Olefin cross-metathesis as a valuable tool for the preparation of renewable polyesters and polyamides from unsaturated fatty acid esters and carbamates

Olefin cross-metathesis of unsaturated fatty acid methyl ester (FAME) derived benzyl carbamates with methyl acrylate is described. The obtained by-product{,} an [small alpha]{,}[small beta]-unsaturated ester{,} was further modified via thia-Michael addition reactions in order to synthesize branched AA-type or AB-type monomers for the preparation of polyesters{,} which are tuneable by oxidation. Cross-metathesis of fatty acid derived carbamates was used as a novel approach to prepare linear AB-type monomers{,} which can be used for the preparation of renewable polyamides PA11{,} PA12 and PA15. The necessary fatty acid carbamates were prepared by applying a catalytic Lossen rearrangement procedure. The presented synthesis strategy has potential for the bio-sourced preparation of monomers for the production of polyamides. All prepared polymers were fully characterized by NMR{,} SEC{,} and DSC analyses. Additionally{,} the Young{\u27}s modulus of the prepared long-chain polyamide PA15 was determined

Olefin cross-metathesis as a valuable tool for the preparation of renewable polyesters and polyamides from unsaturated fatty acid esters and carbamates

Olefin cross-metathesis of unsaturated fatty acid methyl ester (FAME) derived benzyl carbamates with methyl acrylate is described. The obtained by-product{,} an [small alpha]{,}[small beta]-unsaturated ester{,} was further modified via thia-Michael addition reactions in order to synthesize branched AA-type or AB-type monomers for the preparation of polyesters{,} which are tuneable by oxidation. Cross-metathesis of fatty acid derived carbamates was used as a novel approach to prepare linear AB-type monomers{,} which can be used for the preparation of renewable polyamides PA11{,} PA12 and PA15. The necessary fatty acid carbamates were prepared by applying a catalytic Lossen rearrangement procedure. The presented synthesis strategy has potential for the bio-sourced preparation of monomers for the production of polyamides. All prepared polymers were fully characterized by NMR{,} SEC{,} and DSC analyses. Additionally{,} the Young{\u27}s modulus of the prepared long-chain polyamide PA15 was determined

Mott transition in one dimension: Benchmarking dynamical cluster approaches

The variational cluster approach (VCA) is applied to the one-dimensional Hubbard model at zero temperature using clusters (chains) of up to ten sites with full diagonalization and the Lanczos method as cluster solver. Within the framework of the self-energy-functional theory (SFT), different cluster reference systems with and without bath degrees of freedom, in different topologies and with different sets of variational parameters are considered. Static and one-particle dynamical quantities are calculated for half-filling as a function of U as well as for fixed U as a function of the chemical potential to study the interaction- and filling-dependent metal-insulator (Mott) transition. The recently developed Q-matrix technique is used to compute the SFT grand potential. For benchmarking purposes we compare the VCA results with exact results available from the Bethe ansatz, with essentially exact dynamical DMRG data, with (cellular) dynamical mean-field theory and full diagonalization of isolated Hubbard chains. Several issues are discussed including convergence of the results with cluster size, the ability of cluster approaches to access the critical regime of the Mott transition, efficiency in the optimization of correlated-site vs. bath-site parameters and of multi-dimensional parameter optimization. We also study the role of bath sites for the description of excitation properties and as charge reservoirs for the description of filling dependencies. The VCA turns out to be a computationally cheap method which is competitive with established cluster approaches.Comment: 19 pages, 19 figures, v3 with minor corrections, extended discussio

Quantisation of Hopping Magnetoresistance Prefactor in Strongly Correlated Two-Dimensional Electron Systems

We report an universal behaviour of hopping transport in strongly interacting mesoscopic two-dimensional electron systems (2DES). In a certain window of background disorder, the resistivity at low perpendicular magnetic fields follows the expected relation $\rho(B_\perp) = \rho_{\rm{B}}\exp(\alpha B_\perp^2)$. The prefactor $\rho_{\rm{B}}$ decreases exponentially with increasing electron density but saturates to a finite value at higher densities. Strikingly, this value is found to be universal when expressed in terms of absolute resistance and and shows quantisation at $R_{\rm{B}}\approx h/e^2$ and $R_{\rm{B}}\approx 1/2$ $h/e^2$. We suggest a strongly correlated electronic phase as a possible explanation.Comment: 5 pages, 3 figures, Proceedings of EP2DS 17, Reference adde

D-brane interactions in type IIB plane-wave background

The cylinder diagrams that determine the static interactions between pairs of Dp-branes in the type IIB plane wave background are evaluated. The resulting expressions are elegant generalizations of the flat-space formulae that depend on the value of the Ramond-Ramond flux of the background in a non-trivial manner. The closed-string and open-string descriptions consistently transform into each other under a modular transformation only when each of the interacting D-branes separately preserves half the supersymmetries. These results are derived for configurations of euclidean signature D(p+1)-instantons but also generalize to lorentzian signature Dp-branes.Comment: 24 pages, Normalisation of boundary states correcte

Semi-robotic 6 degree of freedom positioning for intracranial high precision radiotherapy; first phantom and clinical results

<p>Abstract</p> <p>Background</p> <p>To introduce a novel method of patient positioning for high precision intracranial radiotherapy.</p> <p>Methods</p> <p>An infrared(IR)-array, reproducibly attached to the patient via a vacuum-mouthpiece(vMP) and connected to the table via a 6 degree-of-freedom(DoF) mechanical arm serves as positioning and fixation system. After IR-based manual prepositioning to rough treatment position and fixation of the mechanical arm, a cone-beam CT(CBCT) is performed. A robotic 6 DoF treatment couch (HexaPOD™) then automatically corrects all remaining translations and rotations. This absolute position of infrared markers at the first fraction acts as reference for the following fractions where patients are manually prepositioned to within ± 2 mm and ± 2° of this IR reference position prior to final HexaPOD-based correction; consequently CBCT imaging is only required once at the first treatment fraction.</p> <p>The preclinical feasibility and attainable repositioning accuracy of this method was evaluated on a phantom and human volunteers as was the clinical efficacy on 7 pilot study patients.</p> <p>Results</p> <p>Phantom and volunteer manual IR-based prepositioning to within ± 2 mm and ± 2° in 6DoF was possible within a mean(± SD) of 90 ± 31 and 56 ± 22 seconds respectively. Mean phantom translational and rotational precision after 6 DoF corrections by the HexaPOD was 0.2 ± 0.2 mm and 0.7 ± 0.8° respectively. For the actual patient collective, the mean 3D vector for inter-treatment repositioning accuracy (n = 102) was 1.6 ± 0.8 mm while intra-fraction movement (n = 110) was 0.6 ± 0.4 mm.</p> <p>Conclusions</p> <p>This novel semi-automatic 6DoF IR-based system has been shown to compare favourably with existing non-invasive intracranial repeat fixation systems with respect to handling, reproducibility and, more importantly, intra-fraction rigidity. Some advantages are full cranial positioning flexibility for single and fractionated IGRT treatments and possibly increased patient comfort.</p

A 490 GHz planar circuit balanced Nb-Al2_\mathbf{2}O3_{\mathbf{3}}-Nb quasiparticle mixer for radio astronomy: Application to quantitative local oscillator noise determination

This article presents a heterodyne experiment which uses a 380-520 GHz planar circuit balanced Nb-$\mathrm{Al_2O_3}$-Nb superconductor-insulator-superconductor (SIS) quasiparticle mixer with 4-8 GHz instantaneous intermediate frequency (IF) bandwidth to quantitatively determine local oscillator (LO) noise. A balanced mixer is a unique tool to separate noise at the mixer's LO port from other noise sources. This is not possible in single-ended mixers. The antisymmetric IV characteristic of a SIS mixer further helps to simplify the measurements. The double-sideband receiver sensitivity of the balanced mixer is 2-4 times the quantum noise limit $h\nu/k_B$ over the measured frequencies with a maximum LO noise rejection of 15 dB. This work presents independent measurements with three different LO sources that produce the reference frequency but also an amount of near-carrier noise power which is quantified in the experiment as a function of the LO and IF frequency in terms of an equivalent noise temperature $T_{LO}$. In a second experiment we use only one of two SIS mixers of the balanced mixer chip, in order to verify the influence of near-carrier LO noise power on a single-ended heterodyne mixer measurement. We find an IF frequency dependence of near-carrier LO noise power. The frequency-resolved IF noise temperature slope is flat or slightly negative for the single-ended mixer. This is in contrast to the IF slope of the balanced mixer itself which is positive due to the expected IF roll-off of the mixer. This indicates a higher noise level closer to the LO's carrier frequency. Our findings imply that near-carrier LO noise has the largest impact on the sensitivity of a receiver system which uses mixers with a low IF band, for example superconducting hot-electron bolometer (HEB) mixers.Comment: 13 pages, 8 figures, 2 tables, see manuscript for complete abstrac