Selective removal of ortho halogens by a diorganolanthanoid

Reaction of halogenobenzoic acids with bis(pentafluorophenyl)ytterbium(II) in tetrahydrofuran results in selective removal of $\text{ortho}$ halogen substituents.     

Improved Molecular Weight Control in Ring‐Opening Metathesis Polymerization (ROMP) Reactions with Ru‐Based Olefin Metathesis Catalysts Using N Donors and Acid: A Kinetic and Mechanistic Investigation

The effect of the addition of H₃PO₄ on the ROMP activity of cyclooctene (COE) with first‐ [Cl₂(PCy₃)₂Ru?CHPh] and second‐generation [(H₂IMes)Cl₂(PCy₃)Ru?CHPh] Grubbs’ catalysts 1 and 4 (Cy=cyclohexyl, Ph=phenyl, Mes=2,4,6‐trimethylphenyl (mesityl)), their inhibited mixtures with 1‐methylimidazole (MIM), as well as their isolated bis‐N,N′‐dimethylaminopyridine (DMAP) derivatives [Cl₂(PCy₃)(DMAP)₂Ru?CHPh)] ( 5 b ) and [Cl₂(H₂IMes)(DMAP)₂Ru?CHPh] ( 7 b ) (DMAP=dimethylaminopyridine), a novel catalyst, has been investigated. The studies include the determination of their initiation rates, as well as a determination of the molecular weights and molecular weight distributions of the polymers obtained with these catalysts and catalyst mixtures from the exo‐7‐oxanorbornene derivative 11 . The structure of catalyst 7 b was confirmed by means of X‐ray diffraction. All N‐donor‐bearing catalysts or N‐donor‐containing catalyst mixtures not only exhibited elevated activity in the presence of acid, but also increased initiation rates. Using the reversible inhibition/activation protocol with MIM and H₃PO₄ enabled us to conduct controlled ROMP with catalyst 4 producing the isolated exo‐7‐oxanorbornene‐based polymer 12 with predetermined molecular weights and narrow molecular weight distributions. This effect was based on fast and efficient catalyst initiation in contrast to the parent catalyst 4 . Hexacoordinate complex 5 b also experienced a dramatic increase in initiation rates upon acid‐addition and the ROMP reactions became well‐controlled in contrast to the acid‐free reaction. In contrast, complex 7 b performs well‐controlled ROMP in the absence of acid, whereas the polymerization of the same monomer becomes less controlled in the presence of H₃PO₄. The closer evaluation of catalysts 5 b and 7 b demonstrated that their initiation rates exhibit a linear dependency on the substrate concentration in contrast to catalysts 1 and 4 . As a consequence, their initiation rates are determined by an associative step, not a dissociative step as seen for catalysts 1 and 4 . A feasible associative metathesis initiation mechanism is proposed.     

Macroscopic evidence of soliton formation in multiterawatt laser-plasma interaction

A novel physical phenomenon has been observed following the interaction of an intense (10(19) W/cm(2)) laser pulse with an underdense plasma. Long-lived, macroscopic bubblelike structures have been detected through the deflection that the associated electric charge separation causes in a proton probe beam. These structures are interpreted as the remnants of a cloud of relativistic solitons generated in the plasma by the ultraintense laser pulse. This interpretation is supported by an analytical study of the soliton cloud evolution, by particle-in-cell simulations, and by a reconstruction of the proton-beam deflection.     

The conductivity of a two-dimensional electronic system of finite width in the presence of a strong perpendicular magnetic field and a random potential

Starting from the Kubo formula the conductivity tensor of a two-dimensional electronic system in a perpendicular magnetic field is evaluated. It is shown that at zero temperature only the states at the Fermi level contribute. The Hall conductivity of a purely periodic system of finite width is calculated and compared with earlier suggestions by Thouless et al. For a system described by a periodic and a random potential the Hall conductivity is calculated as a function of the electron density. The results emphasize the importance of disorder independent current carrying states for the Quantum Hall effect which extend along the boundaries of the system. The plateaux values of the Hall conductivity are related to the number of these states, and are independent of the existence of extended bulk states below the Fermi energy.     

The preparation of hexasilsesquioxane (T6) cages by "non aqueous" hydrolysis of trichlorosilanes

Hexasilsesquioxane cages (T6) have been prepared from a range of alkyl and aryl trichlorosilanes using a "non aqueous" hydrolysis with dimethyl sulfoxide.     

Localization in disordered systems with interactions

We present an improved numerical approach to the study of disorder and interactions in quasi-1D systems which combines aspects of the transfer matrix method and the density matrix renormalization group which have been successfully applied to disorder and interacting problems respectively. The method is applied to spinless fermions in 1D and a generalization to finite cross-sections is outlined.      

Temperature effects on the magnetoplasmon spectrum of a weakly modulated graphene monolayer

In this work, we determine the effects of temperature on the magnetoplasmon spectrum of an electrically modulated graphene monolayer as well as a two-dimensional electron gas (2DEG). The intra-Landau band magnetoplasmon spectrum within the self-consistent field approach is investigated for both the aforementioned systems. Results obtained not only exhibit Shubnikov-de Haas (SdH) oscillations but also commensurability oscillations (Weiss oscillations). These oscillations are periodic as a function of inverse magnetic field. We find that both the magnetic oscillations, SdH and Weiss, have a greater amplitude and are more robust against temperature in graphene compared to a conventional 2DEG. Furthermore, there is a π phase shift between the magnetoplasmon oscillations in the two systems which can be attributed to Dirac electrons in graphene acquiring a Berry's phase as they traverse a closed path in a magnetic field.     

Scaling considerations for modelling the in situ vitrification process

Thermal-electric field interactions occur in many areas of engineering. An example is the in situ vitrification process, a relatively new technology for remediating hazardous wastes. Mathematical and physical modelling of this process requires knowledge of the similarity constraints involving thermal- electric fields. This paper addresses this issue and derives the scaling relationships for modelling the remediation process from fundamental principles. Requirements for maintaining temperature and electric potential field similarity between the model and the prototype are determined as well as requirements for maintaining similarity in off-gas generation rates. A scaling rationale for designing reduced scale experiments is presented, and the results are assessed numerically.     

Secretory protein profiling reveals TNF-α inactivation by selective and promiscuous Sec61 modulators

Cotransins are cyclic heptadepsipeptides that bind the Sec61 translocon to inhibit cotranslational translocation of a subset of secreted and type I transmembrane proteins. The few known cotransin-sensitive substrates are all targeted to the translocon by?a cleavable signal sequence, previously shown to be a critical determinant of cotransin sensitivity. By profiling two cotransin variants against a panel of secreted and transmembrane proteins, we demonstrate that cotransin side-chain differences profoundly affect substrate selectivity. Among the most sensitive substrates we identified is the proinflammatory cytokine tumor necrosis factor alpha (TNF-α). Like all type II transmembrane proteins, TNF-α is targeted to the translocon by its membrane-spanning domain, indicating that a cleavable signal sequence is not strictly required for cotransin sensitivity. Our results thus reveal an unanticipated breadth of translocon substrates whose expression is inhibited by Sec61 modulators.     

Density of states of a two-dimensional electron in a strong magnetic field and a random potential

The density of states of a two-dimensional electron in a strong magnetic field moving in a periodic and a random potential is calculated. The results are compared with the density of states of the Landau model with disorder as obtained in the single band approximation. The limitations of the single band model are discussed.