Slow magnetic relaxation in a europium(II) complex.

Single-ion anisotropy is vital for the observation of Single-Molecule Magnet (SMM) properties (i.e., a slow dynamics of the magnetization) in lanthanide-based systems. In the case of europium, the occurrence of this phenomenon has been inhibited by the spin and orbital quantum numbers that give way to J = 0 in the trivalent state and the half-filled population of the 4f orbitals in the divalent state. Herein, by optimizing the local crystal field of a quasi-linear bis(silylamido) EuII complex, the [EuII(N{SiMePh2}2)2] SMM is described, providing an example of a europium complex exhibiting slow relaxation of its magnetization. This behavior is dominated by a thermally activated (Orbach-like) mechanism, with an effective energy barrier of approximately 8 K, determined by bulk magnetometry and electron paramagnetic resonance. Ab initio calculations confirm second-order spin-orbit coupling effects lead to non-negligible axial magnetic anisotropy, splitting the ground state multiplet into four Kramers doublets, thereby allowing for the observation of an Orbach-like relaxation at low temperatures.

AsymPol-TEKs as efficient polarizing agents for MAS-DNP in glass matrices of non-aqueous solvents.

Two polarizing agents from the AsymPol family, AsymPol-TEK and cAsymPol-TEK (methyl-free version) are introduced for MAS-DNP applications in non-aqueous solvents. The performance of these new biradicals is rationalized in detail using a combination of electron paramagnetic resonance spectroscopy, density functional theory, molecular dynamics and quantitative MAS-DNP spin dynamics simulations. By slightly modifying the experimental protocol to keep the sample temperature low at insertion, we are able to obtain reproducable DNP-NMR data with 1,1,2,2-tetrachloroethane (TCE) at 100 K, which facilitates optimization and comparison of different polarizing agents. At intermediate magnetic fields, AsymPol-TEK and cAsymPol-TEK provide 1.5 to 3-fold improvement in sensitivity compared to TEKPol, one of the most widely used polarizing agents for organic solvents, with significantly shorter DNP build-up times of ∼1 s and ∼2 s at 9.4 and 14.1 T respectively. In the course of the work, we also isolated and characterized two diastereoisomers that can form during the synthesis of AsymPol-TEK; their difference in performance is described and discussed. Finally, the advantages of the AsymPol-TEKs are demonstrated by recording 2D 13C-13C correlation experiments at natural 13C-abundance of proton-dense microcrystals and by polarizing the surface of ZnO nanocrystals (NCs) coated with diphenyl phosphate ligands. For those experiments, cAsymPol-TEK yielded a three-fold increase in sensitivity compared to TEKPol, corresponding to a nine-fold time saving.

Impact of ligand chlorination and counterion tuning on high-field spin relaxation in a series of V(IV) complexes.

Methods of controlling spin coherence by molecular design are essential to efforts to develop molecular qubits for quantum information and sensing applications. In this manuscript, we perform the first studies of how arrangements of 35/37Cl nuclear spins in the ligand shell and counterion selection affect the coherent spin dynamics of V(IV) complexes at a high magnetic field. We prepared eight derivatives of the vanadium triscatecholate complex with varying arrangements of 35/37Cl substitution on the catechol backbone and R3NH+ counterions (R = Et, n-Bu, n-Hex) and investigated these species via structural and spectroscopic methods. Hahn-echo pulsed electron paramagnetic resonance (EPR) experiments at high-frequency (120 GHz) and field (ca. 4.4 T) were used to extract the phase-memory relaxation time (Tm) and spin-lattice relaxation (T1) times of the series of complexes. We found Tm values ranging from 4.8 to 1.1 µs in the temperature range of 5 to 40 K, varying by approximately 20% as a function of substitutional pattern. In-depth analysis of the results herein and comparison with related studies of brominated analogues disproves multiple hypothesized mechanisms for Tm control. Ultimately, we propose that more specific properties of the halogen atoms, e.g. the chemical shift, V⋯Cl hyperfine coupling, and quadrupolar coupling, could be contributing to the V(IV) Tm time.

PyrroTriPol: a semi-rigid trityl-nitroxide for high field dynamic nuclear polarization.

Magic angle spinning (MAS) dynamic nuclear polarization (DNP) has significantly broadened the scope of solid-state NMR to study biomolecular systems and materials. In recent years, the advent of very high field DNP combined with fast MAS has brought new challenges in the design of polarizing agents (PA) used to enhance nuclear spin polarization. Here, we present a trityl-nitroxide PA family based on a piperazine linker, named PyrroTriPol, for both aqueous and organic solutions. These new radicals have similar properties to that of TEMTriPol-I and can be readily synthesized, and purified in large quantities thereby ensuring widespread application. The family relies on a rigid bridge connecting the trityl and the nitroxide offering a better control of the electron spin-spin interactions thus providing improved performance across a broad range of magnetic fields and MAS frequencies while requiring reduced microwave power compared to bis-nitroxides. We demonstrate the efficiency of the PyrroTriPol family under a magnetic field of 9.4, 14.1 and 18.8 T with respect to TEMTriPol-I. In particular, the superiority of PyrroTriPol was demonstrated on γ-Al2O3 nanoparticles which enabled the acquisition of a high signal-to-noise surface-selective 27Al multiple-quantum MAS experiment at 18.8 T and 40 kHz MAS frequency.

Mechanistic origins of methyl-driven Overhauser DNP.

The Overhauser effect in the dynamic nuclear polarization (DNP) of non-conducting solids has drawn much attention due to the potential for efficient high-field DNP as well as a general interest in the underlying principles that enable the Overhauser effect in small molecules. We recently reported the observation of 1H and 2H Overhauser effects in H3C- or D3C-functionalized Blatter radical analogs, which we presumed to be caused by methyl rotation. In this work, we look at the mechanism for methyl-driven Overhauser DNP in greater detail, considering methyl librations and tunneling in addition to classical rotation. We predict the temperature dependence of these mechanisms using density functional theory and spin dynamics simulations. Comparisons with results from ultralow-temperature magic angle spinning-DNP experiments revealed that cross-relaxation at temperatures above 60 K originates from both libration and rotation, while librations dominate at lower temperatures. Due to the zero-point vibrational nature of these motions, they are not quenched by very low temperatures, and methyl-driven Overhauser DNP is expected to increase in efficiency down to 0 K, predominantly due to increases in nuclear relaxation times.

The Effect of Disorder on Endogenous MAS-DNP: Study of Silicate Glasses and Crystals.

In dynamic nuclear polarization nuclear magnetic resonance (DNP-NMR) experiments, the large Boltzmann polarization of unpaired electrons is transferred to surrounding nuclei, leading to a significant increase in the sensitivity of the NMR signal. In order to obtain large polarization gains in the bulk of inorganic samples, paramagnetic metal ions are introduced as minor dopants acting as polarizing agents. While this approach has been shown to be very efficient in crystalline inorganic oxides, significantly lower enhancements have been reported when applying this approach to oxide glasses. In order to rationalize the origin of the difference in the efficiency of DNP in amorphous and crystalline inorganic matrices, we performed a detailed comparison in terms of their magnetic resonance properties. To diminish differences in the DNP performance arising from distinct nuclear interactions, glass and crystal systems of similar compositions were chosen, Li2OCaO·2SiO2 and Li2CaSiO4, respectively. Using Gd(III) as polarizing agent, DNP provided signal enhancements in the range of 100 for the crystalline sample, while only up to around factor 5 in the glass, for both 6Li and 29Si nuclei. We find that the drop in enhancement in glasses can be attributed to three main factors: shorter nuclear and electron relaxation times as well as the dielectric properties of glass and crystal. The amorphous nature of the glass sample is responsible for a high dielectric loss, leading to efficient microwave absorption and consequently lower effective microwave power and an increase in sample temperature which leads to further reduction of the electron relaxation time. These results help rationalize the observed sensitivity enhancements and provide guidance in identifying materials that could benefit from the DNP approach.

Geochemical evolution and the processes controlling groundwater chemistry using ionic ratios, geochemical modelling and chemometric analysis in uMhlathuze catchment, KwaZulu-Natal, South Africa.

The sources of chemical constituents of groundwater and its associated hydrogeochemical processes in the part of Mhlathuze catchment was identified. Groundwater of the area is classified into soft to very hard and the nature is identified as acidic to alkaline. The overall electrical conductivity is < 3000 µS/cm except in three wells. The predominant water type is NaCl (69% of samples) and CaMgCl facies. Gibbs plots, mCa/Mg ratio, mNa/Cl ratio, Ca + Mg vs HCO3+SO4 plot, Na + K vs HCO3 plot, Ca/Na vs HCO3/Na, Chloroalkaline indices (CAI 1, CAI 2) and Ca + Mg-HCO3-SO4 vs Na + K-Cl plots confirm the impact of silicate, carbonate mineral weathering and ion exchange reaction in this aquifer. However, few wells are influenced by the evaporation process. Groundwater is highly undersaturated with sulphate, chloride minerals and saturated with carbonate minerals. CA revealed that Cl and SO4 are derived from anthropogenic sources and a significant positive correlation between HCO3 and Cl reveals that wastewater recharge has most likely simulated the mineral weathering in the vadose zone, which could have further enhanced HCO3 and Cl in the aquifer. PCA resulted in three factors. Factor 1 defines the influence of geogenic and anthropogenic processes while Factors 2 and 3 imply the mineral weathering and nitrification processes. Hierarchical cluster analysis defines that evaporation, anthropogenic input, silicate and carbonate weathering and nitrification process are the sources of chemical constituents of groundwater in this aquifer.

Proton-detected solution-state NMR at 14.1 T based on scalar-driven 13C Overhauser dynamic nuclear polarization.

Overhauser dynamic nuclear polarization (ODNP) NMR of solutions at high fields is usually mediated by scalar couplings that polarize the nuclei of heavier, electron-rich atoms. This leaves 1H-detected NMR outside the realm of such studies. This study presents experiments that deliver 1H-detected NMR experiments on relatively large liquid volumes (60 âˆ¼ 100 µL) and at high fields (14.1 T), while relying on ODNP enhancements. To this end 13C NMR polarizations were first enhanced by relying on a mechanism that utilizes e--13C scalar coupling interactions; the nuclear spin alignment thus achieved was then passed on to neighboring 1H for observation, by a reverse INEPT scheme relying on one-bond JCH-couplings. Such 13C →1H polarization transfer ported the 13C ODNP gains into the 1H, permitting detection at higher frequencies and with higher potential sensitivities. For a model solution of labeled 13CHCl3 comixed with a nitroxide-based TEMPO derivative as polarizing agent, an ODNP enhancement factor of ca. 5x could thus be imparted to the 1H signal. When applied to bigger organic molecules like 2-13C-phenylacetylene and 13C8-indole, ODNP enhancements in the 1.2-3x range were obtained. Thus, although handicapped by the lower γ of the 13C, enhancements could be imparted on the 1H thermal acquisitions in all cases. We also find that conventional 1H-13C nuclear Overhauser enhancements (NOEs) are largely absent in these solutions due to the presence of co-dissolved radicals, adding negligible gains and playing negligible roles on the scalar e-→13C ODNP transfer. Potential rationalizations of these effects as well as extensions of these experiments, are briefly discussed.

Spin-Lattice Relaxation Decoherence Suppression in Vanishing Orbital Angular Momentum Qubits.

Multifrequency electron paramagnetic resonance spectroscopy on oriented single crystals of magnetically dilute Gd(III) ions in Gd0.004Y0.996(trensal) is used to determine the Hamiltonian parameters of the ground 8S7/2 term and its phase memory time, Tm, characterizing its coherent spin dynamics. The vanishing orbital angular momentum of the 8S7/2 term makes it relatively insensitive to spin-lattice relaxation mediated by magnetoelastic coupling and leads to a Tm of 12 µs at 3 K, which is not limited by spin-lattice relaxation.

Treatment of faecal sludge and sewage effluent by pinewood biochar to reduce wastewater bacteria and inorganic contaminants leaching.

Biochar is a valuable treatment option for faecal sludge management (FSM). However, the sanitation application rates of biochar in FSM are not well established. There is also a gap in knowledge about the effect of actual raw sewage effluent and sludge on organic and inorganic contaminants migration of biochar treated soil. This study investigated the concentration and migration rates of N, P, E. coli and faecal coliform bacteria through different soil-bed biochar column treatments leached with raw faecal sludge and sewage effluent. Forty-four soil-bed leaching columns with pinewood biochar rates at 5, 10 and 20 t/ha were set at the Bloemspruit wastewater plant, South Africa. The pinewood biochar used had a pH of 10.21, total C composition of 92%, surface area of 517 m²/g, and a pore size of 1.7 nm. It was found that the 20 t biochar per ha treatment with faecal sludge increased water retention (flows of 33 mm/h. at 0 t/ha compared to 0.8 mm/h. at 20 t/ha) and leachates purification. High detections were observed for faecal coliforms and E.coli above 4331 CFU/100 mL from the effluent and faecal sludge in soils without biochar. Detection of E.coli at 20 t/ha decreased to 1 CFU/100 mL while the faecal coliforms still had counts above 10 CFU/ 100 mL. The results showed a decreasing rate of nitrates, phosphates, zinc and copper with an increasing biochar application rate. Pinewood biochar showed significant removal efficiencies of bacteria (between 89 and 98%) and nitrates and phosphates (between 68 and 98%). Significant differences were seen at P < 0.05 between the means of the treatments with and without biochar. The results from the study show that pinewood biochar applied at rates between 5 and 20 t/ha has a high organic and inorganic contaminants reduction potential for FSM.

Highly Efficient Polarizing Agents for MAS-DNP of Proton-Dense Molecular Solids.

Efficiently hyperpolarizing proton-dense molecular solids through dynamic nuclear polarization (DNP) solid-state NMR is still an unmet challenge. Polarizing agents (PAs) developed so far do not perform well on proton-rich systems, such as organic microcrystals and biomolecular assemblies. Herein we introduce a new PA, cAsymPol-POK, and report outstanding hyperpolarization efficiency on 12.76 kDa U-13 C,15 N-labeled LecA protein and pharmaceutical drugs at high magnetic fields (up to 18.8 T) and fast magic angle spinning (MAS) frequencies (up to 40 kHz). The performance of cAsymPol-POK is rationalized by MAS-DNP simulations combined with electron paramagnetic resonance (EPR), density functional theory (DFT) and molecular dynamics (MD). This work shows that this new biradical is compatible with challenging biomolecular applications and unlocks the rapid acquisition of 13 C-13 C and 15 N-13 C correlations of pharmaceutical drugs at natural isotopic abundance, which are key experiments for structure determination.

Monitoring electron spin fluctuations with paramagnetic relaxation enhancement.

The magnetic interactions between the spin of an unpaired electron and the surrounding nuclear spins can be exploited to gain structural information, to reduce nuclear relaxation times as well as to create nuclear hyperpolarization via dynamic nuclear polarization (DNP). A central aspect that determines how these interactions manifest from the point of view of NMR is the timescale of the fluctuations of the magnetic moment of the electron spins. These fluctuations, however, are elusive, particularly when electron relaxation times are short or interactions among electronic spins are strong. Here we map the fluctuations by analyzing the ratio between longitudinal and transverse nuclear relaxation times T1/T2, a quantity which depends uniquely on the rate of the electron fluctuations and the Larmor frequency of the involved nuclei. This analysis enables rationalizing the evolution of NMR lineshapes, signal quenching as well as DNP enhancements as a function of the concentration of the paramagnetic species and the temperature, demonstrated here for LiMg1-xMnxPO4 and Fe(III) doped Li4Ti5O12, respectively. For the latter, we observe a linear dependence of the DNP enhancement and the electron relaxation time within a temperature range between 100 and 300 K.

The distance between g-tensors of nitroxide biradicals governs MAS-DNP performance: The case of the bTurea family.

Bis-nitroxide radicals are common polarizing agents (PA), used to enhance the sensitivity of solid-state NMR experiments via Magic Angle Spinning Dynamic Nuclear Polarization (MAS-DNP). These biradicals can increase the proton spin polarization through the Cross-Effect (CE) mechanism, which requires PAs with at least two unpaired electrons. The relative orientation of the bis-nitroxide moieties is critical to ensure efficient polarization transfer. Recently, we have defined a new quantity, the distance between g-tensors, that correlates the relative orientation of the nitroxides with the ability to polarize the surrounding nuclei. Here we analyse experimentally and theoretically a series of biradicals belonging to the bTurea family, namely bcTol, AMUPol and bcTol-M. They differ by the degree of substitution on the urea bridge that connects the two nitroxides. Using quantitative simulations developed for moderate MAS frequencies, we show that these modifications mostly affect the relative orientations of the nitroxide, i.e. the length and distribution of the distance between the g-tensors, that in turn impacts both the steady state nuclear polarization/depolarization as well as the build-up times. The doubly substituted urea bridge favours a large distance between the g-tensors, which enables bcTol-M to provide ∊on/off>200 at 14.1 T/600 MHz/395 GHz with build-up times of 3.8 s using a standard homogenous solution. The methodology described herein was used to show how the conformation of the spirocyclic rings flanking the nitroxide function in the recently described c- and o-HydrOPol affects the distance between the g-tensors and thereby polarization performance.

Correction: De novo prediction of cross-effect efficiency for magic angle spinning dynamic nuclear polarization.

Correction for 'De novo prediction of cross-effect efficiency for magic angle spinning dynamic nuclear polarization' by Frédéric Mentink-Vigier et al., Phys. Chem. Chem. Phys., 2019, 21, 2166-2176, DOI: 10.1039/C8CP06819D.

Community Faecal Management Strategies and Perceptions on Sludge Use in Agriculture.

Most people in rural areas in South Africa (SA) rely on untreated drinking groundwater sources and pit latrine sanitations. A minimum basic sanitation facility should enable safe and appropriate removal of human waste, and although pit latrines provide this, they are still contamination concerns. Pit latrine sludge in SA is mostly emptied and disposed off-site as waste or buried in-situ. Despite having knowledge of potential sludge benefits, most communities in SA are reluctant to use it. This research captured social perceptions regarding latrine sludge management in Monontsha village in the Free State Province of SA through key informant interviews and questionnaires. A key informant interview and questionnaire was done in Monontsha, SA. Eighty participants, representing 5% of all households, were selected. Water samples from four boreholes and four rivers were analyzed for faecal coliforms and E.coli bacteria. On average, five people in a household were sharing a pit latrine. Eighty-three percent disposed filled pit latrines while 17% resorted to closing the filled latrines. Outbreaks of diarrhoea (69%) and cholera (14%) were common. Sixty percent were willing to use treated faecal sludge in agriculture. The binary logistic regression model indicated that predictor variables significantly (p ˂ 0.05) described water quality, faecal sludge management, sludge application in agriculture and biochar adaption. Most drinking water sources in the study had detections ˂ 1 CFU/100 mL. It is therefore imperative to use both qualitative surveys and analytical data. Awareness can go a long way to motivate individuals to adopt to a new change.

Subterahertz spin pumping from an insulating antiferromagnet.

Spin-transfer torque and spin Hall effects combined with their reciprocal phenomena, spin pumping and inverse spin Hall effects (ISHEs), enable the reading and control of magnetic moments in spintronics. The direct observation of these effects remains elusive in antiferromagnetic-based devices. We report subterahertz spin pumping at the interface of the uniaxial insulating antiferromagnet manganese difluoride and platinum. The measured ISHE voltage arising from spin-charge conversion in the platinum layer depends on the chirality of the dynamical modes of the antiferromagnet, which is selectively excited and modulated by the handedness of the circularly polarized subterahertz irradiation. Our results open the door to the controlled generation of coherent, pure spin currents at terahertz frequencies.

Controlling Electron Spin Decoherence in Nd-based Complexes via Symmetry Selection.

Long decoherence time is a key consideration for molecular magnets in the application of the quantum computation. Although previous studies have shown that the local symmetry of spin carriers plays a crucial part in the spin-lattice relaxation process, its role in the spin decoherence is still unclear. Herein, two nine-coordinated capped square antiprism neodymium moieties [Nd(CO3)4H2O]5- with slightly different local symmetries, C1 versus C4 (1 and 2), are reported, which feature in the easy-plane magnetic anisotropy as shown by the high-frequency electron paramagnetic resonance (HF-EPR) studies. Detailed analysis of the relaxation time suggests that the phonon bottleneck effect is essential to the magnetic relaxation in the crystalline samples of 1 and 2. The 240 GHz Pulsed EPR studies show that the higher symmetry results in longer decoherence times, which is supported by the first principle calculations.

Fundamental Spin Interactions Underlying the Magnetic Anisotropy in the Kitaev Ferromagnet CrI_{3}.

We lay the foundation for determining the microscopic spin interactions in two-dimensional (2D) ferromagnets by combining angle-dependent ferromagnetic resonance (FMR) experiments on high quality CrI_{3} single crystals with theoretical modeling based on symmetries. We discover that the Kitaev interaction is the strongest in this material with K∼-5.2 meV, 25 times larger than the Heisenberg exchange J∼-0.2 meV, and responsible for opening the ∼5 meV gap at the Dirac points in the spin-wave dispersion. Furthermore, we find that the symmetric off-diagonal anisotropy Γ∼-67.5 µeV, though small, is crucial for opening a ∼0.3 meV gap in the magnon spectrum at the zone center and stabilizing ferromagnetism in the 2D limit. The high resolution of the FMR data further reveals a µeV-scale quadrupolar contribution to the S=3/2 magnetism. Our identification of the underlying exchange anisotropies opens paths toward 2D ferromagnets with higher T_{C} as well as magnetically frustrated quantum spin liquids based on Kitaev physics.

Nuclear-spin-pattern control of electron-spin dynamics in a series of V(iv) complexes.

Achieving control of phase memory relaxation times (T m) in metal ions is an important goal of molecular spintronics. Herein we provide the first evidence that nuclear-spin patterning in the ligand shell is an important handle to modulate T m in metal ions. We synthesized and studied a series of five V(iv) complexes with brominated catecholate ligands, [V(C6H4-n Br n O2)3]2- (n = 0, 1, 2, and 4), where the 79/81Br and 1H nuclear spins are arranged in different substitutional patterns. High-field, high-frequency (120 GHz) pulsed electron paramagnetic resonance spectroscopic analysis of this series reveals a pattern-dependent variation in T m for the V(iv) ion. Notably, we show that it is possible for two molecules to have starkly different (by 50%) T m values despite the same chemical composition. Nuclear magnetic resonance analyses of the protons on the ligand shell suggest that relative chemical shift (δ), controlled by the patterning of nuclear spins, is an important underlying design principle. Here, having multiple ligand-based protons with nearly identical chemical shift values in the ligand shell will, ultimately, engender a short T m for the bound metal ion.