Safe and just Earth system boundaries.

The stability and resilience of the Earth system and human well-being are inseparably linked1-3, yet their interdependencies are generally under-recognized; consequently, they are often treated independently4,5. Here, we use modelling and literature assessment to quantify safe and just Earth system boundaries (ESBs) for climate, the biosphere, water and nutrient cycles, and aerosols at global and subglobal scales. We propose ESBs for maintaining the resilience and stability of the Earth system (safe ESBs) and minimizing exposure to significant harm to humans from Earth system change (a necessary but not sufficient condition for justice)4. The stricter of the safe or just boundaries sets the integrated safe and just ESB. Our findings show that justice considerations constrain the integrated ESBs more than safety considerations for climate and atmospheric aerosol loading. Seven of eight globally quantified safe and just ESBs and at least two regional safe and just ESBs in over half of global land area are already exceeded. We propose that our assessment provides a quantitative foundation for safeguarding the global commons for all people now and into the future.

Comparative pulmonary toxicities of lunar dusts and terrestrial dusts (TiO2 & SiO2) in rats and an assessment of the impact of particle-generated oxidants on the dusts' toxicities.

Humans will set foot on the Moon again soon. The lunar dust (LD) is potentially reactive and could pose an inhalation hazard to lunar explorers. We elucidated LD toxicity and investigated the toxicological impact of particle surface reactivity (SR) using three LDs, quartz, and TiO2. We first isolated the respirable-size-fraction of an Apollo-14 regolith and ground two coarser samples to produce fine LDs with increased SR. SR measurements of these five respirable-sized dusts, determined by their in-vitro ability to generate hydroxyl radicals (•OH), showed that ground LDs > unground LD ≥ TiO2 ≥ quartz. Rats were each intratracheally instilled with 0, 1, 2.5, or 7.5 mg of a test dust. Toxicity biomarkers and histopathology were assessed up to 13 weeks after the bolus instillation. All dusts caused dose-dependent-increases in pulmonary lesions and toxicity biomarkers. The three LDs, which possessed mineral compositions/properties similar to Arizona volcanic ash, were moderately toxic. Despite a 14-fold •OH difference among these three LDs, their toxicities were indistinguishable. Quartz produced the lowest •OH amount but showed the greatest toxicity. Our results showed no correlation between the toxicity of mineral dusts and their ability to generate free radicals. We also showed that the amounts of oxidants per neutrophil increased with doses, time and the cytotoxicity of the dusts in the lung, which supports our postulation that dust-elicited neutrophilia is the major persistent source of oxidative stress. These results and the discussion of the crucial roles of the short-lived, continuously replenished neutrophils in dust-induced pathogenesis are presented.

Exploring cation disorder in mixed-metal pyrochlore ceramics using 17 O NMR spectroscopy and first-principles calculations.

Characterising the local structures (e.g., the cation distribution) of mixed-metal ceramics by NMR spectroscopy is often challenging owing to the unfavourable properties (low γ, large quadrupole moment and/or low abundance) of many metal nuclei. 17 O is an attractive option owing to the prevalence of oxygen within ceramics. The moderate γ and small quadrupole moment of 17 O mean that the greatest barrier to accessing the information available from this nucleus is isotopic enrichment. We explore the challenges of ensuring uniform isotopic enrichment with 17 O2 (g) for the pyrochlore solid solutions, Y2 Snx Ti2-x O7 , La2 Snx Zr2-x O7 and La2 Snx Hf2-x O7 , demonstrating that high enrichment temperatures (900 °C for 12 hr) are required. In addition, for sites with very high symmetry (such as the tetrahedral OY4 and OLa4 sites with CQ ≈ 0 present here), we demonstrate that quantitative 17 O NMR spectra require correction for the differing contributions from the centreband of the satellite transitions, which can be as high as a factor of ~3.89. It is common to use first-principles calculations to aid in interpreting NMR spectra of disordered solids. Here, we use an ensemble modelling approach to ensure that all possible cation arrangements are modelled in the minimum possible number of calculations. By combining uniform isotopic enrichment, quantitative NMR spectroscopy and a comprehensive computational approach, we are able to show that the cation distribution in Y2 Snx Ti2-x O7 is essentially random, whereas in La2 Snx Zr2-x O7 and La2 Snx Hf2-x O7 , OLa2SnZr and OLa2SnHf sites are slightly energetically disfavoured, leading to a weak preference for clustering of like cations.

Suppression of Unwanted ZZ Interactions in a Hybrid Two-Qubit System.

Mitigating crosstalk errors, whether classical or quantum mechanical, is critically important for achieving high-fidelity entangling gates in multiqubit circuits. For weakly anharmonic superconducting qubits, unwanted ZZ interactions can be suppressed by combining qubits with opposite anharmonicity. We present experimental measurements and theoretical modeling of two-qubit gate error for gates based on the cross resonance interaction between a capacitively shunted flux qubit and a transmon, and demonstrate the elimination of the ZZ interaction.

Application of NMR Crystallography to Highly Disordered Templated Materials: Extensive Local Structural Disorder in the Gallophosphate GaPO-34A.

We present an NMR crystallographic investigation of two as-made forms of the recently characterized gallophosphate GaPO-34A, which has an unusual framework composition with a Ga:P ratio of 7:6 and contains both hydroxide and fluoride anions and either 1-methylimidazolium or pyridinium as the structure-directing agent. We combine previously reported X-ray crystallographic data with solid-state NMR spectroscopy and periodic density functional theory (DFT) calculations to show that the structure contains at least three distinct types of disorder (occupational, compositional, and dynamic). The occupational disorder arises from the presence of six anion sites per unit cell, but a total occupancy of five of these, leading to full occupancy of four sites and partial occupancy of the fifth and sixth (which are related by symmetry). The mixture of OH and F present leads to compositional disorder on the occupied anion sites, although the occupancy of some sites by F is calculated to be energetically unfavorable and signals relating to F on these sites are not observed by NMR spectroscopy, confirming that the compositional disorder is not random. Finally, a combination of high-field 71Ga NMR spectroscopy and variable-temperature 13C and 31P NMR experiments shows that the structure directing agents are dynamic on the microsecond time scale, which can be supported by averaging the 31P chemical shifts calculated with the SDA in different orientations. This demonstrates the value of an NMR crystallographic approach, particularly in the case of highly disordered crystalline materials, where the growth of large single crystals for conventional structure determination may not be possible owing to the extent of disorder present.

Phosphorus-Bismuth Peri-Substituted Acenaphthenes: A Synthetic, Structural, and Computational Study.

A series of acenaphthene species with a diisopropylphosphino group and a variety of bismuth functionalities in the peri positions were synthesized and fully characterized, including single-crystal X-ray diffraction. The majority of the reported species feature a relatively rare interpnictogen P-Bi bond. The series includes the phosphine-bismuthine Acenap(PiPr2)(BiPh2) (2; Acenap = acenaphthene-5,6-diyl), which was subjected to a fluorodearylation reaction to produce Acenap(PiPr2)(BiPhX) (5-8 and 10; X = BF4-, Cl, Br, I, SPh), displaying varying degrees of ionicity. The geminally bis(acenaphthyl)-substituted [Acenap(PiPr2)]2BiPh (3) shows a large through-space coupling of 17.8 Hz, formally 8TSJPP. Coupling deformation density calculations confirm the double through-space coupling pathway, in which the P and Bi lone pairs mediate communication between the two 31P nuclei. Several synthetic routes toward the phosphine-diiodobismuthine Acenap(PiPr2)(BiI2) (9) have been investigated; however, the purity of this, surprisingly thermally stable potential synthon, remains poor.

Following the unusual breathing behaviour of 17O-enriched mixed-metal (Al,Ga)-MIL-53 using NMR crystallography.

The breathing behaviour of 17O-enriched (Al,Ga)-MIL-53, a terephthalate-based metal-organic framework, has been investigated using a combination of solid-state nuclear magnetic resonance (NMR) spectroscopy, powder X-ray diffraction (PXRD) and first-principles calculations. These reveal that the behaviour observed for as-made, calcined, hydrated and subsequently dehydrated mixed-metal MIL-53 materials differs with composition, but cannot be described as the compositionally weighted average of the breathing behaviour seen for the two end members. Although the form of MIL-53 adopted by the as-made material is independent of metal composition, upon calcination, materials with higher levels of Al adopt an open pore (OP) form, as found for the Al end member, but substitution of Ga results in mixed pore materials, with OP and narrow pore (NP) forms co-existing. Although the Ga end member is prone to decomposition under the calcination conditions used, a low level of Al in the starting synthesis (5%) leads to an OP mixed-metal MOF that is stable to calcination. Upon hydration, all materials almost exclusively adopt a closed pore (CP) structure, with strong hydrogen bonding interactions with water leading to two distinct resonances from the carboxylate oxygens in 17O NMR spectra. When dehydrated, different framework structures are found for the two end members, OP for Al-MIL-53 and NP for Ga-MIL-53, with the proportion of NP MOF seen to increase systematically with the Ga content in mixed-metal materials, in contrast to the forms seen upon initial calcination. 17O NMR spectra of mixed-metal MIL-53 materials show an increased preference for clustering of like cations as the Ga content increases. This is not a result of the small-scale dry gel conversion reactions used for enrichment, as a similar cation distribution and clustering is also observed for (Al0.5,Ga0.5)-MIL-53 synthesised hydrothermally and enriched with 17O via post-synthetic steaming.

Ensemble-Based Modeling of the NMR Spectra of Solid Solutions: Cation Disorder in Y2(Sn,Ti)2O7.

The sensitivity of NMR to the local environment, without the need for any long-range order, makes it an ideal tool for the characterization of disordered materials. Computational prediction of NMR parameters can be of considerable help in the interpretation and assignment of NMR spectra of solids, but the statistical representation of all possible chemical environments for a solid solution is challenging. Here, we illustrate the use of a symmetry-adapted configurational ensemble in the simulation of NMR spectra, in combination with solid-state NMR experiments. We show that for interpretation of the complex and overlapped lineshapes that are typically observed, it is important to go beyond a single-configuration representation or a simple enumeration of local environments. The ensemble method leads to excellent agreement between simulated and experimental spectra for Y2(Sn,Ti)2O7 pyrochlore ceramics, where the overlap of signals from different local environments prevents a simple decomposition of the experimental spectral lineshapes. The inclusion of a Boltzmann weighting confirms that the best agreement with experiment is obtained at higher temperatures, in the limit of full disorder. We also show that to improve agreement with experiment, in particular at low dopant concentrations, larger supercells are needed, which might require alternative simulation approaches as the complexity of the system increases. It is clear that ensemble-based modeling approaches in conjunction with NMR spectroscopy offer great potential for understanding configurational disorder, ultimately aiding the future design of functional materials.

A Picture of Disorder in Hydrous Wadsleyite-Under the Combined Microscope of Solid-State NMR Spectroscopy and Ab Initio Random Structure Searching.

The Earth's transition zone, at depths of 410-660 km, while being composed of nominally anhydrous magnesium silicate minerals, may be subject to significant hydration. Little is known about the mechanism of hydration, despite the vital role this plays in the physical and chemical properties of the mantle, leading to a need for improved structural characterization. Here we present an ab initio random structure searching (AIRSS) investigation of semihydrous (1.65 wt % H2O) and fully hydrous (3.3 wt % H2O) wadsleyite. Following the AIRSS process, k-means clustering was used to select sets of structures with duplicates removed, which were then subjected to further geometry optimization with tighter constraints prior to NMR calculations. Semihydrous models identify a ground-state structure (Mg3 vacancies, O1-H hydroxyls) that aligns with a number of previous experimental observations. However, predicted NMR parameters fail to reproduce low-intensity signals observed in solid-state NMR spectra. In contrast, the fully hydrous models produced by AIRSS, which enable both isolated and clustered defects, are able to explain observed NMR signals via just four low-enthalpy structures: (i) a ground state, with isolated Mg3 vacancies and O1-H hydroxyls; (ii/iii) edge-sharing Mg3 vacancies with O1-H and O3-H species; and (iv) edge-sharing Mg1 and Mg3 vacancies with O1-H, O3-H, and O4-H hydroxyls. Thus, the combination of advanced structure searching approaches and solid-state NMR spectroscopy is able to provide new and detailed insight into the structure of this important mantle mineral.

Three-Qubit Randomized Benchmarking.

As quantum circuits increase in size, it is critical to establish scalable multiqubit fidelity metrics. Here we investigate, for the first time, three-qubit randomized benchmarking (RB) on a quantum device consisting of three fixed-frequency transmon qubits with pairwise microwave-activated interactions (cross-resonance). We measure a three-qubit error per Clifford of 0.106 for all-to-all gate connectivity and 0.207 for linear gate connectivity. Furthermore, by introducing mixed dimensionality simultaneous RB-simultaneous one- and two-qubit RB-we show that the three-qubit errors can be predicted from the one- and two-qubit errors. However, by introducing certain coherent errors to the gates, we can increase the three-qubit error to 0.302, an increase that is not predicted by a proportionate increase in the one- and two-qubit errors from simultaneous RB. This demonstrates the importance of multiqubit metrics, such as three-qubit RB, on evaluating overall device performance.

Polymorphism, Weak Interactions and Phase Transitions in Chalcogen-Phosphorus Heterocycles.

A series of P-E-containing heterocycles (E=chalcogen) with aromatic backbones were synthesised and characterised by single-crystal and powder XRD, microanalysis and mass spectrometry. Solution- and solid-state 31 P and 77 Se NMR spectroscopy revealed significant differences between the NMR parameters in solution and in the solid state, related to conformational changes in the molecules. Many compounds were shown to exhibit a number of different polymorphic structures (identified by single-crystal XRD), although the bulk material studied by solid-state NMR spectroscopy often contained just one major polymorph. For the unoxidised heterocycles, the presence of weak intermolecular J couplings was also investigated by DFT calculations.

Severity of ocean acidification following the end-Cretaceous asteroid impact.

Most paleo-episodes of ocean acidification (OA) were either too slow or too small to be instructive in predicting near-future impacts. The end-Cretaceous event (66 Mya) is intriguing in this regard, both because of its rapid onset and also because many pelagic calcifying species (including 100% of ammonites and more than 90% of calcareous nannoplankton and foraminifera) went extinct at this time. Here we evaluate whether extinction-level OA could feasibly have been produced by the asteroid impact. Carbon cycle box models were used to estimate OA consequences of (i) vaporization of up to 60 × 10(15) mol of sulfur from gypsum rocks at the point of impact; (ii) generation of up to 5 × 10(15) mol of NOx by the impact pressure wave and other sources; (iii) release of up to 6,500 Pg C as CO2 from vaporization of carbonate rocks, wildfires, and soil carbon decay; and (iv) ocean overturn bringing high-CO2 water to the surface. We find that the acidification produced by most processes is too weak to explain calcifier extinctions. Sulfuric acid additions could have made the surface ocean extremely undersaturated (Ωcalcite <0.5), but only if they reached the ocean very rapidly (over a few days) and if the quantity added was at the top end of literature estimates. We therefore conclude that severe ocean acidification might have been, but most likely was not, responsible for the great extinctions of planktonic calcifiers and ammonites at the end of the Cretaceous.

Solid-State NMR Spectroscopy Proves the Presence of Penta-coordinated Sc Sites in MIL-100(Sc).

Advanced solid-state NMR methods and first-principles calculations demonstrate for the first time the formation of penta-coordinated scandium sites. These coordinatively unsaturated sites were shown during the thermal activation of scandium-based metal-organic frameworks (MOFs). A 45 Sc NMR experiment allows their specific observation in activated Sc3 BTB2 (H3 BTB=1,3,5-tris(4-carboxyphenyl)benzene) and MIL-100(Sc) MOFs. The assignment of the ScO5 groups is supported by the DFT calculations of NMR parameters. The presence of ScO5 Lewis acid sites in MIL-100(Sc) explains furthermore its catalytic activity. The first NMR experiment to probe 13 C-45 Sc distances is also introduced. This advanced solid-state NMR pulse sequence allows the demonstration of the shrinkage of the MIL-100(Sc) network when the activation temperature is raised.

Room Temperature Regioselective Catalytic Hydrodefluorination of Fluoroarenes with trans-[Ru(NHC)4 H2 ] through a Concerted Nucleophilic Ru-H Attack Pathway.

The efficient and highly selective room temperature hydrodefluorination (HDF) of fluoroarenes by the trans-[Ru(IMe4 )4 H2 ] catalyst, 3, is reported. Mechanistic studies show 3 acts directly in catalysis without any ligand dissociation and DFT calculations indicate a concerted nucleophilic attack mechanism. The calculations fully account for the observed selectivities which corroborate earlier predictions regarding the selectivity of HDF.

Investigating Unusual Homonuclear Intermolecular "Through-Space" J Couplings in Organochalcogen Systems.

Although the electron-mediated spin-spin or J coupling is conventionally viewed as transmitted via covalent bonds, examples of J couplings between atoms that are not formally bonded but are in close proximity (termed "through-space" J couplings) have been reported. In this work, we investigate the observation of homonuclear 31P J couplings in organochalcogen heterocycles, which occur between 31P in two separate molecules, confirming without doubt their through-space nature. The presence of this interaction is even more surprising for one compound, where it occurs between crystallographically equivalent species. Although crystallographically equivalent species need not be magnetically equivalent in the solid state, owing to the presence of anisotropic interactions, we demonstrate that it is not the shielding anisotropy that lifts magnetic equivalence, in this case, but the presence of heteronuclear couplings to 77Se. We support our experimental observations with periodic scalar-relativistic density functional theory calculations and coupling density deformation plots to visualize the mechanism of these interesting interactions.

Hunting for hydrogen: random structure searching and prediction of NMR parameters of hydrous wadsleyite.

The structural chemistry of materials containing low levels of nonstoichiometric hydrogen is difficult to determine, and producing structural models is challenging where hydrogen has no fixed crystallographic site. Here we demonstrate a computational approach employing ab initio random structure searching (AIRSS) to generate a series of candidate structures for hydrous wadsleyite (ß-Mg2SiO4 with 1.6 wt% H2O), a high-pressure mineral proposed as a repository for water in the Earth's transition zone. Aligning with previous experimental work, we solely consider models with Mg3 (over Mg1, Mg2 or Si) vacancies. We adapt the AIRSS method by starting with anhydrous wadsleyite, removing a single Mg(2+) and randomly placing two H(+) in a unit cell model, generating 819 candidate structures. 103 geometries were then subjected to more accurate optimisation under periodic DFT. Using this approach, we find the most favourable hydration mechanism involves protonation of two O1 sites around the Mg3 vacancy. The formation of silanol groups on O3 or O4 sites (with loss of stable O1-H hydroxyls) coincides with an increase in total enthalpy. Importantly, the approach we employ allows observables such as NMR parameters to be computed for each structure. We consider hydrous wadsleyite (∼1.6 wt%) to be dominated by protonated O1 sites, with O3/O4-H silanol groups present as defects, a model that maps well onto experimental studies at higher levels of hydration (J. M. Griffin et al., Chem. Sci., 2013, 4, 1523). The AIRSS approach adopted herein provides the crucial link between atomic-scale structure and experimental studies.

High-contrast qubit interactions using multimode cavity QED.

We introduce a new multimode cavity QED architecture for superconducting circuits that can be used to implement photonic memories, more efficient Purcell filters, and quantum simulations of photonic materials. We show that qubit interactions mediated by multimode cavities can have exponentially improved contrast for two qubit gates without sacrificing gate speed. Using two qubits coupled via a three-mode cavity system we spectroscopically observe multimode strong couplings up to 102 MHz and demonstrate suppressed interactions off resonance of 10 kHz when the qubits are ≈600 MHz detuned from the cavity resonance. We study Landau-Zener transitions in our multimode systems and demonstrate quasiadiabatic loading of single photons into the multimode cavity in 25 ns. We introduce an adiabatic gate protocol to realize a controlled-Z gate between the qubits in 95 ns and create a Bell state with 94.7% fidelity. This corresponds to an on/off ratio (gate contrast) of 1000.

Exceedingly Facile Ph-X Activation (X = Cl, Br, I) with Ruthenium(II): Arresting Kinetics, Autocatalysis, and Mechanisms.

[(Ph3P)3Ru(L)(H)2] (where L = H2 (1) in the presence of styrene, Ph3P (3), and N2 (4)) cleave the Ph-X bond (X = Cl, Br, I) at RT to give [(Ph3P)3RuH(X)] (2) and PhH. A combined experimental and DFT study points to [(Ph3P)3Ru(H)2] as the reactive species generated upon spontaneous loss of L from 3 and 4. The reaction of 3 with excess PhI displays striking kinetics which initially appears zeroth order in Ru. However mechanistic studies reveal that this is due to autocatalysis comprising two factors: 1) complex 2, originating from the initial PhI activation with 3, is roughly as reactive toward PhI as 3 itself; and 2) the Ph-I bond cleavage with the just-produced 2 gives rise to [(Ph3P)2RuI2], which quickly comproportionates with the still-present 3 to recover 2. Both the initial and onward activation reactions involve PPh3 dissociation, PhI coordination to Ru through I, rearrangement to a η(2)-PhI intermediate, and Ph-I oxidative addition.

Toxic epidermal necrolysis in a child successfully treated with infliximab.

A 7-year-old boy developed severe toxic epidermal necrolysis (TEN) secondary to carbamazepine and was transferred to our center after further deterioration despite receiving one dose of intravenous immunoglobulin. After administration of one dose of infliximab, there was a clear halting of progression of blistering and an apparent dramatic improvement. We consider it likely that the administration of infliximab led to the improvement in this child and that anti-tumor necrosis factor-alpha therapy may be a logical treatment for TEN, given the possible underlying pathologic process. Well-conducted studies on the safety and efficacy of any such treatment are urgently required.

Slow thermalization between a lattice and free Bose gas.

Using a 3D spin-dependent optical lattice, we study thermalization and energy exchange between two ultracold Bose gases, one of which is strongly correlated and bound to the lattice and another that is free from the lattice potential. Disruption of interspecies thermalization is revealed through measurements of condensate fraction after the lattice is superimposed on the parabolic confining potential. By selectively heating the lattice-bound species and measuring the rate of heat transfer to the free state, suppression of energy exchange is observed. Comparison with a Fermi's golden rule prediction confirms that this effect is caused by a dispersion mismatch that reduces the phase space available for elastic collisions. This result has critical implications for methods proposed to cool strongly correlated lattice gases.