Limits on the transition state geometry for metal insertion into a carbon-hydrogen bond

Using chelating ligands to fix the position of the metal and CH bond, evidence is found which favors a triangular geometry for metal insertion.     

Laser polarization facility

An overview of the laser polarizer facility at ISAC is provided. The charge-exchange cell is described in some detail.     

The chalk drums from Folkton and Lavant: Measuring devices from the time of Stonehenge

Investigating knowledge of mathematics and the use of standard units of measurement in prehistoric societies is a difficult task. For the British Neolithic period (4000–2500 bc), attempts to refine our understanding of mathematical knowledge for this period have been largely unsuccessful until now. Following recent research, we propose that there is a direct link between the design of the monument of Stonehenge and the chalk artefacts known as the Folkton and Lavant Drums, in which the Drums represent measurement standards that were essential for accurate and reproducible monument construction. This has important implications for future analyses of artefacts and monuments for this period.     

Spectroscopy of francium in a magneto optical trap

The francium atom offers an excellent laboratory to study electron-nucleus interactions. As the heaviest alkali, its atomic properties can be calculated with high precision, and laser trapping methods now allow precision optical spectroscopy of many isotopes. Recent measurements of the 7P_1/2 hyperfine structure, when coupled with previous measurements of the ground state hyperfine structure reveal a hyperfine anomaly. The change in anomaly between an even-N isotope and an odd-N isotope is sensitive to the radial distribution of the neutron magnetization. This revised version was published online in August 2006 with corrections to the Cover Date.     

Elongational flow behavior of viscoelastic liquids: Modelling bubble dynamics with viscoelastic constitutive relations

Summary Earlier parts of this series have described a technique based on the collapse of single bubbles in the fluids for studying the elongational rheology of viscoelastic solutions and melts of moderate viscosities ( ₀ > 10²p) at relatively high strain rates . The present paper describes the modelling of bubble collapse with both rate and integral type constitutive relations using a body coordinate system. Predictions of the stress at the bubble wall as a function of time during collapse from a BKZ model and a modified corotational Maxwell model compared favorably with experimental data for two polymer solutions, 1% polyacrylamide in water/glycerine and 2% hydroxypropyl cellulose in water.

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Zusammenfassung In vorangehenden Veröffentlichungen dieser Reihe wurde eine Methode beschrieben, mit Hilfe derer man aus dem Zerfall von einzelnen Blasen in einer Flüssigkeit auf die Dehn-Rheologie viskoelastischer Lösungen und Schmelzen mittlerer Viskosität ( ₀ > 10² P) bei relativ hohen Dehngeschwindigkeiten schließen kann. Die vorliegende Untersuchung beschreibt Modelle des Blasenzerfalls mit Hilfe von Stoffgleichungen sowohl vom rate- als auch vom Integral-Typ, wobei ein körperfestes Koordinatensystem benutzt wird. Die Voraussagen der Spannung an der Blasenwand als Funktion der Zeit während des Zerfalls bei Verwendung eines BKZ- und eines modifizierten korotatorischen Maxwell-Modells zeigen eine recht gute Übereinstimmung mit experimentellen Werten, die an zwei Polymerlösungen, nämlich einer 1%igen Polyacrylamid-Lösung in einer Wasser-Glycerin-Mischung und einer 2%igen wäßrigen Hydropropylcellulose, erhalten worden sind.

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Nomenclature a material constant - b material constant - g metric tensor, space coordinates - m material constant - n material constant - p pressure - P _G pressure within bubble - P _R pressure outside bubble at the wall - P pressure far away from the bubble - R bubble radius - dR/dt - R ₀ initial bubble radius - t time - u velocity - U potential function - Y R/R ₀ Greek symbols covariant body metric tensor - surface tension - rate of deformation matrix, II -second invariant of - strain rate - ₀ zero shear rate viscosity - _e elongational viscosity - _ef effective viscosity - ¹, ², ³ coordinates in body system - ^{1 1}/R ₀ ³ - body stress tensor - density - space stress tensor - relaxation time - _ef effective relaxation time - bubble pressure function, defined in eq. [19] - vorticity tensor With 11 figures and 1 table     

Structural Optimization of Photoswitch Ligands for Surface Attachment of α‐Chymotrypsin and Regulation of Its Surface Binding

A modified gold surface that allows photoregulated binding of α‐chymotrypsin has previously been reported. Here the development of this surface is reported, through the synthesis of a series of trifluoromethyl ketones and α‐keto esters containing the azobenzene group and a surface attachment group as photoswitch inhibitors of α‐chymotrypsin. All of the compounds are inhibitors of the enzyme, with activity that can be modulated by photoisomerization. The best photoswitch shows a reversible change in IC₅₀ inhibition constant of >5.3 times on photoisomerization. The trifluoromethyl ketone 1 exhibited excellent photoswitching and was attached to a gold surface in a two‐step procedure involving an azide–alkyne cycloaddition. The resulting modified surface bound α‐chymotrypsin to a degree that could be modulated by UV/Vis irradiation, showing “slow‐tight” enzyme binding as observed for inhibitors in solution.     

Intramolecular Diels-Alder reactions of ester linked 1,3,9-decatrienes: cis/trans selectivity in thermal and Lewis acid promoted reactions of ethylene-tethered and benzo-tethered systems

High cis (i.e., endo) diastereoselectivities are witnessed in heat-promoted intramolecular Diels-Alder (IMDA) reactions of ethylene-tethered hexadienyl acrylates. The cis stereoselectivity is improved by promotion with Et2AlCl. The first examples of Et2AlCl catalyzed intramolecular Diels-Alder reactions of ester-activated dienophiles are reported. In contrast, the corresponding benzo-tethered hexadienyl acrylates undergo moderately trans (i.e., exo) selective IMDA reactions. Very high trans stereoselection is obtained upon promotion with ATPH. The outcomes of these reactions are essentially insensitive to dienophile (C10) geometry and substitution. DFT (B3LYP/6-31+G(d)) computed cis/trans product distributions-based on Boltzmann transition structure populations-are in good agreement with the experimental results. These computational investigations provide useful insights into the origins of stereoselection in these systems. The stereoselectivity exhibited by the ethylene-tethered hexadienyl acrylates is ascribed to stabilizing secondary orbital interactions at play in the cis-transition structures (TSs). In the benzo-tethered series, this effect is overridden by stabilizing pi-conjugative interactions, between the benzo moiety and the 1,3-diene component, which are stronger in trans TSs, compared to the cis TSs. The computed TS geometries generally exhibit advanced peripheral bond forming asynchronicity, with the tether carbonyl group in conjugation with the dienophile. Such TS features significantly weaken the stereodirecting influence of terminal dienophile substituents.