tolerance are given for periodic systems, as are algorithms to compute them. Some methods are presented for general, aperiodic systems. Additionally, sufficient conditions for the convergence of solutions of impulse extension equations to the solutions of their associated impulsive differential equation are proven. Counterexamples are provided.     

T2-shortening of 3He gas by magnetic microspheres

In a gas-filled material like the lung parenchyma, the transverse relaxation time (T2) for 3He is shortened by the deposition of magnetic microspheres and rapid molecular diffusion through induced field distortions. Here, this unique relaxation process is described theoretically and predicted T2-shortening is validated using pressurized 3He gas in a foam model of alveolar airways. Results demonstrate that: (1) significant T2-shortening is induced by microsphere deposition, (2) shortened 3He T2s are accurately predicted, and (3) measured relaxation times are exploitable for quantifying local deposition patterns. Based on these findings the feasibility of imaging inhaled particulates in vivo with hyperpolarized 3He is examined and performance projections are formulated.     

Mode-locked fiber laser frequency-controlled with an intracavity electro-optic modulator

We demonstrate a mode-locked, erbium-doped fiber laser with its repetition frequency synchronized to a second fiber laser via an intracavity electro-optic modulator (EOM). With servo control from the EOM (bandwidth approximately 230 kHz) and a slower speed intracavity piezoelectric transducer (resonance at approximately 20 kHz), we demonstrate stabilization of the repetition frequency with an in-loop rms timing jitter of 10 fs, integrated over a bandwidth from 1 Hz to 100 kHz. This represents what is to our knowledge the first time an EOM has been introduced inside a mode-locked laser cavity for fast servo action and the lowest timing jitter reported for a mode-locked fiber laser.