Synthesis and Study of Olefin Metathesis Catalysts Supported by Redox-Switchable Diaminocarbene 3 Ferrocenophanes

A redox-switchable ligand, N,N'-dimethyldiaminocarbene[3]ferrocenophane (5), was synthesized and incorporated into a series of Ir- and Ru-based complexes. Electrochemical and spectroscopic analyses of (5) Ir(CO)(2)Cl (15) revealed that 5 displayed a Tolman electronic parameter value of 2050 cm(-1) in the neutral state and 2061 cm(-1) upon oxidation. Moreover, inspection of X-ray crystallography data recorded for (5) Ir(cis,cis-1,5-cyclooctadiene)Cl (13) revealed that 5 was sterically less bulky (%V-Bur = 28.4) than other known diaminocarbene[3]ferrocenophanes, which facilitated the synthesis of (5)(PPh3)Cl2Ru-(3-phenylindenylid-1-ene) (18). Complex 18 exhibited quasi-reversible electrochemical processes at 0.79 and 0.98 V relative to SCE, which were assigned to the Fe and Ru centers in the complex, respectively, based on UV-vis and electron pair resonance spectroscopic measurements. Adding 2,3-dichloro-5,6-dicyanoquinone over the course of a ring-opening metathesis polymerization of cis, cis-1,5-cyclooctadiene catalyzed by 18 ([monomer](0)/[18](0) = 2500) reduced the corresponding rate constant of the reaction by over an order of magnitude (pre-oxidation: k(obs) = 0.045 s(-1); post-oxidation: k(obs) = 0.0012 s(-1)). Subsequent reduction of the oxidized species using decamethylferrocene restored catalytic activity (post-reduction: k(obs) = up to 0.016 s(-1), depending on when the reductant was added). The difference in the polymerization rates was attributed to the relative donating ability of the redox-active ligand (i.e., strongly donating 5 versus weakly donating 5(+)) which ultimately governed the activity displayed by the corresponding catalyst.U. S. Army Research Office W911NF-09-1-0446Chemistr

Inversion symmetric 3-monopoles and the Atiyah-Hitchin manifold

We consider 3-monopoles symmetric under inversion symmetry. We show that the moduli space of these monopoles is an Atiyah-Hitchin submanifold of the 3-monopole moduli space. This allows what is known about 2-monopole dynamics to be translated into results about the dynamics of 3-monopoles. Using a numerical ADHMN construction we compute the monopole energy density at various points on two interesting geodesics. The first is a geodesic over the two-dimensional rounded cone submanifold corresponding to right angle scattering and the second is a closed geodesic for three orbiting monopoles.Comment: latex, 22 pages, 2 figures. To appear in Nonlinearit

New hyper-Kaehler manifolds by fixing monopoles

The construction of new hyper-Kaehler manifolds by taking the infinite monopole mass limit of certain Bogomol'nyi-Prasad-Sommerfield monopole moduli spaces is considered. The one-parameter family of hyperkaehler manifolds due to Dancer is shown to be an example of such manifolds. A new family of fixed monopole spaces is constructed. They are the moduli spaces of four SU(4) monopoles, in the infinite mass limit of two of the monopoles. These manifolds are shown to be nonsingular when the fixed monopole positions are distinct.Comment: Version in Phys. Rev. D. 11 pp, RevTeX, 14 Postscript diagram

Chaos in free electron laser oscillators

The chaotic nature of a storage-ring Free Electron Laser (FEL) is investigated. The derivation of a low embedding dimension for the dynamics allows the low-dimensionality of this complex system to be observed, whereas its unpredictability is demonstrated, in some ranges of parameters, by a positive Lyapounov exponent. The route to chaos is then explored by tuning a single control parameter, and a period-doubling cascade is evidenced, as well as intermittence.Comment: Accepted in EPJ

Real-time and Multichannel Measurement of Contractility of hiPSC-Derived 3D Skeletal Muscle using Fiber Optics-Based Sensing

As the field of cardiac and skeletal muscle tissue engineering expands, so does the need for accurate and reliable systems to generate in vitro 3D tissues and analyze their functional properties. In this study, the Cuore is introduced, a system that integrates sensors based on optical fibers and uses the principle of light interferometry to detect the contraction of 3D Tissue Engineered Skeletal Muscles (3D-TESMs). The technology employed in the Cuore allows for reproducible and multichannel force measurements down to a nano-Newtons resolution while maintaining sterility and permitting continuous non-invasive recording within and outside standard tissue culture incubators. Thanks to the integrated electrodes for electrical pulse stimulation (EPS), 3D-TESMs generated from three independent hiPSC-derived myogenic progenitors (MPs) lines are stimulated and the contractility is recorded over the course of a week. Through the modulation of different EPS parameters, the optimal combination to induce the 3D-TESMs in producing fully fused tetani without causing damage is determined. Furthermore, 3D-TESMs from different lines exhibit characteristic signatures of spontaneous contractility and response to caffeine, verapamil, and the β-agonist clenbuterol. The ease of use, high sensitivity, and the integrated electrodes and sensors make the Cuore an ideal technology to investigate the biology of contractile tissues and their response to drugs.</p

Synthesis of Fluorine-18 Functionalized Nanoparticles for use as in vivo Molecular Imaging Agents

Nanoparticles containing fluorine-18 were prepared from block copolymers made by ring opening metathesis polymerization (ROMP). Using the fast initiating ruthenium metathesis catalyst (H_2IMes)(pyr)_2(Cl)_2Ru=CHPh, low polydispersity amphiphilic block copolymers were prepared from a cinnamoyl-containing hydrophobic norbornene monomer and a mesyl-terminated PEG-containing hydrophilic norbornene monomer. Self-assembly into micelles and subsequent cross-linking of the micelle cores by light-activated dimerization of the cinnamoyl groups yielded stable nanoparticles. Incorporation of fluorine-18 was achieved by nucleophilic displacement of the mesylates by the radioactive fluoride ion with 31% incorporation of radioactivity. The resulting positron-emitting nanoparticles are to be used as in vivo molecular imaging agents for use in tumor imaging

Time--delay autosynchronization of the spatio-temporal dynamics in resonant tunneling diodes

The double barrier resonant tunneling diode exhibits complex spatio-temporal patterns including low-dimensional chaos when operated in an active external circuit. We demonstrate how autosynchronization by time--delayed feedback control can be used to select and stabilize specific current density patterns in a noninvasive way. We compare the efficiency of different control schemes involving feedback in either local spatial or global degrees of freedom. The numerically obtained Floquet exponents are explained by analytical results from linear stability analysis.Comment: 10 pages, 16 figure

M-theory on `toric' G_2 cones and its type II reduction

We analyze a class of conical G_2 metrics admitting two commuting isometries, together with a certain one-parameter family of G_2 deformations which preserves these symmetries. Upon using recent results of Calderbank and Pedersen, we write down the explicit G_2 metric for the most general member of this family and extract the IIA reduction of M-theory on such backgrounds, as well as its type IIB dual. By studying the asymptotics of type II fields around the relevant loci, we confirm the interpretation of such backgrounds in terms of localized IIA 6-branes and delocalized IIB 5-branes. In particular, we find explicit, general expressions for the string coupling and R-R/NS-NS forms in the vicinity of these objects. Our solutions contain and generalize the field configurations relevant for certain models considered in recent work of Acharya and Witten.Comment: 45 pages, references adde

Randomizing world trade. II. A weighted network analysis

Based on the misleading expectation that weighted network properties always offer a more complete description than purely topological ones, current economic models of the International Trade Network (ITN) generally aim at explaining local weighted properties, not local binary ones. Here we complement our analysis of the binary projections of the ITN by considering its weighted representations. We show that, unlike the binary case, all possible weighted representations of the ITN (directed/undirected, aggregated/disaggregated) cannot be traced back to local country-specific properties, which are therefore of limited informativeness. Our two papers show that traditional macroeconomic approaches systematically fail to capture the key properties of the ITN. In the binary case, they do not focus on the degree sequence and hence cannot characterize or replicate higher-order properties. In the weighted case, they generally focus on the strength sequence, but the knowledge of the latter is not enough in order to understand or reproduce indirect effects.Comment: See also the companion paper (Part I): arXiv:1103.1243 [physics.soc-ph], published as Phys. Rev. E 84, 046117 (2011