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.     

Near-Ultraviolet Circular Dichroism and Two-Dimensional Spectroscopy of Polypeptides

A fully quantitative theory of the relationship between protein conformation and optical spectroscopy would facilitate deeper insights into biophysical and simulation studies of protein dynamics and folding. In contrast to intense bands in the far-ultraviolet, near-UV bands are much weaker and have been challenging to compute theoretically. We report some advances in the accuracy of calculations in the near-UV, which were realised through the consideration of the vibrational structure of the electronic transitions of aromatic side chains.     

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.     

Inverse Problem for a Mathematical Model of Adsorption Dynamics

A mixed problem is considered for a system of partial differential equations modeling the process of adsorption dynamics. An existence and uniqueness theorem is proved for this problem, and the solution properties are investigated. The inverse problem is posed, involving the determination of the system coefficient given additional information about the solution. A uniqueness theorem is proved for the solution of the inverse problem.__________Translated from Prikladnaya Matematika i Informatika, No. 16, pp. 5 – 14, 2004.     

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.     

Experimental investigation and theoretical modeling of liquid entrainment in a horizontal tee with a vertical-up branch

This article describes a comprehensive literature review of liquid entrainment in horizontal pipes with vertical-up branches. Deficiencies in the available data and correlations were identified. The Air–water Test Loop for Advanced Thermal–hydraulic Studies (ATLATS) was constructed and entrainment onset and steady-state data were collected for a wide range of flow conditions. Using new insights gained from experimental testing, the authors developed a model for predicting the onset of entrainment and steady-state entrainment rate. Previously published correlations, along with the new model, are compared against all available data. The new model shows very good agreement with the onset data, but is not very good at predicting branch quality at high liquid flow rates.