Ionic galleries: a bilayered host-guest cocrystal of C-propyl pyrogallol[4]arene with an ionic liquid

We report on a cocrystal between C-propyl pyrogallol[4]arene and the ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate exhibiting a remarkable bilayer topology comprising two unique host-guest complexes resulting from the ionic liquid cation binding in two distinctive orientations relative to the macrocycle.     

Preliminary demonstration of an IonCCD as an alternative pixelated anode for direct MCP readout in a compact MS-based detector

We report on the preliminary testing of a new position-sensitive detector (PSD) by combining a microchannel plate (MCP) and a charge-sensitive pixilated anode with a direct readout based on charge-coupled detector (CCD) technology, which will be referred to as IonCCD (Hadjar et al. J Am Soc Mass Spectrom 22(4):612–623, 2011; Johnson et al. J Am Soc Mass Spectrom 22(8):1388–1394, 2011; Hadjar et al. J Am Soc Mass Spectrom 22(10):1872–1884, 2011). This work exploits the recently discovered electron detection capability of the IonCCD (Hadjar et al. J Am Soc Mass Spectrom 22(4):612–623, 2011), allowing it to be used directly behind an MC. This MCP-IonCCD configuration potentially obviates the need for electro-optical ion detector systems (EOIDs), which typically feature a relatively difficult-to-implement 5-kV power source as well as a phosphorus screen behind the MCP for conversion of electrons to photons prior to signal generation in a photosensitive CCD. Thus, the new system (MCP-IonCCD) has the potential to be smaller, simpler, more robust, and more cost efficient than EOID-based technologies in many applications. The use of the IonCCD as direct MCP readout anode, as opposed to its direct use as an ion detector, will benefit from the instant three-to-four-order-of-magnitude gain of the MCP with virtually no additional noise. The signal/noise gain can be used for either sensitivity or speed enhancement of the detector. The speed enhancement may motivate the development of faster IonCCD readout speeds (currently at 2.7 ms) to achieve the 2 kHz frame rate for which the IonCCD chip was designed, a must for transient signal applications. The presented detector exhibits clear potential not only as a trace analysis detector in scan-free mass spectrometry and electron spectroscopy but also as a compact detector for photon and particle imaging applications.     

Aromaticity rules for cycles with arbitrary numbers of half-twists

A simple proof is given that the Hückel aromaticity rules generalise to cycles with an arbitrary number of half-twists, T; addition/removal of half-twists two at a time preserves all eigenvalues and degeneracies, so that closed-shell aromatic systems occur at pi-electron counts 4N+ 2, and antiaromatic at 4N for even T, and vice versa for odd T.     

Synthesis and biological evaluation of leucine enkephalin turn mimetics

A cyclic Leu-enkephalin mimetic containing a 7-membered ring, and two linear analogues, has been prepared on solid phase. In the cyclic mimetic the intramolecular (1-4) hydrogen bond found in crystalline Leu-enkephalin has been replaced by an ethylene bridge. In addition, the amide bond between Tyr1 and Gly2 has been replaced by a methylene ether isostere and Gly3 has been deleted. The two linear analogues both contain the methylene ether isostere instead of the Tyr1-Gly2 amide bond and the shorter of the two lacks Gly3. The three compounds, and a beta-turn mimetic analogous to the 7-membered turn mimetic but with Gly3 included, were evaluated for specific binding to micro- and delta-opioid receptors in rat brain membranes. With the exception of the beta-turn mimetic the three other Leu-enkephalin analogues all bound with varying affinity to the micro- and delta-opioid receptors. From the results it could be concluded that Leu-enkephalin binds in a turn conformation to the opiate receptors, but that this conformation is not a (1-4) beta-turn.     

Cusp size bounds from singular surfaces in hyperbolic 3-manifolds

Singular maps of surfaces into a hyperbolic 3-manifold are utilized to find upper bounds on meridian length, -curve length and maximal cusp volume for the manifold. This allows a proof of the fact that there exist hyperbolic knots with arbitrarily small cusp density and that every closed orientable 3-manifold contains a knot whose complement is hyperbolic with maximal cusp volume less than or equal to 9. We also find particular upper bounds on meridian length, -curve length and maximal cusp volume for hyperbolic knots in depending on crossing number. Particular improved bounds are obtained for alternating knots.

     

Catalytic site-selective thiocarbonylations and deoxygenations of vancomycin reveal hydroxyl-dependent conformational effects

We have examined peptide-based catalysts for the site-selective thiocarbonylation of a protected form of vancomycin. Several catalysts were identified that either enhanced or altered the inherent selectivity profile exhibited by the substrate. Two catalysts, one identified through screening and another through rational design, were demonstrated to be effective on 0.50-g scale. Deoxygenations led ultimately to two new deoxy-vancomycin derivatives, and surprising conformational consequences of deoxygenation were revealed for one of the new compounds. These effects were mirrored in the biological activities of the new analogues and support a structural role for certain hydroxyls in the native structure.     

Detecting change in UK extreme precipitation using results from the climate<Emphasis Type="Italic">prediction</Emphasis>.net BBC climate change experiment

We investigate a question posed by policy makers, namely, “when will changes in extreme precipitation due to climate change be detectable?” To answer this question we use climateprediction.net (CPDN) model simulations from the BBC Climate Change Experiment (CCE) over the UK. These provide us with the unique opportunity to compare 1-day extreme precipitation generated from climate altered by observed forcings (time period 1920–2000) and the SRES A1B emissions scenario (time period 2000–2080) (the Scenario) to extreme precipitation generated by a constant climate for year 1920 (the Control) for the HadCM3L General Circulation Model (GCM). We fit non-stationary Generalized Extreme Value (GEV) models to the Scenario output and compare these to stationary GEV models fit to the parallel Control. We define the time of detectable change as the time at which we would reject a hypothesis at the α = 0.05 significance level that the 20-year return level of the two runs is equal. We find that the time of detectable change depends on the season, with most model runs indicating that change to winter extreme precipitation may be detectable by the year 2010, and that change to summer extreme precipitation is not detectable by 2080. We also investigate which climate model parameters affect the weight of the tail of the precipitation distribution and which affect the time of detectable change for the winter season. We find that two climate model parameters have an important effect on the tail weight, and two others seem to affect the time of detection. Importantly, we find that climate model simulated extreme precipitation has a fundamentally different behavior to observations, perhaps due to the negative estimate of the GEV shape parameter, unlike observations which produce a slightly positive (～0.0–0.2) estimate.