Oxygen isotope effects on electron transfer to O2 probed using chemically modified flavins bound to glucose oxidase

Apo-glucose oxidase has been reconstituted with flavins modified in the 7 and 8 positions and characterized with regard to the catalytic rate of O(2) reduction and oxygen-18 isotope effects on this process. Kinetic studies as a function of driving force indicate a reorganization energy for electron transfer to O(2) of lambda = 28 kcal mol(-)(1) at optimal pH, which is similar to the value obtained earlier from temperature dependencies of rates (Roth, J. P.; Klinman, J. P. Proc. Natl. Acad. Sci. U.S.A. 2003, 100, 62-67). For the various enzyme-bound flavins, competitive oxygen-18 kinetic isotope effects fall within the narrow range of 1.0266(5) to 1.0279(6), apparently because of the dominant contribution of outer-sphere reorganization to the activation barrier; within the context of semiclassical and quantum mechanical electron transfer theories, the magnitude of the isotope effects reveals the importance of nuclear tunneling.     

Photophysical properties of glucoconjugated chlorins and porphyrins and their associations with cyclodextrins

Glucoconjugated analogues of the meta-hydroxyphenyl porphyrin (m-THPP) and meta-hydroxyphenyl chlorin (m-THPC) has been recently synthesized. The characteristics of their triplet states have been determined with regard to their involvement in the photodynamic (PDT) efficiency. In the case of porphyrin derivatives, triplet quantum yields (Phi(T)) were ranging from 0.42 to 0.55 and triplet life times (tau(T)) from 1 to 5 micros. High reaction rate constants (k(q)) with molecular oxygen (k(q): 1.2-1.6 x 10(9)s(-1)) have been found. The triplet lifetimes of chlorin derivatives were about four times higher than those of porphyrins whereas the Phi(T) and k(q) values remained quite similar. Singlet oxygen yields of glucosylated and non-glucosylated porphyrins and chlorins were not significantly different within experimental errors (Phi(Delta)((1)O(2)): 0.41-0.58). Furthermore, it has been shown that glucoconjugated photosensitizers could undergo associations with the methyl-beta-cyclodextrin (Me-beta-CD) which exhibit high triplet lifetimes and singlet oxygen yields ranging from 0.27 to 0.48.     

From Canards of Folded Singularities to Torus Canards in a Forced van der Pol Equation

In this article, we study canard solutions of the forced van der Pol equation in the relaxation limit for low-, intermediate-, and high-frequency periodic forcing. A central numerical observation made herein is that there are two branches of canards in parameter space which extend across all positive forcing frequencies. In the low-frequency forcing regime, we demonstrate the existence of primary maximal canards induced by folded saddle nodes of type I and establish explicit formulas for the parameter values at which the primary maximal canards and their folds exist. Then, we turn to the intermediate- and high-frequency forcing regimes and show that the forced van der Pol possesses torus canards instead. These torus canards consist of long segments near families of attracting and repelling limit cycles of the fast system, in alternation. We also derive explicit formulas for the parameter values at which the maximal torus canards and their folds exist. Primary maximal canards and maximal torus canards correspond geometrically to the situation in which the persistent manifolds near the family of attracting limit cycles coincide to all orders with the persistent manifolds that lie near the family of repelling limit cycles. The formulas derived for the folds of maximal canards in all three frequency regimes turn out to be representations of a single formula in the appropriate parameter regimes, and this unification confirms the central numerical observation that the folds of the maximal canards created in the low-frequency regime continue directly into the folds of the maximal torus canards that exist in the intermediate- and high-frequency regimes. In addition, we study the secondary canards induced by the folded singularities in the low-frequency regime and find that the fold curves of the secondary canards turn around in the intermediate-frequency regime, instead of continuing into the high-frequency regime. Also, we identify the mechanism responsible for this turning. Finally, we show that the forced van der Pol equation is a normal form-type equation for a class of single-frequency periodically driven slow/fast systems with two fast variables and one slow variable which possess a non-degenerate fold of limit cycles. The analytic techniques used herein rely on geometric desingularisation, invariant manifold theory, Melnikov theory, and normal form methods. The numerical methods used herein were developed in Desroches et al. (SIAM J Appl Dyn Syst 7:1131–1162, 2008, Nonlinearity 23:739–765 2010).     

Sigmatropic Rearrangement of Vinyl Aziridines: Expedient Synthesis of Cyclic Sulfoximines from Chiral Sulfinimines

A novel rearrangement of 2‐vinyl aziridine 2‐carboxylates to unusual chiral cyclic sulfoximines is described herein. The method allows the synthesis of substituted cyclic sulfoximines in high yields with complete stereocontrol, and tolerates a wide substrate scope. A one‐pot process starting directly from sulfinimines provides access to complex chiral sulfoximines in only two steps from commercially available aldehydes. A mechanistic hypothesis and synthetic application in the formal synthesis of trachelanthamidine, by transformation of a cyclic sulfoximine into a pyrroline, is also disclosed.     

DNA‐Templated [2+2] Photocycloaddition: A Straightforward Entry into the Aplysinopsin Family of Natural Products

Biosynthetic considerations inspired us to harness the templating properties offered by DNA to promote a [2+2] photoinduced cycloaddition. The method was developed based on the dimerization of (E)‐aplysinopsin, which was previously shown to be unproductive in solution. In sharp contrast, exposure of this tryptophan‐derived olefin to light in the presence of salmon testes DNA (st‐DNA) reproducibly afforded the corresponding homo‐dimerized spiro‐fused cyclobutane in excellent yields. DNA provides unique templating interactions enabling a singular mimic of the solid‐state aggregation necessary for the [2+2] photocycloaddition to occur. This method was ultimately used to promote the prerequisite dimerizations leading to both dictazole B and tubastrindole B, thus constituting the first example of a DNA‐mediated transformation to be applied to the total synthesis of a natural product.     

Room‐Temperature,Strain‐Tunable Orientation of Magnetization in a Hybrid Ferromagnetic Co Nanorod–Liquid Crystalline Elastomer Nanocomposite

Hybrid nanocomposites based on magnetic nanoparticles dispersed in liquid crystalline elastomers are fascinating emerging materials. Their expected strong magneto‐elastic coupling may open new applications as actuators, magnetic switches, and for reversible storage of magnetic information. We report here the synthesis of a novel hybrid ferromagnetic liquid crystalline elastomer. In this material, highly anisotropic Co nanorods are aligned through a cross‐linking process performed in the presence of an external magnetic field. We obtain a highly anisotropic magnetic material which exhibits remarkable magneto‐elastic coupling. The nanorod alignment can be switched at will at room temperature by weak mechanical stress, leading to a change of more than 50 % of the remnant magnetization ratio and of the coercive field.     

New three- and four-armed flexible bridging ligands for use in metallosupramolecular chemistry: syntheses and X-ray structures

Preparations are described of twelve new tritopic and tetratopic ligands by coupling of two phenolic precursors with a range of heterocyclic units. X-ray crystal structures of four representative examples revealed the conformations in the solid state with the nitrogen donor atoms separated by distances ranging from 10.9 to 18.2 Å.