A Bifunctional Electrocatalyst for OER and ORR based on a Cobalt(II) Triazole Pyridine Bis-[Cobalt(III) Corrole] Complex.

As alternative energy sources are essential to reach a climate-neutral economy, hydrogen peroxide (H2 O2 ) as futuristic energy carrier gains enormous awareness. However, seeking for stable and electrochemically selective H2 O2 ORR electrocatalyst is yet a challenge, making the design of-ideally-bifunctional catalysts extremely important and outmost of interest. In this study, we explore the application of a trimetallic cobalt(II) triazole pyridine bis-[cobalt(III) corrole] complex CoII TP[CoIII C]2 3 in OER and ORR catalysis due to its remarkable physicochemical properties, fast charge transfer kinetics, electrochemical reversibility, and durability. With nearly 100 % selective catalytic activity towards the two-electron transfer generated H2 O2 , an ORR onset potential of 0.8 V vs RHE and a cycling stability of 50 000 cycles are detected. Similarly, promising results are obtained when applied in OER catalysis. A relatively low overpotential at 10 mA cm-2 of 412 mV, Faraday efficiency 98 % for oxygen, an outstanding Tafel slope of 64 mV dec-1 combined with superior stability.

A Bifunctional Electrocatalyst for OER and ORR based on a Cobalt(II) Triazole Pyridine Bis-[Cobalt(III) Corrole] Complex.

As alternative energy sources are essential to reach a climate-neutral economy, hydrogen peroxide (H2O2) as futuristic energy carrier gains enormous awareness. However, seeking for stable and electrochemically selective H2O2 ORR electrocatalyst is yet a challenge, making the design of-ideally-bifunctional catalysts extremely important and outmost of interest. In this study, we explore the application of a trimetallic cobalt(II) triazole pyridine bis-[cobalt(III) corrole] complex CoIITP[CoIIIC]2 3 in OER and ORR catalysis due to its remarkable physicochemical properties, fast charge transfer kinetics, electrochemical reversibility, and durability. With nearly 100 % selective catalytic activity towards the two-electron transfer generated H2O2, an ORR onset potential of 0.8 V vs RHE and a cycling stability of 50 000 cycles are detected. Similarly, promising results are obtained when applied in OER catalysis. A relatively low overpotential at 10 mA cm-2 of 412 mV, Faraday efficiency 98 % for oxygen, an outstanding Tafel slope of 64 mV dec-1 combined with superior stability.

Chiral Lewis Base-Catalysed Asymmetric Syntheses of Benzo-fused ϵ-Lactones.

We herein report a two-step protocol for the asymmetric synthesis of novel chiral benzofused ϵ-lactones starting from O-protected hydroxymethyl-para-quinone methides and activated aryl esters. By using chiral isothiourea Lewis base catalysts a broad variety of differently substituted products could be obtained in yields of around 50 % over both steps with high levels of enantioselectivities, albeit low diastereoselectivities only.

Oxidative decarboxylative ammonium hypoiodite-catalysed dihydrobenzofuran synthesis.

The catalytic use of quaternary ammonium iodides under oxidative conditions allows for the direct conversion of readily available ß-ketolactones into dihydrobenzofurans via a decarboxylative oxidative cycloetherification sequence facilitated by an in situ formed ammonium hypoiodite species.

Spin noise gradient echoes.

Nuclear spin noise spectroscopy in the absence of radio frequency pulses was studied under the influence of pulsed field gradients (PFGs) on pure and mixed liquids. Under conditions where the radiation-damping-induced line broadening is smaller than the gradient-dependent inhomogeneous broadening, echo responses can be observed in difference spectra between experiments employing pulsed field gradient pairs of the same and opposite signs. These observed spin noise gradient echoes (SNGEs) were analyzed through a simple model to describe the effects of transient phenomena. Experiments performed on high-resolution nuclear magnetic resonance (NMR) probes demonstrate how refocused spin noise behaves and how it can be exploited to determine sample properties. In bulk liquids and their mixtures, transverse relaxation times and translational diffusion constants can be determined from SNGE spectra recorded following tailored sequences of magnetic field gradient pulses.

Interhelical interactions within the STIM1 CC1 domain modulate CRAC channel activation.

The calcium release activated calcium channel is activated by the endoplasmic reticulum-resident calcium sensor protein STIM1. On activation, STIM1 C terminus changes from an inactive, tight to an active, extended conformation. A coiled-coil clamp involving the CC1 and CC3 domains is essential in controlling STIM1 activation, with CC1 as the key entity. The nuclear magnetic resonance-derived solution structure of the CC1 domain represents a three-helix bundle stabilized by interhelical contacts, which are absent in the Stormorken disease-related STIM1 R304W mutant. Two interhelical sites between the CC1α1 and CC1α2 helices are key in controlling STIM1 activation, affecting the balance between tight and extended conformations. Nuclear magnetic resonance-directed mutations within these interhelical interactions restore the physiological, store-dependent activation behavior of the gain-of-function STIM1 R304W mutant. This study reveals the functional impact of interhelical interactions within the CC1 domain for modifying the CC1-CC3 clamp strength to control the activation of STIM1.

Nuclear spin noise tomography in three dimensions with iterative simultaneous algebraic reconstruction technique (SART) processing.

We report three-dimensional spin noise imaging (SNI) of nuclear spin density from spin noise data acquired by Faraday detection. Our approach substantially extends and improves the two-dimensional SNI method for excitation-less magnetic resonance tomography reported earlier (Müller and Jerschow, 2006). This proof of principle was achieved by taking advantage of the particular continuous nature of spin noise acquired in the presence of constant magnitude magnetic field gradients and recent advances in nuclear spin noise spectroscopy acquisition as well as novel processing techniques. In this type of projection-reconstruction-based spin noise imaging the trade-off between signal-to-noise ratio (or image contrast) and resolution can be adjusted a posteriori during processing of the original time-domain data by iterative image reconstruction in a unique way not possible in conventional rf-pulse-dependent magnetic resonance imaging (MRI). The 3D SNI is demonstrated as a proof of concept on a commercial 700 MHz high-resolution NMR spectrometer, using a 3D-printed polymeric phantom immersed in water.

Structural characterization of aerogels derived from enzymatically oxidized galactomannans of fenugreek, sesbania and guar gums.

Aerogels are obtained by laccase/2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO)-oxidation of galactomannans (GMs) from the leguminous plants fenugreek (Trigonella foenum-graecum), sesbania (Sesbania bispinosa) and guar (Cyamopsis tetragonolobus). GM oxidation in aqueous solutions causes a viscosity increase, resulting in structured and stable hydrogels. Upon lyophilization, water-insoluble aerogels are obtained, capable of water uptake up to several times their own weight. The materials derived from the three gums have been analyzed and compared. Chemical modifications have been studied by electrospray-ionization mass spectrometry (ESI-MS) and Fourier-transform infrared spectroscopy (FTIR). Polymer structure has been determined by liquid-state and semi-quantitative solid-state nuclear magnetic resonance (NMR) spectroscopy and chemical stability by incubation under variable conditions of pH, ionic strength and solvent nature. The results show that hydrogel formation is due to oxidation of primary hydroxyl groups to carbonyl and carboxyl groups and subsequent formation of hemiacetal and ester bonds. Fenugreek displays the highest stability, compared to guar and sesbania rehydrated aerogels. This feature could be interpreted by its higher degree of substitution (Gal:Man = 1:1) and consequently higher amount of galactose primary alcohols, leading to more extensive crosslinking.

Spin-Noise-Detected Two-Dimensional Nuclear Magnetic Resonance at Triple Sensitivity.

A major breakthrough in speed and sensitivity of 2 D spin-noise-detected NMR is achieved owing to a new acquisition and processing scheme called "double block usage" (DBU) that utilizes each recorded noise block in two independent cross-correlations. The mixing, evolution, and acquisition periods are repeated head-to-tail without any recovery delays and well-known building blocks of multidimensional NMR (constant-time evolution and quadrature detection in the indirect dimension as well as pulsed field gradients) provide further enhancement and artifact suppression. Modified timing of the receiver electronics eliminates spurious random excitation. We achieve a threefold sensitivity increase over the original snHMQC (spin-noise-detected heteronuclear multiple quantum correlation) experiment (K. Chandra et al., J. Phys. Chem. Lett. 2013, 4, 3853) and demonstrate the feasibility of spin-noise-detected long-range correlation.

On the Tautomerism of N-Substituted Pyrazolones: 1,2-Dihydro-3H-pyrazol-3-ones versus 1H-Pyrazol-3-ols.

The tautomerism of 1-phenyl-1,2-dihydro-3H-pyrazol-3-One was investigated. An X-ray crystal structure analysis exhibits dimers of 1-phenyl-1H-pyrazol-3-ol units. Comparison of NMR (nuclear magnetic resonance) spectra in liquid state (¹H, 13C, 15N) with those of "fixed" derivatives, as well as with the corresponding solid state NMR spectra reveal this compound to exist predominantly as 1H-pyrazol-3-ol molecule pairs in nonpolar solvents like CDCl3 or C6D6, whereas in DMSO-d6 the corresponding monomers are at hand. Moreover, the NMR data of different related 1H-pyrazol-3-ol derivatives are presented.

Spin Noise Detection of Nuclear Hyperpolarization at 1.2†K.

We report proton spin noise spectra of a hyperpolarized solid sample of commonly used "DNP (dynamic nuclear polarization) juice" containing TEMPOL (4-hydroxy-2,2,6,6-tetramethylpiperidine N-oxide) and irradiated by a microwave field at a temperature of 1.2 K in a magnetic field of 6.7 T. The line shapes of the spin noise power spectra are sensitive to the variation of the microwave irradiation frequency and change from dip to bump, when the electron Larmor frequency is crossed, which is shown to be in good accordance with theory by simulations. Small but significant deviations from these predictions are observed, which can be related to spin noise and radiation damping phenomena that have been reported in thermally polarized systems. The non-linear dependence of the spin noise integral on nuclear polarization provides a means to monitor hyperpolarization semi-quantitatively without any perturbation of the spin system by radio frequency irradiation.

Genetic algorithms and solid state NMR pulse sequences.

The use of genetic algorithms for the optimisation of magic angle spinning NMR pulse sequences is discussed. The discussion uses as an example the optimisation of the C7(2)(1) dipolar recoupling pulse sequence, aiming to achieve improved efficiency for spin systems characterised by large chemical shielding anisotropies and/or small dipolar coupling interactions. The optimised pulse sequence is found to be robust over a wide range of parameters, requires only minimal a priori knowledge of the spin system for experimental implementations with buildup rates being solely determined by the magnitude of the dipolar coupling interaction, but is found to be less broadbanded than the original C7(2)(1) pulse sequence. The optimised pulse sequence breaks the synchronicity between r.f. pulses and sample spinning.

MAS NMR with and without double-quantum filtration at and near the n=0 rotational resonance condition.

Spectral lineshapes of MAS NMR spectra of dipolar (re)coupled spin pairs exhibiting considerable chemical shielding anisotropies at and near the so-called n=0 rotational resonance (R2) condition are considered. The n=0 R2 condition is found to be not extremely sharp. Anisotropic interaction parameters such as chemical shielding tensor orientations and the magnitude of the dipolar coupling constant remain sensitively encoded in such lineshapes even when differences in isotropic chemical shielding values of up to 400 Hz (corresponding to ca. half the size of the dipolar coupling constant) are present. Additional double-quantum filtration (DQF) may enhance the sensitivity of spectral lineshapes to anisotropic interaction parameters for even larger differences in isotropic chemical shielding values. The dependence of the DQF efficiency on spin-system parameters as well as on external parameters (Larmor and MAS frequencies) is investigated. Away from R2 conditions a trend to lower DQF efficiencies is found whereas some spin-system parameters are more sensitively encoded in the corresponding spectral lineshapes. Our study is based on numerical simulations, with the known parameters of the 31P spin pair in Na4P2O7.10H2O representing our model case.

Double-quantum filtered 1H MAS NMR spectra.

It is shown that straightforward double-quantum filtered (1)H MAS NMR experiments yield spectral lineshapes that permit to estimate the minimum number of (1)H spins in a cluster. The approach may offer an alternative to multiple-quantum experiments for the characterisation of (1)H spin clusters of moderate size. The duration of the double-quantum excitation period has to be chosen suitably, it is necessary to find a practical compromise between optimum double-quantum filtration efficiency and optimum information content of the spectral lineshapes. Some (1)H MAS NMR experiments on partially deuterated maleic acid are reported as well as numerical simulations.

Magnitudes and orientations of 31P chemical shielding tensors in Pt(II)-phosphine complexes and other four-fold coordinated phosphorus sites.

31P MAS and double-quantum filtered 31P MAS NMR experiments at and near the n = 0 rotational resonance condition, as well as off-magic angle spinning 31P NMR experiments on two polycrystalline samples of Pt(II)-phosphine thiolate complexes are reported. Numerical simulations yield complete descriptions of the two 31P spin pairs. 195Pt MAS NMR spectra are straightforward to obtain but sensitively reflect only some parameters of the 195Pt(31P)2 three-spin system. Based on the 31P NMR results obtained and in conjunction with a large body of literature data and irrespective of the chemical nature of the specimen, a unified picture of the dominating motif of 31P chemical shielding tensor orientations of phosphorus sites with 4-fold coordination is identified as a local (pseudo)plane rather than the directions of P element bond directions.

X-[1H, 19F] triple resonance with a X-[1H] CP MAS probe and characterisation of a 29Si-19F spin pair.

An economic approach for implementing X-[1H,19F] double-decoupling MAS NMR experiments with a conventional X-[1H] dual-channel CP MAS probe is demonstrated. The parameters characterising the isolated 29Si-19F spin pair in an organosilicon compound R(3)SiF (R = 9-anthryl) are determined. In addition, we discuss the optimum choice of experimental parameters for determining all 29Si-19F spin-pair parameters from straightforward 29Si MAS NMR spectra with only 1H decoupling applied during acquisition.

Double-quantum filtered MAS NMR in the presence of chemical shielding anisotropies and direct dipolar and J couplings.

Double-quantum filtered MAS NMR spectra of an isolated homonuclear spin-1/2 pair are considered, at and away from rotational resonance conditions. The pulse sequence used is the solid-state NMR equivalent of double-quantum filtered COSY, known from solution-state NMR. The 119Sn spin pair in [(chex3Sn)2S] is characterized by a difference in isotropic chemical shielding smaller than the two chemical shielding anisotropies and by direct dipolar and isotropic J-coupling constants of similar magnitudes. At rotational resonance, one-dimensional double-quantum filtered 119Sn lineshapes yield the relative orientation of the two 119Sn chemical shielding tensors. Good double-quantum filtration efficiencies are found at and away from rotational resonance conditions, despite the presence of large chemical shielding anisotropies. Numerical simulations illustrate the interplay of the direct dipolar and J-coupling pathways and identify the latter as the main pathway even at rotational resonance conditions.