Nuclear magnetic resonance spectroscopy of rat ventricles following chronic hypoxia: A model of right ventricular hypertrophy

Nuclear magnetic resonance spectroscopy was used to study the effect of chronic hypoxia on both right (RV) and left ventricular and septal (LV + S) muscle. Rats in the hypoxic group, kept in a hypobaric chamber at $\text{1}\text{2}$ atm pressure for 2 weeks, developed right, but not left, ventricular hypertrophy (p < 0.001). Tissues were studied within 2.5 h of return to air. T₁ and T₂ relaxation times of RV, LV + S and thigh muscle (Th) from hypoxic and control rats were compared. The T₂ value distinguished hypoxic from control RV (p < 0.002), but not hypoxic from control LV + S or Th, indicating that the change in relaxation time reflects cellular hypertrophy, and not hypoxemia. For hypoxic rats only the T₂ value distinguished each muscle type: RV from LV + S (p < 0.009), RV from Th (p < 0.001) and LV + S from Th (p < 0001). The T₁ value did not identify either the hypoxic or control group or the type of muscle. Percent water content was similar for all tissues. For hypoxic RV, T₂ correlated with the percent water content (r = 0.89; p < 0.01). The sensitivity of T₂ to the cellular changes associated with hypoxic RV hypertrophy could provide a means of detecting right ventricular hypertrophy.     

Liquid-crystalline cyclic trimers derived from benzene-1,3,5-tricarboxylic acid

A new class of structurally complex materials whose constituent molecules are composed of three rod-like units, each attached to a central disc-like unit via a flexible spacer have been synthesized and their phase behaviour investigated. They are found to exhibit a rich and unusual liquid-crystalline polymorphism.     

Stereocontrolled Assembly of Cis or Trans Angularly Substituted Hydrindenes by the Unactivated Intramolecular Diels-Alder Reaction

The unactivated intramolecular Diels-Alder reaction has become a powerful tool for the construction of polycyclic natural products. Nevertheless, the factors that govern diastereoselectivity in these cyclizations have not been fully understood. We here report that through the choice of the proper substituents, it is possible to make the unactivated intramolecular Diels-Alder reaction proceed to give either the cis angularly-substituted hydrindene 12b or the trans product 19a.     

Intramolecular hydrophosphination/cyclization of phosphinoalkenes and phosphinoalkynes catalyzed by organolanthanides: scope, selectivity, and mechanism

Organolanthanide complexes of the general type Cp'(2)LnE(TMS)(2) (Cp' = eta(5)-Me(5)C(5); Ln = La, Sm, Y, Lu; E = CH, N; TMS = SiMe(3)) serve as effective precatalysts for the rapid intramolecular hydrophosphination/cyclization of the phosphinoalkenes and phosphinoalkynes RHP(CH(2))(n)()CH=CH(2) (R = Ph, H; n = 3, 4) and H(2)P(CH(2))(n)C triple bond C-Ph (n = 3, 4) to afford the corresponding heterocycles and respectively. Kinetic and mechanistic data for these processes exhibit parallels to, as well as distinct differences from, organolanthanide-mediated intramolecular hydroamination/cyclizations. The turnover-limiting step of the present catalytic cycle is insertion of the carbon-carbon unsaturation into the Ln-P bond, followed by rapid protonolysis of the resulting Ln-C linkage. The rate law is first-order in [catalyst] and zero-order in [substrate] over approximately one half-life, with inhibition by heterocyclic product intruding at higher conversions. The catalyst resting state is likely a lanthanocene phosphine-phosphido complex, and dimeric [Cp'(2)YP(H)Ph](2) was isolated and cystallographically characterized. Lanthanide identity and ancillary ligand structure effects on rate and selectivity vary with substrate unsaturation: larger metal ions and more open ligand systems lead to higher turnover frequencies for phosphinoalkynes, and intermediate-sized metal ions with Cp'(2) ligands lead to maximum turnover frequencies for phosphinoalkenes. Diastereoselectivity patterns also vary with substrate, lanthanide ion, and ancillary ligands. Similarities and differences in hydrophosphination vis-à-vis analogous organolanthanide-mediated hydroamination are enumerated.     

Cyclopentane construction by Rh-catalyzed intramolecular C-h insertion: relative reactivity of a range of catalysts

The preparation and Rh-mediated cyclization of the alpha-diazoester 1 are outlined, and its utility in determining the elements that contribute to the reactivity of the intermediate Rh-carbenoid is presented. The rate of disappearance of diazo ester 1 catalyzed by several representative Rh(II) complexes was determined. The observed relative rate constants for the reaction of the Rh(II) complexes with 1 varied over a range of >10(7). The reactivity of the Rh-carbenoid intermediate was explored using the ratio of the sum of (3 + 4 + 5) to 2 (cyclization vs elimination), the ratio of 3 to the sum of (4 + 5) (chemoselectivity), and the ratio of 4 to 5 (diastereoselectivity). It is striking that these four measures of reactivity were found to be independent of each other.     

Synthesis of the enediol isofurans, endogenous oxidation products of arachidonic acid

Isofurans (IsoF's) are a new class of human arachidonic acid oxidation products. They are produced in vivo by a free radical mechanism, independent of the cyclooxygenase enzymes. These new compounds are available from natural sources only in microgram quantities as mixtures. The enantioselective preparation of two enediol isofurans, 15-epi-ent-SC-Delta13-8-IsoF and ent-SC-Delta13-8-IsoF, is described. A key transformation in the synthesis is the selective cascade cyclization of a diol epoxide benzenesulfonate to give the substituted tetrahydrofuran skeleton of the isofurans. This synthesis will make these metabolites available for physiological evaluation.     

Triangle,Parallelogram, and Trapezoid Orders

In his 1998 paper, Ryan classified the sets of unit, proper, and plain trapezoid and parallelogram orders. We extend this classification to include unit, proper, and plain triangle orders. We prove that there are 20 combinations of these properties that give rise to distinct classes of ordered sets, and order these classes by containment.     

Improved peak capacity for CE separations of enzyme inhibitors with activity‐based detection using magnetic bead microreactors

A technique for separating and detecting enzyme inhibitors was developed using CE with an enzyme microreactor. The on‐column enzyme microreactor was constructed using NdFeB magnet(s) to immobilize alkaline phosphatase‐coated superparamagnetic beads (2.8 μm diameter) inside a capillary before the detection window. Enzyme inhibition assays were performed by injecting a plug of inhibitor into a capillary filled with the substrate, AttoPhos. Product generated in the enzyme microreactor was detected by LIF. Inhibitor zones electrophoresed through the capillary, passed through the enzyme microreactor, and were observed as negative peaks due to decreased product formation. The goal of this study was to improve peak capacities for inhibitor separations relative to previous studies, which combined continuous engagement electrophoretically mediated microanalysis and transient engagement electrophoretically mediated microanalysis to study enzyme inhibition. The effects of electric field strength, bead injection time and inhibitor concentrations on peak capacity and peak width were investigated. Peak capacities were increased to ≥20 under optimal conditions of electric field strength and bead injection time for inhibition assays with arsenate and theophylline. Five reversible inhibitors of alkaline phosphatase (theophylline, vanadate, arsenate, L ‐tryptophan and tungstate) were separated and detected to demonstrate the ability of this technique to analyze complex inhibitor mixtures.