Design and Synthesis of Nonequilibrium Systems

The active transport of ions and molecules across cell membranes is essential to creating the concentration gradients that sustain life in all living organisms, be they bacteria, fungi, plants, animals or Homo sapiens. Nature uses active transport everywhere for everything. Molecular biologists have long been attracted to the study of active transport and continue to this day to investigate and elucidate the tertiary structures of the complex motor proteins that sustain it, while physicists, interested in nonequilibrium statistical mechanics, have developed theoretical models to describe the driven ratcheting motions that are crucial to its function. The increasingly detailed understanding that contemporary science has acquired relating to active transport, however, has yet to lead to the design and construction of artificial molecular motors capable of employing ratchet-driven motions that can also perform work against concentration gradients. Mechanically interlocked molecules (MIMs) in the form of pseudo- and semirotaxanes are showing some encouraging signs in meeting these goals. This review summarizes recent progress in making artificial molecular motors that can perform work by “pumping” tetracationic rings into high-energy states. The launching pad is a bistable [2]rotaxane whose dumbbell component contains two electron-donating recognition sites, one, a tetrathiafulvalene (TTF) unit, which interacts more strongly with the ring component, cyclobis(paraquat-p-phenylene) (CBPQT4+), containing two electron-accepting bipyridinium units, than does the other 1,5-dioxynaphthalene (DNP) unit. Switching can be induced electrochemically by oxidizing the TTF unit to a TTF•+ radical cation, whereupon Coulombic repulsion takes care of moving the ring to the DNP unit. Reduction of the radical cation resets the switch. Molecular switches operate at, or close to, equilibrium. Any work done during one switching event is undone during the reset. Molecular motors, on the other hand, rely on a flux of energy, and a ratchet mechanism to make periodic changes to the potential energy surface of a system in order to move molecules uphill to higher energy states. Forging a path from molecular switches to motors involved designing a molecular pump prototype. An asymmetric dumbbell with a 2-isopropylphenyl (neutral) end and a 3,5-dimethylpyridinium (charged) end with a DNP recognition site to entice CBPQT4+ rings out of solution exhibits relative unidirectional movement of the rings with respect to the dumbbell. Redox chemistry does the trick. During the oxidative cycle, the rings enter the dumbbell by passing over the neutral end onto the recognition site; in the reduction cycle, much of the recognition is lost and the rings find their way back into solution by leaving the dumbbell from the charged end. This on-one-end, off-the-other process can be repeated over and over again using light as the energy source in the presence of a photosensitizer and a compound that shuttles electrons back and forth. Although this prototype demonstrates ratchet-driven translational motion, no work is done. A ring enters the dumbbell from one end and leaves from the other end. Another deficiency of the prototype is the fact that, although the recognition site is muted on reduction, it retains some attraction for the ring. What if the recognition site was attractive initially and then became repulsive? This question was answered by turning to radical chemistry and employing the known stabilization behavior of a bipyridinium radical cation and the bisradical dication, generated on reduction of the CBPQT4+ ring, to pluck rings out of solution and thread them over the charged end of the pump portion of a semidumbbell. On subsequent oxidation, the pump is primed and the rings pass through a one-way door, given a little thermal energy, onto a collecting-chain where they find themselves accumulating where they would rather not be present. In this manner, an artificial molecular pump mimics the pumping machinery commonplace in biological systems. Looking beyond this state-of-the-art artificial molecular pump, we discuss, from a theoretical standpoint, the measures that would need to be taken in order to render its operation autonomous

Hadronic B decays in the MSSM with large tan(beta)

We present an analysis of non-leptonic B decays in the minimally flavour-violating MSSM with large tan(beta). We relate the Wilson coefficients of the relevant hadronic scalar operators to leptonic observables, showing that the present limits on the Bs->mu+ mu- and B+->tau nu_tau branching fractions exclude any visible effect in hadronic decays. We study the transverse helicity amplitudes of B->VV decays, which exhibit an enhanced sensitivity to the scalar operators, showing that even though an order one modification relative to the SM is not excluded in some of these amplitudes, they are too small to be detected at B factories.Comment: 16 pages, 2 figure

Flavor symmetry breaking and scaling for improved staggered actions in quenched QCD

We present a study of the flavor symmetry breaking in the pion spectrum for various improved staggered fermion actions. To study the effects of link fattening and tadpole improvement, we use three different variants of the p4 action - p4fat3, p4fat7, and p4fat7tad. These are compared to Asqtad and also to naive staggered. To study the pattern of symmetry breaking, we measure all 15 meson masses in the 4-flavor staggered theory. The measurements are done on a quenched gauge background, generated using a one-loop improved Symanzik action with $\beta=10/g^2 = 7.40, 7.75,$ and 8.00, corresponding to lattice spacings of approximately a = .31 fm., .21 fm., and .14 fm. We also study how the lattice scale set by the $\rho$ mass on each of these ensembles compares to one set by the static quark potential.Comment: 18 pages, 6 figure

Phenolic Compound Profiles in Grape Skins of Cabernet Sauvignon, Merlot, Syrah and Marselan Cultivated in the Shacheng Area (China)

The phenolic compounds in the grape skins of Cabernet Sauvignon (CS), Merlot (ML), Syrah (SY) and Marselan (MS) from Shacheng, in China, were compared using HPLC-MS/MS. The results showed that the types and levels of phenolic compounds varied greatly with cultivars. Malvidin derivatives were the main anthocyanins. CS and ML showed a higher content of malvidin-3-O-(6-O-acetyl)-glucoside than malvidin-3-O-(trans-6-O- coumaryl)-glucoside, while SY and MS differed from CS and ML. ML had higher delphinidin and cyanidin derivatives, SY had higher peonidin derivatives, while malvidin and petunidin were higher in MS. The total content of flavonols, flavan-3-ols, phenolic acids and stilbenes in grape skins showed no difference among CS, ML and MS. Isorhamnetin-3-O-glucoside (CS, ML, MY), quercetin-3O-glucoside (SY), procyanidin trimer (SY, MS), procyanidin dimer (CS, ML), syringetin-3-O-glucoside, trans-cinnamic acid and resveratrol were the most abundant non-anthocyanin phenolic compounds. Cluster analysis showed that CS and ML, and SY and MS had similar phenolic profiles

New Physics and CP Violation in Hyperon Nonleptonic Decays

The sum of the CP-violating asymmetries A(Lambda_-^0) and A(Xi_-^-) in hyperon nonleptonic decays is presently being measured by the E871 experiment. We evaluate contributions to the asymmetries induced by chromomagnetic-penguin operators, whose coefficients can be enhanced in certain models of new physics. Incorporating recent information on the strong phases in Xi->Lambda pi decay, we show that new-physics contributions to the two asymmetries can be comparable. We explore how the upcoming results of E871 may constrain the coefficients of the operators. We find that its preliminary measurement is already better than the epsilon parameter of K-Kbar mixing in bounding the parity-conserving contributions.Comment: 12 pages, 2 figure

Final State Rescattering and Color-suppressed \bar B^0-> D^{(*)0} h^0 Decays

The color-suppressed \bar B^0-> D^{(*)0}\pi^0, D^{(*)0}\eta, D^0\omega decay modes have just been observed for the first time. The rates are all larger than expected, hinting at the presence of final state interactions. Considering \bar B^0-> D^{(*)0}\pi^0 mode alone, an elastic D^{(*)}\pi -> D^{(*)}\pi rescattering phase difference \delta \equiv \delta_{1/2} - \delta_{3/2} \sim 30^\circ would suffice, but the \bar B^0-> D^{(*)0}\eta, D^0\omega modes compel one to extend the elastic formalism to SU(3) symmetry. We find that a universal a_2/a_1=0.25 and two strong phase differences 20^\circ \sim \theta < \delta < \delta^\prime \sim 50^\circ can describe both DP and D^*P modes rather well; the large phase of order 50^\circ is needed to account for the strength of {\it both} the D^{(*)0}\pi^0 and D^{(*)0}\eta modes. For DV modes, the nonet symmetry reduces the number of physical phases to just one, giving better predictive power. Two solutions are found. We predict the rates of the \bar B^0-> D^{+}_s K^-, D^{*+}_s K^-, D^0\rho^0, D^+_s K^{*-} and D^0\phi modes, as well as \bar B^0-> D^{0}\bar K^0, D^{*0}\bar K^0, D^{0}\bar K^{*0} modes. The formalism may have implications for rates and CP asymmetries of charmless modes.Comment: REVTeX4, 18 pages, 5 figures, to appear in Phys. Rev.

Vector and Scalar Meson Resonances in K→πππK\rightarrow\pi\pi\pi Decays

Corrections to $K\rightarrow\pi\pi\pi$ induced by vector and scalar meson exchange are investigated within chiral perturbation theory.Comment: 15pages, Latex-file, TUM-T31-41/9