Selective saturation of step-edges as a tool to control the growth of molecular fibres

The formation of molecular fibres is often hampered by defects such as step edges, which act as nucleation sites. Here, we present a concept of how exposure of the support to oxygen or even air disables the formation of such defect-driven fibres.

Sensitivity enhancement of homonuclear multidimensional NMR correlations for labile sites in proteins, polysaccharides, and nucleic acids

Multidimensional TOCSY and NOESY are central experiments in chemical and biophysical NMR. Limited efficiencies are an intrinsic downside of these methods, particularly when targeting labile sites. This study demonstrates that the decoherence imparted on these protons through solvent exchanges can, when suitably manipulated, lead to dramatic sensitivity gains per unit time in the acquisition of these experiments. To achieve this, a priori selected frequencies are encoded according to Hadamard recipes, while concurrently subject to looped selective inversion or selective saturation procedures. Suitable processing then leads to protein, oligosaccharide and nucleic acid cross-peak enhancements of ≈200–1000% per scan, in measurements that are ≈10-fold faster than conventional counterparts. The extent of these gains will depend on the solvent exchange and relaxation rates of the targeted sites; these gains also benefit considerably from the spectral resolution provided by ultrahigh fields, as corroborated by NMR experiments at 600 MHz and 1 GHz. The mechanisms underlying these experiments’ enhanced efficiencies are analyzed on the basis of three-way polarization transfer interplays between the water, labile and non-labile protons, and the experimental results are rationalized using both analytical and numerical derivations. Limitations as well as further extensions of the proposed methods, are also discussed.

Gold and tin mineralisation in the ultramafic-hosted Cheoeum vent field, Central Indian Ridge

The Cheoeum vent field (CVF) is the first example of an inactive ultramafic-hosted seafloor massive sulphide (SMS) deposit identified in the middle part of the Central Indian Ridge. Here, we report on the detailed mineralogy and geochemistry of ultramafic-hosted sulphide sample atop a chimney, together with a few small fragments. Hydrothermal chimneys are characterised by high concentrations of Au (up to 17.8 ppm) and Sn (up to 1720 ppm). The sulphide mineralisation in the CVF shows (1) early precipitation of anhedral sphalerite and pyrite–marcasite aggregates under relatively low-temperature (< 250 °C) fluid conditions; (2) intensive deposition of subhedral pyrrhotite, isocubanite, chalcopyrite, Fe-rich sphalerite (Sp-III), and electrum from high-temperature (250–365 °C) and reduced fluids in the main mineralisation stage; and (3) a seawater alteration stage distinguished by the mineral assemblage of marcasite pseudomorphs, altered isocubanite phase, covellite, amorphous silica, and Fe-oxyhydroxides. Electrum (< 2 μm in size) is the principal form of Au mineralisation and is mainly associated with the main mineralisation stage. The consistently high fineness of electrum (801 to 909‰) is indicative of the selective saturation of Au over Ag in the fluid during high-temperature mineralisation, which differs from the Au mineralisation associated with typical basaltic-hosted hydrothermal systems on mid-ocean ridges. Tin is mainly substituted in structures of sphalerite, isocubanite, and chalcopyrite as a solid solution, and not as mineral inclusions. The continuously ascending hydrothermal fluids enable the early formed Sn-bearing sulphide to be dissolved and reprecipitated, producing significantly Sn-enriched replacement boundaries between isocubanite and Sp-III. This study suggests that Au–Sn mineralisation could be facilitated by the low redox potential of ultramafic-hosted hydrothermal systems such as in the CVF, which may be a common occurrence along slow-spreading mid-ocean ridges.

Pulse Shaped Dynamic Nuclear Polarization Under Magic Angle Spinning

In this paper, we report on an entirely novel way of improving the MAS-DNP efficiency by shaped μw pulse train irradiation for fast and broad-banded (FAB) saturation of the electron spin resonance. FAB-DNP achieved with Arbitrary Wave Generated shaped μw pulse trains facilitates effective and selective saturation of a defined fraction of the total electron spins, and provides superior control over the DNP efficiency under MAS. Experimental and quantum-mechanics based numerically simulated results together demonstrate that FAB-DNP significantly outperforms CW-DNP when the EPR-line of PAs is broadened by conformational distribution and exchange coupling. We demonstrate that the maximum benefit of FAB DNP is achieved when the electron spin-lattice relaxation is fast relative to the MAS frequency, i.e. at higher temperatures and/or when employing metals as PAs. Calculations predict that under short T_1econditions AWG-DNP can achieve as much as ~4-fold greater enhancement compared to CW-DNP.

Pulse Shaped Dynamic Nuclear Polarization Under Magic Angle Spinning

In this paper, we report on an entirely novel way of improving the MAS-DNP efficiency by shaped μw pulse train irradiation for fast and broad-banded (FAB) saturation of the electron spin resonance. FAB-DNP achieved with Arbitrary Wave Generated shaped μw pulse trains facilitates effective and selective saturation of a defined fraction of the total electron spins, and provides superior control over the DNP efficiency under MAS. Experimental and quantum-mechanics based numerically simulated results together demonstrate that FAB-DNP significantly outperforms CW-DNP when the EPR-line of PAs is broadened by conformational distribution and exchange coupling. We demonstrate that the maximum benefit of FAB DNP is achieved when the electron spin-lattice relaxation is fast relative to the MAS frequency, i.e. at higher temperatures and/or when employing metals as PAs. Calculations predict that under short T_1econditions AWG-DNP can achieve as much as ~4-fold greater enhancement compared to CW-DNP.

Direct observation of Ru-alkylidene forming into ethylene in ring-closing metathesis from hyperpolarized 1H NMR

With hyperpolarization and selective saturation, we identified an observable intermediate as Ru-alkylidene transferring its protons to ethylene in ring-closing metathesis.