Building block libraries and structural considerations in the self-assembly of polyoxometalate and polyoxothiometalate systems

Inorganic metal-oxide clusters form a class of compounds that are unique in their topological and electronic versatility and are becoming increasingly more important in a variety of applications. Namely, Polyoxometalates (POMs) have shown an unmatched range of physical properties and the ability to form structures that can bridge several length scales. The formation of these molecular clusters is often ambiguous and is governed by self-assembly processes that limit our ability to rationally design such molecules. However, recent years have shown that by considering new building block principles the design and discovery of novel complex clusters is aiding our understanding of this process. Now with current progress in thiometalate chemistry, specifically polyoxothiometalates (POTM), the field of inorganic molecular clusters has further diversified allowing for the targeted development of molecules with specific functionality. This chapter discusses the main differences between POM and POTM systems and how this affects synthetic methodologies and reactivities. We will illustrate how careful structural considerations can lead to the generation of novel building blocks and further deepen our understanding of complex systems

Interface mediated interactions between particles -- a geometrical approach

Particles bound to an interface interact because they deform its shape. The stresses that result are fully encoded in the geometry and described by a divergence-free surface stress tensor. This stress tensor can be used to express the force on a particle as a line integral along any conveniently chosen closed contour that surrounds the particle. The resulting expression is exact (i.e., free of any "smallness" assumptions) and independent of the chosen surface parametrization. Additional surface degrees of freedom, such as vector fields describing lipid tilt, are readily included in this formalism. As an illustration, we derive the exact force for several important surface Hamiltonians in various symmetric two-particle configurations in terms of the midplane geometry; its sign is evident in certain interesting limits. Specializing to the linear regime, where the shape can be analytically determined, these general expressions yield force-distance relations, several of which have originally been derived by using an energy based approach.Comment: 18 pages, 7 figures, REVTeX4 style; final version, as appeared in Phys. Rev. E. Compared to v2 several minor mistakes, as well as one important minus sign in Eqn. (18a) have been cured. Compared to v1, this version is significantly extended: Lipid tilt degrees of freedom for membranes are included in the stress framework, more technical details are given, estimates for the magnitude of forces are mad

Prospects in the orbital and rotational dynamics of the Moon with the advent of sub-centimeter lunar laser ranging

Lunar Laser Ranging (LLR) measurements are crucial for advanced exploration of the laws of fundamental gravitational physics and geophysics. Current LLR technology allows us to measure distances to the Moon with a precision approaching 1 millimeter. As NASA pursues the vision of taking humans back to the Moon, new, more precise laser ranging applications will be demanded, including continuous tracking from more sites on Earth, placing new CCR arrays on the Moon, and possibly installing other devices such as transponders, etc. Successful achievement of this goal strongly demands further significant improvement of the theoretical model of the orbital and rotational dynamics of the Earth-Moon system. This model should inevitably be based on the theory of general relativity, fully incorporate the relevant geophysical processes, lunar librations, tides, and should rely upon the most recent standards and recommendations of the IAU for data analysis. This paper discusses methods and problems in developing such a mathematical model. The model will take into account all the classical and relativistic effects in the orbital and rotational motion of the Moon and Earth at the sub-centimeter level. The new model will allow us to navigate a spacecraft precisely to a location on the Moon. It will also greatly improve our understanding of the structure of the lunar interior and the nature of the physical interaction at the core-mantle interface layer. The new theory and upcoming millimeter LLR will give us the means to perform one of the most precise fundamental tests of general relativity in the solar system.Comment: 26 pages, submitted to Proc. of ASTROCON-IV conference (Princeton Univ., NJ, 2007

Densities and filling factors of the DIG in the Solar neighbourhood

For the first time we have combined dispersion measures and emission measures towards 38 pulsars at KNOWN distances from which we derived the mean electron density in clouds, N_c, and their volume filling factor, F_v, averaged along the line of sight. The emission measures were corrected for absorption by dust and contributions from beyond the pulsar distance. Results: The scale height of the electron layer for our sample is 0.93+/-0.13 kpc and the midplane electron density is 0.023+/-0.004 cm^-3, in agreement with earlier results. The average density along the line of sight is = 0.018+/-0.002 cm^-3 and nearly constant. Since = F_v N_c, an inverse relationship between F_v and N_c is expected. We find F_v(N_c) = (0.011+/-0.003) N_c^{-1.20+/-0.13}, which holds for the ranges N_c = 0.05-1 cm^-3 and F_v = 0.4-0.01. Near the Galactic plane the dependence of F_v on N_c is significantly stronger than away from the plane. F_v does not systematically change along or perpendicular to the Galactic plane, but the spread about the mean value of 0.08+/-0.02 is considerable. Conclusions: The inverse F_v-N_c relation is consistent with a hierarchical, fractal density distribution in the diffuse ionized gas (DIG) caused by turbulence. The observed near constancy of then is a signature of fractal structure in the ionized medium, which is most pronounced outside the thin disk.Comment: 9 pages, 9 figures. Accepted for publication in A&

Crossover between Thermally Assisted and Pure Quantum Tunneling in Molecular Magnet Mn12-Acetate

The crossover between thermally assisted and pure quantum tunneling has been studied in single crystals of high spin (S=10) uniaxial molecular magnet Mn12 using micro-Hall-effect magnetometry. Magnetic hysteresis and relaxation experiments have been used to investigate the energy levels that determine the magnetization reversal as a function of magnetic field and temperature. These experiments demonstrate that the crossover occurs in a narrow (0.1 K) or broad (1 K) temperature interval depending on the magnitude of the field transverse to the anisotropy axis.Comment: 5 pages, 4 figure

Bacterial porin disrupts mitochondrial membrane potential and sensitizes host cells to apoptosis

The bacterial PorB porin, an ATP-binding beta-barrel protein of pathogenic Neisseria gonorrhoeae, triggers host cell apoptosis by an unknown mechanism. PorB is targeted to and imported by host cell mitochondria, causing the breakdown of the mitochondrial membrane potential (delta psi m). Here, we show that PorB induces the condensation of the mitochondrial matrix and the loss of cristae structures, sensitizing cells to the induction of apoptosis via signaling pathways activated by BH3-only proteins. PorB is imported into mitochondria through the general translocase TOM but, unexpectedly, is not recognized by the SAM sorting machinery, usually required for the assembly of beta-barrel proteins in the mitochondrial outer membrane. PorB integrates into the mitochondrial inner membrane, leading to the breakdown of delta psi m. The PorB channel is regulated by nucleotides and an isogenic PorB mutant defective in ATP-binding failed to induce delta psi m loss and apoptosis, demonstrating that dissipation of delta psi m is a requirement for cell death caused by neisserial infection

Superspreading: Mechanisms and Molecular Design

The intriguing ability of certain surfactant molecules to drive the superspreading of liquids to complete wetting on hydrophobic substrates is central to numerous applications that range from coating flow technology to enhanced oil recovery. Despite significant experimental efforts, the precise mechanisms underlying superspreading remain unknown to date. Here, we isolate these mechanisms by analyzing coarse-grained molecular dynamics simulations of surfactant molecules of varying molecular architecture and substrate affinity. We observe that for superspreading to occur, two key conditions must be simultaneously satisfied: the adsorption of surfactants from the liquid–vapor surface onto the three-phase contact line augmented by local bilayer formation. Crucially, this must be coordinated with the rapid replenishment of liquid–vapor and solid–liquid interfaces with surfactants from the interior of the droplet. This article also highlights and explores the differences between superspreading and conventional surfactants, paving the way for the design of molecular architectures tailored specifically for applications that rely on the control of wetting

Genetic noise control via protein oligomerization

Gene expression in a cell entails random reaction events occurring over disparate time scales. Thus, molecular noise that often results in phenotypic and population-dynamic consequences sets a fundamental limit to biochemical signaling. While there have been numerous studies correlating the architecture of cellular reaction networks with noise tolerance, only a limited effort has been made to understand the dynamic role of protein-protein interactions. Here we have developed a fully stochastic model for the positive feedback control of a single gene, as well as a pair of genes (toggle switch), integrating quantitative results from previous in vivo and in vitro studies. We find that the overall noise-level is reduced and the frequency content of the noise is dramatically shifted to the physiologically irrelevant high-frequency regime in the presence of protein dimerization. This is independent of the choice of monomer or dimer as transcription factor and persists throughout the multiple model topologies considered. For the toggle switch, we additionally find that the presence of a protein dimer, either homodimer or heterodimer, may significantly reduce its random switching rate. Hence, the dimer promotes the robust function of bistable switches by preventing the uninduced (induced) state from randomly being induced (uninduced). The specific binding between regulatory proteins provides a buffer that may prevent the propagation of fluctuations in genetic activity. The capacity of the buffer is a non-monotonic function of association-dissociation rates. Since the protein oligomerization per se does not require extra protein components to be expressed, it provides a basis for the rapid control of intrinsic or extrinsic noise

Compact symmetric objects and supermassive binary black holes in the VLBA Imaging and Polarimetry Survey

We present multifrequency Very Long Baseline Array (VLBA) follow-up observations of VLBA Imaging and Polarimetry Survey sources identified as likely compact symmetric objects (CSOs) or supermassive binary black holes (SBBHs). We also present new spectroscopic redshifts for 11 sources observed with the Hobby-Eberly Telescope. While no new SBBHs can be confirmed from these observations, we have identified 24 CSOs in the sample, 15 of which are newly designated, and refuted 52 candidates leaving 33 unconfirmed candidates. This is the first large uniform sample of CSOs which can be used to elicit some of the general properties of these sources, including morphological evolution and environmental interaction. We have detected polarized emission from two of these CSOs the properties of which are consistent with active galactic nuclei unification schemes

Infrared optical properties of Pr2CuO4

The ab-plane reflectance of a Pr2CuO4 single crystal has been measured over a wide frequency range at a variety of temperatures, and the optical properties determined from a Kramers-Kronig analysis. Above ~ 250 K, the low frequency conductivity increases quickly with temperature; the resistivity follows the form e^(E_a/k_BT), where E_a ~ 0.17 eV is much less than the inferred optical gap of ~ 1.2 eV. Transport measurements show that at low temperature the resistivity deviates from activated behavior and follows the form e^[(T_0/T)^1/4], indicating that the dc transport in this material is due to variable-range hopping between localized states in the gap. The four infrared-active Eu modes dominate the infrared optical properties. Below ~ 200 K, a striking new feature appears near the low-frequency Eu mode, and there is additional new fine structure at high frequency. A normal coordinate analysis has been performed and the detailed nature of the zone-center vibrations determined. Only the low-frequency Eu mode has a significant Pr-Cu interaction. Several possible mechanisms related to the antiferromagnetism in this material are proposed to explain the sudden appearance of this and other new spectral features at low temperature.Comment: 11 pages, 7 embedded EPS figures, REVTeX