Towards a systematic understanding of the influence of temperature on glycosylation reactions

Glycosidic bond formation is a continual challenge for practitioners. Aiming to enhance the reproducibility and efficiency of oligosaccharide synthesis, we studied the relationship between glycosyl donor activation and reaction temperature. A novel semi-automated assay revealed diverse responses of members of a panel of thioglycosides to activation at various temperatures. The patterns of protecting groups and the thiol aglycon combine to cause remarkable differences in temperature sensitivity among glycosylating agents. We introduce the concept of donor activation temperature to capture experimental insights, reasoning that glycosylations performed below this reference temperature evade deleterious side reactions. Activation temperatures enable a simplified temperature treatment and facilitate optimization of glycosylating agent (building block) usage. Isothermal glycosylation below the activation temperature halved the equivalents of building block required in comparison to the standard ‘ramp’ regime used in solution- and solid-phase oligosaccharide synthesis to-date

Spectroscopy of 26^{26}F

The structure of the weakly-bound $^{26}_{\;\;9}$F$_{17}$ odd-odd nucleus, produced from $^{27,28}$Na nuclei, has been investigated at GANIL by means of the in-beam $\gamma$-ray spectroscopy technique. A single $\gamma$-line is observed at 657(7) keV in $^{26}_{9}$F which has been ascribed to the decay of the excited J=$2^+$ state to the J=1$^+$ ground state. The possible presence of intruder negative parity states in $^{26}$F is also discussed.Comment: 3 pages, 1 figure, accepted for publication in Physical Review

Expanding the palette of phenanthridinium cations

5,6-Disubstituted phenanthridinium cations have a range of redox, fluorescence and biological properties. Some properties rely on phenanthridiniums intercalating into DNA, but the use of these cations as exomarkers for the reactive oxygen species (ROS), superoxide, and as inhibitors of acetylcholine esterase (AChE) do not require intercalation. A versatile modular synthesis of 5,6-disubstituted phenanthridiniums that introduces diversity by Suzuki–Miyaura coupling, imine formation and microwave-assisted cyclisation is presented. Computational modelling at the density functional theory (DFT) level reveals that the novel displacement of the aryl halide by an acyclic N-alkylimine proceeds by an SNAr mechanism rather than electrocyclisation. It is found that the displacement of halide is concerted and there is no stable Meisenheimer intermediate, provided the calculations consistently use a polarisable solvent model and a diffuse basis set

Coulomb excitation of 73Ga

The B(E2; Ii -> If) values for transitions in 71Ga and 73Ga were deduced from a Coulomb excitation experiment at the safe energy of 2.95 MeV/nucleon using post-accelerated beams of 71,73Ga at the REX-ISOLDE on-line isotope mass separator facility. The emitted gamma rays were detected by the MINIBALL-detector array and B(E2; Ii->If) values were obtained from the yields normalized to the known strength of the 2+ -> 0+ transition in the 120Sn target. The comparison of these new results with the data of less neutron-rich gallium isotopes shows a shift of the E2 collectivity towards lower excitation energy when adding neutrons beyond N = 40. This supports conclusions from previous studies of the gallium isotopes which indicated a structural change in this isotopical chain between N = 40 and N = 42. Combined with recent measurements from collinear laser spectroscopy showing a 1/2- spin and parity for the ground state, the extracted results revealed evidence for a 1/2-; 3/2- doublet near the ground state in 73 31Ga42 differing by at most 0.8 keV in energy

Fast-growing till over ancient ice in Beacon Valley, Antarctica

We analyze published cosmogenic 3He depth profiles through the till that covers relict glacier ice in Beacon Valley, Antarctica, in order to derive rigorous constraints on the till thickness history, and on the amount and rate of ice loss by sublimation. The till is a residue of debris-laden ice that sublimed. The 3He profiles show that the lower 80% of the till formed in the past 310–43 k.y. under sublimation rates averaging >7 m·m.y.−1 (meters per million years). Such rapid recent growth of the till contradicts previous interpretations that it is older than 8.1 Ma at an adjacent site, where it encloses volcanic ash of this age. We question whether the ash provides a valid age constraint for the ice. Cosmogenic nuclide analysis of the till where the ash was collected for dating should resolve this question

Collective and noncollective states in (120)Te

High-spin states in (120)Te were populated in the reaction (80)Se((48)Ca, alpha 4n)(120)Te at a beam energy of 207 MeV and gamma-ray coincidences were measured using the Gammasphere spectrometer. The previously known level scheme is extended to higher spin and new interband transitions and side-feeding branches are established. Five highly deformed rotational bands, extending up to almost I = 50, are observed for the first time. The bands are compared with similar structures found recently in neighboring nuclei. The experimental results are interpreted within the framework of the cranked Nilsson-Strutinsky model. Configuration assignments to several terminating states and to the high-spin bands are discussed

Collective and broken pair states of 65,67Ga

Excited states of 65Ga and 67Ga nuclei were populated through the 12C(58Ni,αp) and 12C(58Ni,3p) reactions, respectively, and investigated by in-beam γ-ray spectroscopic methods. The NORDBALL array equipped with a charged particle ball and 11 neutron detectors was used to detect the evaporated particles and γ rays. The level schemes of 65,67Ga were constructed on the basis of γγ-coincidence relations up to 8.6 and 10 MeV excitation energy, and Iπ=27/2 and 33/2+ spin and parity, respectively. The structure of 65,67Ga nuclei was described in the interacting boson-fermion plus broken pair model, including quasiproton, quasiproton-two-quasineutron, and three-quasiproton fermion configurations in the boson-fermion basis states. Most of the states were assigned to quasiparticle + phonon and three quasiparticle configurations on the basis of their electromagnetic decay properties

Terrain physical properties derived from orbital data and the first 360 sols of Mars Science Laboratory Curiosity rover observations in Gale Crater

Physical properties of terrains encountered by the Curiosity rover during the first 360 sols of operations have been inferred from analysis of the scour zones produced by Sky Crane Landing System engine plumes, wheel touch down dynamics, pits produced by Chemical Camera (ChemCam) laser shots, rover wheel traverses over rocks, the extent of sinkage into soils, and the magnitude and sign of rover‐based slippage during drives. Results have been integrated with morphologic, mineralogic, and thermophysical properties derived from orbital data, and Curiosity‐based measurements, to understand the nature and origin of physical properties of traversed terrains. The hummocky plains (HP) landing site and traverse locations consist of moderately to well‐consolidated bedrock of alluvial origin variably covered by slightly cohesive, hard‐packed basaltic sand and dust, with both embedded and surface‐strewn rock clasts. Rock clasts have been added through local bedrock weathering and impact ejecta emplacement and form a pavement‐like surface in which only small clasts (<5 to 10 cm wide) have been pressed into the soil during wheel passages. The bedded fractured (BF) unit, site of Curiosity's first drilling activity, exposes several alluvial‐lacustrine bedrock units with little to no soil cover and varying degrees of lithification. Small wheel sinkage values (<1 cm) for both HP and BF surfaces demonstrate that compaction resistance countering driven‐wheel thrust has been minimal and that rover slippage while traversing across horizontal surfaces or going uphill, and skid going downhill, have been dominated by terrain tilts and wheel‐surface material shear modulus values