Unconventional Secondary Structure Mimics: Ladder-Rungs

Secondary structures tend to be recognizable because they have repeating structural motifs, but mimicry of these does not have to follow such well-defined patterns. Bioinformatics studies to match side-chain orientations of a novel hydantoin triazole chemotype ( 1 ) to protein-protein interfaces revealed it tends to align well across parallel and antiparallel sheets, like rungs on a ladder. One set of these overlays was observed for the protein-protein interaction uPA⋅uPAR. Consequently, chemotype 1 was made with appropriate side-chains to mimic uPA at this interface. Biophysical assays indicate these compounds did in fact bind uPAR, and elicit cellular responses that affected invasion, migration, and wound healing.     

T1Effects in Sequential Dynamic Susceptibility Contrast Experiments

Residual effects of an initial bolus of gadolinium contrast agent have been previously demonstrated in sequential dynamic susceptibility contrast MR experiments. While these residual effects quickly reach a saturation steady state, their etiology is uncertain, and they can lead to spurious estimates of hemodynamic parameters in activation experiments. The possible influence ofT₁effects is now investigated with experiments in whichT₁weighting is varied as well as with serial regionalT₁measurements. Little evidence for significant residualT₁effects is found, suggesting instead that susceptibility effects underlie these observations. An initial saturation dose of contrast agent minimizes this effect.     

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     

Hexaphyrin(1.0.1.0.0.0). A new colorimetric actinide sensor

Hexaphyrin(1.0.1.0.0.0) (isoamethyrin) undergoes a significant color change in the presence of UO₂²⁺, PuO₂²⁺, and NpO₂²⁺. The complexation of the first of these dioxo actinide cations was studied in semi-quantitative fashion in 1:1 MeOH-CH₂Cl₂. Under these conditions, the detection limit for UO₂²⁺ was found to be ca. 5.8 ppm by naked eye monitoring and <28 ppb by UV-vis spectroscopy. Isoamethyrin does not undergo a color change in the presence of most transition metals or when exposed to Gd(III). Isoamethyrin thus constitutes an attractive alternative to 2,2′(1,8-dihydroxy-3,6-disulfonaphthylene-2,7-bisazo)-bisbenzenarsonic acid (AzIII) and 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol (BrPADAP), systems currently used as actinide cation sensors.     

Convective Heat Transfer past Small Cylindrical Bodies

Convective heat transfer from an array of small, cylindrical bodies of arbitrary shape in an unbounded, two-dimensional domain is a singular perturbation problem involving an infinite logarithmic expansion in the small parameter ε, representing the order of magnitude of the size of the bodies. Using the method of matched asymptotic expansions, we formulate a hybrid asymptotic-numerical method to solve for the dimensionless, steady-state temperature. We assume that the velocity field of the fluid surrounding the bodies is arbitrary but known. From our asymptotic solution for an arbitrary velocity field, we present the results for two special cases: a uniform flow field and a simple shear flow field. We demonstrate the asymptotic results of the hybrid method through a number of examples and, in a particular case, we compare these results to an exact analytical solution.     

The Geometry of the Newton Method on Non-Compact Lie Groups

An important class of optimization problems involve minimizing a cost function on a Lie group. In the case where the Lie group is non-compact there is no natural choice of a Riemannian metric and it is not possible to apply recent results on the optimization of functions on Riemannian manifolds. In this paper the invariant structure of a Lie group is exploited to provide a strong interpretation of a Newton iteration on a general Lie group. The paper unifies several previous algorithms proposed in the literature in a single theoretical framework. Local asymptotic quadratic convergence is proved for the algorithms considered.     

On the Representation of Band-Dominant Functions on the Sphere Using Finitely Many Bits

A band-dominant function on the Euclidean sphere embedded in R ^q+1 is the restriction to this sphere of an entire function of q+1 complex variables having a finite exponential type in each of its variables. We develop a method to represent such a function using finitely many bits, using the values of the function at scattered sites on the sphere. The number of bits required in our representation is asymptotically the same as the metric entropy of the class of such functions with respect to any of the L ^p norms on the sphere.