"Inosaminoacids": novel inositol-amino acid hybrid structures accessed by microbial arene oxidation

Microbial 1,2-dihydroxylation of sodium benzoate permits the rapid construction of novel inositol-amino acid hybrid structures. Both β- and γ-amino acids are accessible by means of an acylnitroso Diels-Alder cycloaddition.     

Palladium catalyzed ring opening of furans as a route to α,β-unsaturated aldehydes

Furans may be ring opened via pallado-catalyzed reactions leading to α,β-unsaturated aldehydes and ketones tethered to indole and isoquinoline moieties. Besides their synthetic interest, these fragmentations bring interesting elements into the discussion around the reaction mechanisms involved in palladium C-H activations of electron-rich heterocycles.     

Minimizing convex quadratics with variable precision conjugate gradients

We investigate the method of conjugate gradients, exploiting inaccurate matrix‐vector products, for the solution of convex quadratic optimization problems. Theoretical performance bounds are derived, and the necessary quantities occurring in the theoretical bounds estimated, leading to a practical algorithm. Numerical experiments suggest that this approach has significant potential, including in the steadily more important context of multiprecision computations.     

Massive: The Hunt for the God Particle,by Ian Sample

For almost a hundred years the diffraction grating has been among the most important of scientific tools. The methods of ruling gratings for use in all regions of the spectrum from the soft x-ray region to the infra-red are described. The properties of ideal and imperfect gratings are considered and an account of present-day scientific and industrial uses is given.     

Measurement and Interpretation of Ethanol 13C Chemical Shifts Variations in Different Organic Solvents - Comparison with Aqueous Solvent

The carbon chemical shifts of ethanol are measured in varied aqueous and organic solvents. We determine the hydrogen bonding effect between alcohol and bases by correcting the experimental values from anisotropy and non specific medium effects.     

New techniques for high pressure falling sphere viscosimetry in DIA-type large volume presses

Here we report recent technical advances that enable viscosity measurements in two DIA-type multi-anvil apparatus with a maximum of 250 tons and 1750 tons. We anticipate that this system will enable viscosity measurements for the pressures up to about 30 GPa. The deformation of the cell assemblies were analyzed by X-ray absorption tomography at beamline W II at DESY/HASYLAB after the high pressure runs. This analysis gave considerable insights into strategies for improving the cell assembly with the result that the optimized assemblies could be used at much higher pressures without blow-outs. We demonstrate using of X-ray transparent cubic boron nitride-anvils (single-stage DIA) and slotted carbide anvils (double-stage DIA) to make the whole melting chamber accessible for the high pressure X-radiography system. Results are demonstrated with viscosity measurements following Stokes’ Law by evaluation of X-radiography sequences taken by a camera equipped with a charge-coupled device sensor (CCD-camera) at pressures of 5 GPa as well as 10 GPa and temperatures of 1890 K.     

Antiferromagnetic Ordering of Magnetic Clusters Units in Nb6F15

We have studied the magnetic cluster compound Nb₆F₁₅ which has an odd number of 15 valence electrons per (Nb₆F₁₂)³⁺ cluster core, as a function of temperature using nuclear magnetic resonance, magnetic susceptibility, electron magnetic resonance and neutron powder diffraction. Nuclear magnetic resonance of the ¹⁹F nuclei shows two lines corresponding to the apical F^a?a nucleus, and to the inner Fⁱ nuclei. The temperature dependence of the signal from the Fⁱ nuclei reveals an antiferromagnetic ordering at T < 5 K, with a hyperfine field of ~2 mT. Magnetic susceptibility exhibits a Curie–Weiss behavior with T _N ~5 K, and μ _eff ~1.57 μ_B close to the expected theoretical value for one unpaired electron (1.73 μ_B). Electron magnetic resonance linewidth shows a transition at 5 K. Upon cooling from 10 to 1.4 K, the neutron diffraction shows a decrease in the intensity of the low-angle diffuse scattering below Q ~0.27 Å^?1. This decrease is consistent with emergence of magnetic order of large magnetic objects (clusters). This study shows that Nb₆F₁₅ is paramagnetic at RT and undergoes a transition to antiferromagnetic order at 5 K. This unique antiferromagnetic ordering results from the interaction between magnetic spins delocalized over each entire (Nb₆F ₁₂ ⁱ )³⁺ cluster core, rather than the common magnetic ordering.     

Kinetics of nanoconfined benzyl methacrylate radical polymerization

The effect of nanoconfinement on the kinetics of benzyl methacrylate radical polymerization is investigated using differential scanning calorimetry. Controlled pore glass (CPG), ordered mesoporous carbons, and mesoporous silica are used as confinement media with pore sizes from 2 to 8 nm. The initial polymerization rate in CPG and mesoporous silica increases relative to the bulk and increases linearly with reciprocal pore size; whereas, the rate in the carbon mesopores decreases linearly with reciprocal pore size; the changes are consistent with the rate being related to the ratio of the pore surface area to pore volume. Induction times are longer for nanoconfined polymerizations, and in the case of CPG and carbon mesopores, autoacceleration occurs earlier, presumably due to the limited diffusivity and lower termination rates for the confined polymer chains. The molecular weight of the polymer synthesized in the nanopores is generally higher than that obtained in the bulk except at the lowest temperatures investigated. The equilibrium conversion under nanoconfinement decreases with decreasing temperature and with confinement size, exhibiting what appears to be a floor temperature at low temperatures.