Cyclopropane-aldehyde annulations at quaternary donor sites: stereoselective access to highly substituted tetrahydrofurans

A diastereoselective synthesis of pentasubstituted tetrahydrofurans via a Lewis acid catalyzed (3 + 2)-annulation of quaternary donor site cyclopropanes and aldehydes is described. The reaction is catalyzed by Sn(OTf)(2), SnCl(4), or Hf(OTf)(4) in yields up to 95% and diastereomeric ratios as high as 99:1.     

Cannabisol, a novel Δ-THC dimer possessing a unique methylene bridge, isolated from Cannabis sativa

Cannabisol (1), a unique dimer of Δ⁹-tetrahydrocannabinol (Δ⁹-THC) with a methylene bridge, was isolated from Cannabis sativa. This is the first example of a C-bridged dimeric cannabinoid. The structure of 1 was unambiguously deduced by HRESIMS, GCMS, and NMR spectroscopy. A plausible biogenesis of 1 is described.     

Temperature effects on retention and efficiency of butyl and lauryl acrylate porous polymer monoliths in capillary electrochromatography

The development of organic porous polymer monoliths represents an alternative approach to stationary phase design. The use of these materials has helped to rekindle interest in capillary electrochromatography. Although a large number of investigations have explored different monolith recipes, polymerization conditions, and application challenges, few investigations have addressed the fundamentals of this separation mode with this type of material. This study addresses the thermodynamics of the reversed phase retention mechanism on 100% butyl acrylate and 1:3 butyl:lauryl acrylate (volume/volume ratio) porous polymer monoliths used in a capillary electrochromatography mode. Linear van't Hoff plots yield enthalpies of retention of ?3.9 to ?14.3 kJ/mol on two different, but related columns for five selected hydrophobic analytes across a thirty degree temperature range. Minimum plate heights were only moderately impacted over this temperature range.     

The ExoMars rover locomotion subsystem

ExoMars is the European Space Agency (ESA) mission to Mars planned for launch in 2018, focusing on exobiology with the primary objective of searching for any traces of extant or extinct carbon-based micro-organisms. The on-surface mission is performed by a near-autonomous mobile robotic vehicle (also referred to as the rover) with a mission design life of 180 sols. The rover has a 6 × 6 × 6 with 6 wheel-walking drive configuration (all 6 wheels are driven, steered and have a ‘walking’ capability) and has flexible wheels providing enhanced traction compared to rigid wheels of the same diameter. The suspension is a passive ‘3-bogie’ system which offers the same 6 wheel contact on uneven ground and mobility performance as the NASA-JPL ‘rocker-bogie’ suspension used on previous Mars rovers, but permits elimination of the differential linkage present in that design. Mars presents several challenges to the rover locomotion subsystem with its rock-strewn surface, sand dunes, rocky outcrops, craters and slopes. The unknown nature of the terrain to be traversed imposes several constraints on the locomotion subsystem design that need to be evaluated and incorporated within the flight model for its successful operation on Mars. In addition, accommodation within the confines of the lander and successful egress from it over deflated airbags places stringent constraints on locomotion subsystem mass, stowage envelope, deployment and wheel design. This paper documents the evolution of the ExoMars rover vehicle locomotion configuration from an early design concept to the current mission baseline design. The discussion involves various tradeoffs supported by mechanical and terramechanical analyses, simulations and testing performed on full-scale locomotion breadboard models at single wheel level and system level.     

NMR Study of proton transport in crystalline antimonic acid

Pulsed ¹H NMR measurements are reported for polycrystalline antimonic acid (Sb₂O₅·nH₂O) in the temperature range 145 K<T<330 K at 60 MHz. Motional narrowing occurs at T>220 K and the relaxation behaviour is compatible with fast proton transport with a distribution of activation energies.     

NMR study of hydrogen molybdenum bronzes: H1.71MoO3 and H0.36MoO3

Proton NMR relaxation times (T₂T₁, and T_1?) and absorption spectra are reported for the compounds H_1.71MoO₃ (red monoclinic) and H_0.36MoO₃ (blue orthorhombic) in the temperature range 77 K < T < 450 K. Rigid lattice dipolar spectra show that both compounds contain proton pairs, as OH₂ groups coordinated to Mo atoms in H_1.71MoO₃ and as pairs of OH groups in H_0.36MoO₃. The room temperature lineshape for H_1.71MoO₃ shows that the average chemical shielding tensor has a total anisotropy of 20.1 ppm. The relaxation measurements confirm that hydrogen diffusion occurs and give E_A = 22 kJ mole^?1 and $\text{τ}{}^0{}_{\mathrm{<mtext>C</mtext>}}\text{? 10}{}^{\mathrm{?13}}\text{sec}$ for H_1.71MoO₃ and E_A = 11 kJ mole^?1 and $\text{τ}{}^0{}_{\mathrm{<mtext>C</mtext>}}\text{? 3 × 10}{}^{\mathrm{?8}}\text{sec}$ for H_0.36MoO₃.     

The diffusive phase of a model of self-interacting walks

Summary We consider simple random walk onZ ^d perturbed by a factor exp[T ^–P J _T], whereT is the length of the walk and . Forp=1 and dimensionsd2, we prove that this walk behaves diffusively for all – < <₀, with ₀ > 0. Ford>2 the diffusion constant is equal to 1, but ford=2 it is renormalized. Ford=1 andp=3/2, we prove diffusion for all real (positive or negative). Ford>2 the scaling limit is Brownian motion, but ford2 it is the Edwards model (with the wrong sign of the coupling when >0) which governs the limiting behaviour; the latter arises since for ,T ^–p J _T is the discrete self-intersection local time. This establishes existence of a diffusive phase for this model. Existence of a collapsed phase for a very closely related model has been proven in work of Bolthausen and Schmock.