Ionic liquids containing the triply negatively charged tricyanomelaminate anion and a B(C6F5)3 adduct anion

Room‐temperature ionic liquids containing the triply charged tricyanomelaminate (tcmel) ion [C₃N₆(CN)₃]^3? were synthesized. The 1‐methyl‐3‐methylimidazolium (MMIm), 1‐ethyl‐3‐methylimidazolium (EMIm), and 1‐butyl‐3‐methylimidazolium (BMIm) salts of the tricyanomelaminate ion have glass transition temperatures (?6, ?20, and ?30 °C) similar to those found for the analogous monomeric dicyanoamide salts. They are thermally stable up to over 200 °C and dissolve in polar organic solvents. Addition of B(C₆F₅)₃ to M₃[tcmel] (M=Na, MMIm, EMIm, BMIm) yields salts containing the very voluminous adduct ion [C₃N₆{CN ? B(C₆F₅)₃}₃]^3? (tcmel_3B). The solid‐state structure of [MMIm]₃[tcmel] shows only long cation ??? anion contacts but in large number, while the solid‐state structure of [Na(THF)₃]₃[tcmel_3B] ? 1.76 THF displays strong interactions of the sodium cation with the amido nitrogen atoms of the anion. Hence this adduct anion cannot be regarded as a weakly coordinating anion. A similar situation is found for the MMIm salt, [MMIm]₃[tcmel_3B] ? 2.66 CH₂Cl₂, in which weak hydrogen bonds with the acidic proton of the MMIm ion are observed. On the basis of computations the energetics, structural trends, and charge transfer of adduct anion formation were studied.     

Water exchange reactivity and stability of cobalt polyoxometalates under catalytically relevant pH conditions: insight into water oxidation catalysis

Water exchange on a molecular, purely inorganic cobalt-based water oxidation catalyst, [Co(4)(II)(H(2)O)(2)(α-P(1)W(9)O(34))(2)](10-) (1), in the catalytically relevant pH region (pH 6-10) is studied using (17)O-NMR spectroscopy and ultrahigh-resolution electrospray ionization mass spectrometry. The results are compared with those of the inactive [Co(II)(H(2)O)(1)Si(1)W(11)O(39)](6-) (2), which is stable in the same pH region. The results obtained provide mechanistic details of the elementary reaction step related to the water oxidation on homogeneous metal oxide catalysts under catalytically relevant conditions. It is shown that the structural integrity of 1 and 2 is maintained, no deprotonation of the aqua ligands on the Co(II) centers occurs, and the water exchange does not undergo any mechanistic changeover at the catalytic pH conditions. We have demonstrated that the water exchange process is influenced by the cluster environment surrounding the water binding sites and is fast enough to not be rate-limiting for the water oxidation catalysis.     

Amphiphilic 1-deoxynojirimycin derivatives through click strategies for chemical chaperoning in N370S Gaucher cells

In Gaucher disease (GD), mutant β-glucocerebrosidases (β-GCase) that are misfolded are recognized by the quality control machinery of the endoplasmic reticulum (ER) and degraded proteolytically. Hydrophobic iminosugars can be used as pharmacological chaperones to provide an improvement in the folding of the enzyme and promote trafficking from the ER. We have developed here an efficient click procedure to tether hydrophobic substituents to N-azidopropyl-1-deoxynojirimycin. A set of 14 original iminosugars was designed and evaluated for inhibition of commercially available glucosidases. Most of the compounds were micromolar inhibitors of those enzymes. In vitro inhibition assays with the N370S β-GCase revealed that the sublibrary containing the derivatives with aromatic aglycons displayed the highest inhibitory potency. Chaperone activity of the whole set of synthetic compounds was also explored in mutant Gaucher cells. The most active compound gave a nearly 2-fold increase in enzyme activity at 20 μM, a significantly higher value than the 1.33-fold recorded for the reference compound N-nonyl-1-deoxynojirimycin (N-nonyl-DNJ). As previously reported with bicyclic sp(2)-iminosugars (Luan, Z.; Higaki, K.; Aguilar-Moncayo, M.; Ninomiya, H.; Ohno, K.; Garci?a-Moreno, M. I.; Ortiz Mellet, C.; Garci?a Ferna?ndez, J. M.; Suzuki, Y. ChemBioChem 2009, 10, 2780), in vitro inhibition of β-GCase measured for the compounds did not correlate with the cellular chaperone activity. The potency of new iminosugar chaperones is therefore not predictable from structure-activity relationships studies based on the in vitro β-GCase inhibition.     

A linear single-molecule magnet based on [Ru(III)(CN)6]3-

We report the synthesis, structure and magnetic properties of the first molecular cluster and single-molecule magnet to incorporate [Ru(III)(CN)(6)](3-). Frequency-domain Fourier-transform THz-EPR (FDFT THz-EPR) and magnetic susceptibility measurements indicate strongly anisotropic Mn-Ru exchange interactions.     

Optimal Stopping of Stochastic Differential Equations with Delay Driven by Lévy Noise

We study an optimal stopping problem for a stochastic differential equation with delay driven by a Lévy noise. Approaching the problem by its infinite-dimensional representation, we derive conditions yielding an explicit solution to the problem. Applications to the American put option problem are shown.     

Non-Abelian operations on Majorana fermions via single-charge control

We demonstrate that non-Abelian rotations within the degenerate ground-state manifold of a set of Majorana fermions can be realized by the addition or removal of single electrons, and propose an implementation using Coulomb blockaded quantum dots. The exchange of electrons generates rotations similar to braiding, though not in real space. Unlike braiding operations, rotations by a continuum of angles are possible, while still being partially robust against perturbations. The quantum dots can also be used for readout of the state of the Majorana system via a charge measurement.     

Nonlocal screening of plasmons in graphene by semiconducting and metallic substrates: first-principles calculations

We investigate the role of substrates on the collective excitations of graphene by using a first-principles implementation of the density response function within the random-phase approximation. Specifically, we consider graphene adsorbed on SiC(0001) and Al(111) as representative examples of a semiconducting and metallic substrate. On SiC(0001), the long wavelength π plasmons are significantly damped although their energies remain almost unaltered. On Al(111), the long wavelength π plasmons are completely quenched due to the coupling to the metal surface plasmon. The strong damping of the plasmon excitations occurs despite the fact that the single-particle band structure of graphene is completely unaffected by the substrates illustrating the nonlocal nature of the effect.     

Anomalous small-angle x-ray scattering from mesoporous noble metal catalysts

We present the analysis of a catalyst containing platinum nanoparticles supported on mesoporous MCM-41 silica by anomalous small-angle x-ray scattering (ASAXS). The analysis of this composite system by ASAXS is first studied by use of model calculation. Here, it is shown that the full analysis must proceed by decomposing the scattering data measured at different energies of the incident beam into three partial intensities. This evaluation is compared to a simplified method in which scattering curves measured at two different energies are subtracted from each other. The different methods are applied to experimental data obtained from platinum nanoparticles on an MCM-41 support material. The model calculations show that the simplified method leads to large deviations especially at low q in ordered systems. In the semi-ordered material MCM-41, these deviations are less pronounced, and the method of simple subtraction proves to be a good approximation for q values higher than 0.1 nm^?1.     

2,6,9-Trioxabicyclo[3.3.1]nona-3,7-dienes and 2,4,6,8-Tetraoxaadamantanes: Novel Chiral Spacer Units in Macrocyclic Polyethers

The unusual chiral heterocyclic systems, trioxabicyclo[3.3.1]nona-3,7-dienes ("bridged bisdioxines"), are incorporated as novel spacer molecules into macrocyclic polyether ring systems of various sizes (8, 9 as well as 11-15) by cyclocondensation reaction of the bisacid chloride 4b or bisesters 6,7 and 10, with several ethylene glycols. The 2:2 macrocycles 12-14 are obtained in approximately 50:50 mixtures of diastereomers. These conclusions are mainly based on HPLC data presented in Table I as well as X-ray analyses of (1R,5R)-8c (space group Pbca, a =10.163(3) Å, b =18.999(4) Å, c =36.187(10) Å, V =6987(3) ų , Z =8, d _calc =1.218 g cm^{m 3}, 6974 reflections, R =0.0553), meso/rac-11 (space group P1 ¥ , a =10.472(5) Å, b=16.390(5) Å, c =17.211(5) Å, f =98.69(2)°, g =93.04(2)°, n =98.52(2)°, V =2879.3(18) Å 3 , Z =2, d _calc =1.173 g cm m 3 , 11,162 reflections, R =0.0945) and meso-12 (space group P2₁/c, a =9.927(2), b =18.166(3), c =17.820(3) Å, g =96.590(10)°, V =3192.3(10) Å 3 , Z =4, D _c =1.109 g cm^{m 3}, 3490 reflections, R =0.0646). The 1:1 macrocycles 8b,c are also formed by intramolecular transesterification of the open-chain bisesters 7b,c and their formation is favored by the use of metal ions as templates. The bridged bisdioxine moieties in 8b and 12 are converted into the corresponding chiral tetraoxaadamantane spacers to afford macrocycles 16 and 17. Preliminary metal ion complexation studies with selected species (8c, 11-14) were also performed.     

Pooling of spare parts between multiple users: How to share the benefits?

Companies that maintain capital goods (e.g., airplanes or power plants) often face high costs, both for holding spare parts and due to downtime of their technical systems. These costs can be reduced by pooling common spare parts between multiple companies in the same region, but managers may be unsure about how to share the resulting costs or benefits in a fair way that avoids free riders. To tackle this problem, we study several players, each facing a Poisson demand process for an expensive, low-usage item. They share a stock point that is controlled by a continuous-review base stock policy with full backordering under an optimal base stock level. Costs consist of penalty costs for backorders and holding costs for on-hand stock. We propose to allocate the total costs proportional to players’ demand rates. Our key result is that this cost allocation rule satisfies many appealing properties: it makes all separate participants and subgroups of participants better off, it stimulates growth of the pool, it can be easily implemented in practice, and it induces players to reveal their private information truthfully. To obtain these game theoretical results, we exploit novel structural properties of the cost function in our (S − 1, S) inventory model.